EPA-600/2-76-242
December 1976
Environmental Protection Technology Series
DEVELOPMENT OF A
HYDROPHOBIC SUBSTANCE TO
MITIGATE PAVEMENT ICE ADHESION
Municipal Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia-22161.
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EPA-600/2-76-242
December 1976
DEVELOPMENT OF A HYDROPHOBIC SUBSTANCE
TO MITIGATE PAVEMENT ICE ADHESION
By
G. H. Ahlborn
H. C. Poehlmann, Jr.
Ball Brothers Research Corporation
Boulder, Colorado 80302
Contract No. 68-03-0359
Project Officer
Hugh E. Masters
Storm and Combined Sewer Section
Wastewater Research Division
Municipal Environmental Research Laboratory (Cincinnati)
Edison, New Jersey 08817
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been rev.iewed by the Municipal Environmental
Research Laboratory, U. S. Environmental Protection Agency and
approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the
U. S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
11
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FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the
health and welfare of the American people. Noxious air, foul water,
and spoiled land are tragic testimony to the deterioration of our
natural environment. The complexity of the environment and the
interplay between its components require a concentrated and integrated
attack on the problem.
Research and development is that necessary first step in problem
solution and it involves defining the problem, measuring its impact,
and searching for solutions. The Municipal Environment Research
Laboratory develops new and improved technolpgy and systems for the
prevention, treatment, and management of wastewater and solid and
hazardous waste pollutant discharges from municipal and community
sources, for the preservation and treatment of public drinking water
supplies, and to minimize the adverse economic, social, health, and
aesthetic effects of pollution. This publication is one of the
products of that research; a most vital communications link between
the researcher and the user community.
The program described here was undertaken to investigate the
feasibility of the use of hydrophobic substances on highways to
reduce ice adhesion. Such a coating could reduce or eliminate
the possibility of pollution of ground water by currently used
deicing chemicals and the multi-billion dollar yearly cost of
automotive frame, bridge deck and highway surface deterioration
caused by such chemicals. The feasibility of this approach is
demonstrated and specific recommendations are presented to
optimize the concepts developed in this program.
Francis .T. Mayo
Director
Municipal Environmental Research
Laboratory
iii
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ABSTRACT
This research was directed specifically to the development of
hydrophobic material coatings for highway surfaces to reduce
the adhesion of ice on such surfaces. In addition to the tech-
nical goal of functional usefulness, other primary ground rules
included:
Cos.t effectiveness as compared to conventional de-
icing methods
Minimum pollution of the environment during applica-
tion and subsequent runoff water exposure
Employment of standard road coating equipment and
techniques
Consideration of only hydrophobic materials as
opposed to conventional materials used to melt ice
and snow
Maximum coating life permitting, as a goal, once-
per-season application
Minimum corrosiveness to automotive frames and bridge
substructures, minimum deleterious effect on highway
surfaces, and maximum safety in use
Investigation of only existing commercially available
materials with no synthesis of new compounds
The following four-phase program was conducted:
Phase I. Identify through literature searches, vendor contacts
and consultants, as many commercial products as possible which
might meet the requirements.
Phase II. From the list compiled in Phase I, select materials
for laboratory characterization and functional testing and con-
duct such tests.
Phase III. From the data of Phase II
Rate materials and material combinations on the basis
of the ground rules listed above
iv
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Establish selection criteria for road testing
Consider application techniques and calibrate the
application equipment
Phase IV. Conduct highway and parking lot evaluation of three
formulations from Phase III.
Of the three coatings applied and tested in Phase IV (the
applied cost for these three ranged from 8^/m2 to 69<ฃ/m2), two
demonstrated considerable promise. These two exhibited satis-
factory traction on wet roads, produced very low runoff water
contamination and demonstrated a significant reduction in ice
adhesion. However, they were inadequate in meeting the goal
of a season-long effective life. The components of these two
formulations comprise three classes of materials which, if opti-
mized, should yield effective coatings.
In addition, several test methods were developed by BBRC that
should prove useful in this and other fields.
This report Is submitted in partial fulfillment of BBRC Project
Number 2075 under the sponsorship of EPA Contract 68-03-0359.
Work was completed as of July 1975.
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CONTENTS
Foreword iii
Abstract iv
Figures :....... x
Tables ,....,. .xฑ
Acknowledgment , , . , xii
1. RECOMMENDATIONS AND SUMMARY 1
2. THEORY ' 9
1.0 Basic and Applied Wetting Theory and
Modifications . 9
1.1 Practical Modifications of the Basic Theory 10
1.2 Applied Theory and Water/Ice Phobicity 12
2.0 Literature Surveys 15
2.1 Dispersion Forces and Work of Adhesion 16
2.2 Hydrophilic Sites and Temperature Effects 17
3.0 Surface Energy and Contact Angle 18
3. PHASE I 20
1.0 Search- Summary 20
1.1 Search Literature 20
1.2 Search Comments " 22
1.3 References 22
2.0 Theoretical Studies 22
3.0 Test Programs 22
3-1 General Comments 22
3.2 Common Results of Tests . . , 23
3.3 Anomalous Results . . . .23
4.0 Material Properties and Selection Criteria 24
4.1 Hydrophobicity 24
4.2 Problems in Property Identification 24
4.3 General Selection Criteria 25
5.0 Contacts ........... 30
5.1 Vendor Contacts 30
5.2 Other Contacts .' . . . 31
6.0 Phase II Material's List 33
6.1 Materials 33
6.2 Material Combination Philosophy 35
4. PHASE II SCREENING TESTS 36
1.0 Infrared Analysis and Other Material Characteristics ... 36
2.0 Surface Energy and Wetting Characteristics ........ 37
2.1 General Approach 37
2.2 Numerical Data 39
2.3 Photos 45
2.4 Conclusion 47
3.0 Comments on Other Tests 51
vii
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4.0 Ice Adhesion Screening Tests t 51
4.1 Test Procedure 51
4.2 Numerical Data 52
4.3 Photos 52
4.4 Conclusion 52
5.0 Highway Wear Tests < .... 55
5.1 Procedure 55
5.2 Data and Results 55
5.3 Photos 57
5.4 Conclusion .57
6.0 Friction and Degradation Tests 57
6.1 Procedure 61
6.2 Numerical Data and Observations .61
6.3 Photos 61
6.4 Skid Value Interpretation .65
6.5 Conclusion 71
7.0 Ultraviolet Stability Tests 71
7.1 Theory * 71
7.2 Procedure a 73
7.3 Numerical Data 75
7.4 Photos * 75
7.5 Conclusion 75
8.0 Solubility Data 75
9.0 Environmental Impact Tests ..... 77
9.1 Procedure > ' 77
9.2 Numerical Data and Observation 77
9.3 Conclusion 79
5. PHASE III APPLICATION STUDY 4 .... 80
1.0 Inroduction 80
2.0 Rating Factors and Formulation Selection 80
2.1 The Ratings 81
2.2 Discussion : 84
3.0 Composition Summary .84
4.0 Cost/Coverage Summary 86
5.0 Application Formula * .88
6.0 Cost Summaries and Comparisons 89
6.1 Hydrophobic Material Application Cost ....... .... 89
6.2 Salting Cost 89
7.0 Spray Techniques and Calibration 90
7.1 Spray Application Techniques 90
7.2 Application and Equipment Calibration 91
8.0 Environmental Impact Summary ' 92
8.1 Solid Wear Debris 92
8.2 Water Soluble Matter 93
8.3 Air-Borne Contamination 93
6. PHASE IV HIGHWAY APPLICATION AND TESTING 95
1.0 Introduction 95
2.0 Site Selection and Description 95
2.1 Site Selection Decisions 95
2.2 Geographical Site Location 97
2.3 Site Application Configuration - ... 98
Vlll
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3.0 Application of Coatings 98
3.1 Coating Application Factors ,...,,,,.,,.,,,, 98
3.2 Conditions and Observations 99
3.3 Photos 100
3.4 Conclusion 104
4.0 Winter of 1974 - 1975 Observations 106
4.1 Measurement Methods 106
4.2 Observations and Data 106
4.3 Photos Ill
4.4 Conclusion 116
5.0 Post - Test Data 116
5.1 Wear - Life Estimates 118
5.2 Skid Test Measurements 118
5.3 Ice Adhesion Tests 121
5.4 Additonal Environmental Data 123
6.0 Phase IV Conclusions 126
References 127
Appendices
A. Houser Laboratories Reports 133
Reference 54 133
Reference 55 148
Reference 56 153
Reference 57 158
Reference 58 160
Reference 59 162
Reference 60 165
Reference 61 171
B. Contact Reports 175
Reference 62 175
General References 185
C. Test Site Maps and Charts 189
D. Colorado Highway Department Accident Reports 194
Reference 63 194
Reference 64 199
Glossary 202
IX
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FIGURES
Number Page
4-1 Steel Test Discs and Contact-Angle-Measurement Apparatus 46
4-2 Water Droplets on Various Materials for Contact Angle
Measurements 48
4-3 Water Droplets on Various Materials for Contact Angle
Measurements 49
4-4 Test Discs and Plates Used for Evaluation of Various Materials. .50
4-5 Ice Adhesion Core Samples and Test Apparatus 54
4-6 Application of Prospective Materials for Phase II Wear Tests . . 58
4-7 Results of Phase II Wear Tests on Asphalt After 35 Days 59
4-8 Results of Phase II Wear Tests on Asphalt After 75 Days 60,
4-9 Tests of Various Materials on BBRC Asphalt Parking Lot 64
4-10 Tests of Various Materials on BBRC Asphalt Parking Lot 66
4-11 Tests of Various Materials on BBRC Asphalt Parking Lot 67
4-12 Severely Degraded Test Sections on BBRC Asphalt Parking Lot . . .68
4-13 Tests of Various Materials on BBRC Concrete Sidewalk 69
4-14 ASTM E303-69 Portable Skid Tester 70
4-15 Correlation of Friction Coefficient With Skid Value From
Portable Skid Tester 70
4-16 Ultraviolet Stability Test Samples and Apparatus 76
6-1 Application Truck on Highway 36 Showing Barrels of Coating
Formulations and Spray Apparatus . .101
6-2 Entire Application Rig During Coating of Highway 36 102
6-3 Application of Coating on Highway 36 Concrete Showing Level
of Edge Control Obtainable 102
6-4 First One-Half Lane Strip of Formulation B Applied
to Highway 36 Concrete 103
6-5 Application of Formulation A to Highway 36 Concrete Showing
Even Spray Pattern and Small Amount of Vapor Drift 103
6-6 Completed Application of Formulation B to Highway 36
Concrete 104
6-7 Formulations A, B and C on BBRC Asphalt Test Site 105
6-8 BBRC Asphalt Test Site, Showing Overall View and
Hydrophobicity of Tested Formulations A, B and C 113
6-9 BBRC Asphalt Test Site Showing Release of Ice From
Sections Treated with Formulations A and C Compared to
Lack of Release From Untreated Sections 114
6-10 BBRC Asphalt Test Site Showing Release of Ice From
Sections Treated with Formulations A, B and C 115
6-11 BBRC Concrete Test Site Showing Insulating Effect,
Hydrophobicity and Degradation of Various Coating Materials . . 117
6-12 Ice Adhesion Test Core Samples from Highway 7 and BBRC Asphalt..121
x
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TABLES
Numb er Page
3-1 EPA Literature Search Summary 21
3-2 Hydrophobia Highway Materials 26-29
3-3 Contacts Other Than Vendors 32
4-1 Infrared Analyses and Other Material Characteristics 38
4-2 Contact Angles of Water on Various Substrates 39
4-3 Materials or Formulations Rejected for Further Consideration . . 40
4-4 Contact Angles of Oil and Water on Prospective Materials .... 41
4-5 Contact Angles of Qil and Water on Prospective
Binder Materials 42
4-6 Contact Angles of Oil and Water on Protective
Coating Formulations 43-44
4-7 Ice Adhesion Screening Test Results 53
4-8 Highway Wear Tests - City of Boulder 56
4-9 Friction (ASTM E303) and Degradation Tests 62-63
4-10 Suggested Values of 'Skid Resistance' For Use With the
Portable Tester 72
4-11 Ultraviolet Degradation Screening 74
4-12 Environmental Screening Test Results 78
5-1 Material/Formulation Rating Sheet 82
5-2 Compositions of Rated Coatings 85
5-3 Basic Material Cost/Coverage Data 87
6-1 Weather Data During Road Test Period 107
6-2 Road Test Observations on Highway 36 109
6-3 Road Test Observations on Highway 7 and Pearl Street 110
6-4 Observations on BBRC Asphalt and Concrete Sites 112
6-5 Phase IV Highway Skid Test Values 120
6-6 Phase IV Highway Core Ice Adhesion Test Results . 122
6-7 High Temperature Water Extraction Data 124
XI
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ACKNOWLEDGMENTS
Many individuals in the following organizations have made sig-
nificant contributions of time and material and their partici-
pation is gratefully acknowledged. Special recognition is due
the Colorado Highway Divisions and Boulder Street Department
listed below for their contribution of technical advice and
background data and their active participation in applying
coatings and obtaining core samples.
Akron Paint and Varnish Company, Akron, Ohio
Ashland Chemical, Kansas City, Missouri
Cabot Corporation, Boston, Massachusetts
Central Technical Information Service, University of
Colorado, Boulder, Colorado
Chemfil Corporation, Troy, Michigan
City of Boulder Street Department, Boulder, Colorado
Colorado Department of Highways, Boulder Region, Boulder,
Colorado
Colorado Department of Highways, District 4, Greeley,
Colorado
Colorado Department of Highways, State Headquarters,
Denver, Colorado
Coronado Paint Company, Edgewater, Florida
DAP, Incorporated, Dayton, Ohio
DeBell and Richardson Company, Enfield, Connecticut
Pecora, Incorporated, Philadelphia, Pennsylvania
Department of Transportation, Federal Aviation Adminis-
tration, Denver, Colorado
Dow-Corning Corporation, Midland, Michigan
Federal Aviation Administration, Jeffco Facility,
Broomfield, Colorado
Flatiron Paving Company, Boulder, Colorado
Frekote, Incorporated, Indianapolis, Indiana
General Electric Company, Schenectady, New York
General Mills Chemicals, Incorporated, Minneapolis,
Minnesota
xii
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Goodyear Tire and Rubber Company, Chemical Division,
Akron, Ohio
Government Services Administration, Denver, Colorado
Hauser Laboratories, Incorporated, Boulder, Colorado
Highpoint Chemical Corporation, Highpoint, North Carolina
Jorgenson Paint Company, Denver, Colorado
J. P. Stevens, Incorporated, Garfield, New Jersey
Kaiser Agricultural Chemicals, Savannah, Georgia
Koehler Mclister Paints, Denver, Colorado
Kwal Paint Company, Denver, Colorado
Merix Chemical Company, Chicago, Illinois
Minnesota Mining and Manufacturing, Minneapolis, Minnesota
NASA, Lewis Research Center, Cleveland, Ohio
National Weather Service, Denver, Colorado
Naval Civil Engineering Laboratory, Port Hueneme,
California
Naval Research Laboratory, Chemistry Division, Washington,
D. C.
Onyx Chemical, Jersey City, New Jersey
Philadelphia Quartz Company, Valley Forge, Pennsylvania
Phillips Petroleum Company, Bartelsville, Oklahoma
Sandoz Colors and Chemicals, New Jersey
Stauffer Chemical Company, New York, New York
Transcontinental Research and Development, Tucson, Arizona
Union Carbide, Tarrytown, New York
United States Army Cold Regions Research and Engineering
Laboratories, Hanover, New Hampshire
W. F. Nye, Incorporated, New Bedford, Massachusetts
Whitford Corporation, Weschester, Pennsylvania
XIM Products, Incorporated, Westlake, Ohio
xui
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We acknowledge with gratitude the support of this effort by
the Storm and Combined Sewer Section (Edison, New Jersey) of
the EPA Municipal Environmental Research Laboratory,
Cincinnati, Ohio. We extend special thanks to Mr. Richard
Field, Chief, and Mr. Hugh Masters, Project Officer, in the
above Section, and to Dr. Herbert Skovronek of the Industrial
Environmental Research Laboratory, Cincinnati, Ohio, for their
guidance, suggestions and inputs, and for their thorough re-
view of this manuscript.
xiv
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' Chapter 1
RECOMMENDATIONS AND SUMMARY
THE PROBLEM
The use of salt (and other deicing chemicals such as calcium
chloride, urea and glycol mixtures) and sand to remove ice
from highway surfaces in winter is the commonly accepted method
used in the United States and Canada. For example, three
years ago, usage was cited (Ref. 4*) as over nine billion kilo-
grams (ten million tons) per year in the U. S. Application
rates are also cited (Ref. 4) as high as 14,000 kg per lane km
(25 tons per lane mile) in some areas per season. While other
deicing chemicals present somewhat fewer problems in vehicle
damage and bridge deck/highway surface deterioration, they are
more expensive, are less effective and some increase the oxygen
demand of runoff water in the areas where they are used. Thus,
the primary objections to the use of chemical deicers are:
Direct environmental impact.
Indirect environmental effects including vehicle
corrosion and pavement and bridge deck structure
damage, with consequent safety hazards and considerable
economic loss in all cases .
The specific problem to which this report is addressed is the
development of a hydrophobic substance to mitigate the adhesion
of ice to pavement as an alternative to deicing chemicals.
The factors involved in evaluating this concept are outlined
below.
Economics. The coating used to reduce ice adhesion must be
economically justified. Considering only salt replacement,
elimination of vehicle damage and reduction of highway struc-
ture damage, the latest data (see Chapter 5, Section 6 of this
report) indicate that the cost of a coating applied onee-peT-
season must be less than about 28<ฃ/m2. Note that reduction
* For'reasons discussed later, cited references in this report
are not necessarily numbered in the same order as they first
appear in the text.
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of pavement damage and virtual elimination of direct environ-
mental impact costs are not considered. These latter effects
could substantially increase the above allowable cost.
Safety. The principal safety aspects to be considered are
toxicity, flammability and other potentially hazardous proper-
ties of the coatings. Such considerations apply equally to
the formulation before application, conditions present during
application to the pavement and the dried film on the highway.
Storage requirements are defined by Occupational Safety and
Health Administration (OSHA) flammability and toxicity require-
ments. Hazards during application are defined by the State of
Colorado version of EPA Regulation No. 7 (attached as part
of Reference 62 in Appendix B). The dried coating hazards
are discussed in Chapter 4 of this report. It was also hypoth-
esized that oleophilic (oil attracting) coatings might create
a skid hazard.
Environmental Impact. The environmental impact of currently
used deicing materials (primarily inorganic chlorides) is
known to be severe. Current estimates (Ref. 70) indicate
annual damages to water supplies, health, vegetation and
utilities in excess of $100 million. In addition to these
damages, any alternative coating must be evaluated in terms
of water solubility, application hazards and personnel hazards.
In relatively thin coatings (say, 0.01 cm), inert hydrophobic
coatings overcome most of the above impact problems. As shown
in this report, application hazards constitute the one area
requiring further work.
Coating Effectiveness. Although effectiveness is certainly the
most basic criterion for an ice-release coating, it is perhaps
the most difficult to define in quantitative terms. Deicing
chemicals either do or do not melt snow and ice at a given
temperature whereas ice release is a function of temperature,
shear rate, substrate roughness, applied force vector and
other factors. The approach in this work was to demonstrate
hydrophobicity and to rank shear adhesion force for the coat-
ings by laboratory test, followed by real-life field testing.
In the same way, coating effective life (involving, among
others, factors of coating/substrate chemistry, coating-to-
substrate adhesion, abrasion resistance, shear strength,
traffic patterns and densities and the presence of salt, sand,
dirt, etc.), was evaluated by actual highway wear testing.
To be effective, the coating must not create, in itself, the
very condition it is intended to alleviate, namely, slippery
roadway surfaces. In fact, demonstration of this property was
found to be the primary concern of the Colorado Department
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of Highways and a large amount of friction-coefficient data
was obtained for the coatings on asphaltic and concrete sur-
faces .
Finally, stability in the presence of ultraviolet radiation
(sunlight) and oxygen is required. This was evaluated by
both laboratory and outdoor exposure methods.
Potential Pavement Damage. In order to avoid potential pave-
ment damage, strong acidic or basic water solutions must be
avoided, especially on concrete, and any application-phase
solvents must not degrade asphaltic surfaces. It was also
demonstrated in this program that oleophilic materials badly
degrade asphaltic surfaces. To be even more economically
attractive than deicing chemicals, hydrophobic ice-release
coatings should actually protect highway surfaces from water
penetration and subsequent freeze-thaw damage.
RECOMMENDATIONS
As a result of this program, two coating formulations (exact
formulae are given in Chapter 5 of this report), have been
identified as showing considerable promise as semi-permanent,
hydrophobic, road coatings with reduced ice adhesion. They
are:
A modified (no pigment) Federal Specification
TT-P-115D traffic paint containing a room-temperature-
curing silicone rubber (Dow Corning DC732) as a re-
lease agent. Formulation is identified as A in the
Phase IV road test evaluation.
e A silicqne resin waterproofing compound (Dow Corning
DRI-SIL-73) combined with the same silicone rubber as
above and identified as formulation C in Phase IV.
One major achievement in this program was the discovery of a
method for stabilizing the highly reactive silicone rubber in
a fluid solution for spraying.
As applied to roadway surfaces in dried films about 0.01 cm
(0.004-inch) thick, these two coatings:
Show greatly reduced ice adhesion until physically
wo rn away.
Have an applied cost of about 40ฃ/m2 and 69^/m2 (33<ฃ
and 58<ฃ/yd2) as of December, 1974.
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Show excellent stability to weathering.
Exhibit total water-soluble material equivalent to a
maximum of about 18 grams per lane meter (64 pounds
per lane mile) (see Section 9.3 of Chapter 4).
Have low pollution impact.
Show negligible corrosiveness and zero road damage.
Can be applied with standard spray truck techniques.
Require a maximum lane closure time of one to three
hours depending on ambient temperature.
Do not greatly reduce rubber-to-road friction coeffi-
cient .
The deficiencies of these formulations are:
1. An estimated effective wear life of only 150,000 to
300,000 vehicle passes (one to two months on the tested
roads) for the thickness employed.
2. The release of flammable vapors, mostly VMP naphtha,
into the atmosphere during application.
In view of the above and other program data, the following
specific recommendations are made:
Neither formulation fully meets the target goals of
a material that easily releases ice and can be applied
only once per season to existing roadway surfaces.
However, Formulation A above should be useful and
nearly invisible on low traffic areas suc.h as concrete
driveways and sidewalks, while Formulation C above,
applied at perhaps twice the rate used here, should
release ice from and help protect asphalt-surfaced
bridge decks. Other processes for surface sealing,
such as in Reference 39, are estimated to cost more
than five times as much.
Both formulations should be optimized by variation
of component ratios for minimum ice adhesion. In
addition, the paint formulation contains components
such as clays and other extenders that are probably
hydrophilic and therefore harmful in this application.
Variations of the basic paint formula should be tested.
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Future road tests should be conducted in more
consistently colder regions.
Laboratory ice adhesion testing should be performed on
real substrates over a wider range of temperatures and
shear rates than those used here (see Chapter 4,
Section 4.2).
Water-based emulsion systems coupled with elevated
temperature curing should be studied. Slow evapora-
tion and the primarily budgetary limitation of ambient
temperature curing resulted in long lane-closure times
and negative results for such systems in this study.
However, such systems remain attractive from material
cost and pollution-during-application standpoints.
One ground rule of the present work was the applica-
tion of the coatings to existing road surfaces. How-
ever, roads are resurfaced and incorporation of hydro-
phobic materials in the resurfacing mix should vastly
extend the effective wear life. This should be in-
vestigated, especially with respect to Petroset AT and
Viscospin-B (see Appendix B).
In view of the current expense of highway repair, a
separate study is also needed of the substrate protec-
tion afforded by hydrophobic materials applied with
the asphalt or concrete.
INTENT OF REPORT
The purpose of this report is fourfold, namely:
To describe the work conducted in sufficient detail to
permit evaluation of the data by independent investi-
gators .
To explain the material selection/screening procedures
and justify the conclusions reached.
To record data which, while not directly applicable to
the stated goals, might be useful in other work. Two
examples are the tabulation of unsuccessful material
combinations in Phase II and the citation of refer-
ences, including some not specifically used in this
report, as background material in this field.
To present recommendations which appear to be a logi-
cal extension of this basic study.
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SUMMARY OF REPORT
Since some sections of this report may be of only limited in-
terest in some cases, such as theoretical discussions might be
to those interested primarily in practical results, this por-
tion summarizes the contents of the chapters presented herein.
Chapter 2, Theory. In this chapter are presented the basic
theory of wetting, surface energy balance considerations as
applied to hydrophobicity, work of adhesion as related to
water and ice and practical modifications of theory applicable
to this study.
Chapter 3, Phase I. In this description of the Phase I pro-
gram work are included the results of a complete literature
survey, a review of applicable test programs, a summary of
all contacts made with vendors and other organizations and a
review of the material candidates to be evaluated in the Phase
II screening tests.
In tabular form are presented all the materials considered and
the test/reject criteria employed. Tabulated are over 55
materials and material classes.
Chapiter 4, Phase II. The laboratory and outdoor property
screening of 33 materials are presented in this chapter. In-
cluded are contact angle data (a measure of hydrophobicity),
infrared analyses and vendor-supplied data, ice adhesion test
results, friction coefficient data for the coatings on asphalt
and concrete, environmental hazard test results, ultraviolet-
exposure and other degradation evaluations and highway wear
test results. Also included are an extensive list of rejected
materials and material combinations and the criteria employed.
Chapter 5, Phase III. Phase-III, the application study, in-
cludes the following:
Rating factors for 28 materials and the selection pro-
cedure used for the three highway-tested coatings.
A summary of the exact composition for the coatings
as applied.
Material property (composition, density, etc.) data
required to determine the bulk application rates
desired.
Formulae used to determine application-vehicle speeds
required during application.
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A discussion of spray techniques, spray rate calibra-
tion and application-vehicle speed calibration.
A summary of applied-coating-cost computations.
A summary of environmental impact considerations.
Chapter 6, Phase IV. Evaluation of the three selected formu-
lations on asphalt and concrete is discussed in Chapter 6.
Presented are:
Weather data
Visual observations
Qualitative skid data
Ice release data
for three high-traffic-density areas, one low-traffic-density
area and two zero-traffic-density locations.
Also included are:
Wear life estimates
Additional quantitative friction coefficient data
Supplemental laboratory ice adhesion data
Additional environmental impact test data
As required by the funding contract, the International System
of Units is employed "except when the use of such units would
obviously impair communication or reduce the usefulness of a
report to the primary recipients" (Ref. 38). Two specific
examples where such impairment would result are:
Ice Adhesion Shear Force. The use of kg/cm2 (as
opposed to N/mz)results in conveniently small numbers
facilitating comparison of values
kg/cm2 x 9.8 x 10" = N/m2
Surface Energy and Dispersion Energy. The use of
ergs/cm2is so common in theliterature that compari-
s'on would be difficult without retention of these
units.
ergs/cm2 x 1.0 x 10"3 = N/m
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Finally, for one-time computations used in illustrative ex-
amples where only relative values are important (such as those
in Paragraph 5.4.3, Chapter 6), conventional metric (though
not SI units) are employed.
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Chapter 2
THEORY
This chapter is concerned with the theoretical and applied sur-
face physics and chemistry technology of wetting phenomena as
specifically related to the objective of producing a water or
ice repellant. The various parameters involved in wetting and
the testing of wetting phenomena are discussed together with
the chemical types desired for candidate screening. Theoreti-
cal studies from the literature survey of Phase I are then
discussed. Finally, the derivation of surface energy values
from laboratory contact angle measurements is reviewed.
1.0 BASIC AND APPLIED WETTING THEORY AND MODIFICATIONS
The basic theory of wetting, of which hydrophobicity is a
specialized case, has been extensively treated in the litera-
ture (see References 3, 67, 41 and 2): The initial concept is
shown in the sketch below. This shows the equilibrium forces
for a drop of fluid on a flat substrate.
Substrate
(Coating)
where
6 = Contact angle
o
sv
YeVฐ = Interfacial free energy of solid/saturated
vapor interface
Interfacial free energy of liquid/saturated
vapor interface (this is sometimes erroneously
used as identical with liquid surface tension)
Interfacial free energy of solid/fluid interface
-------
For equilibrium,
V ฐ Y = Y ฐ
*SV " SL *LV
It is apparent that the smaller the left-hand side of the
equation (which is related to the surface free energy of the
solid coating), the greater is 8.
From Reference 3,
WA =
where
W. = The work of adhesion
Ygฐ = The surface energy of the solid in vacuum
Substituting (1) in (2):
WA = V - YSVฐ + YLVฐ Cl + cos 6) (3)
the so-called Dupre equation. The first two terms represent
the decrease of the specific free energy of the solid when
immersed in the saturated liquid vapor. This quantity can
rarely be quantitatively determined, but however it is deter-
mined, it will be smaller the lower the specific free energy
of the solid. YTVฐ is fixed for water, so the only other
variable is 6.
From the above equations, if the work of adhesion is to be mini-
mized :
The surface free energy of the coating must be as
small as possible
8 should be as large as possible
From the above alone, for minimum adhesion it would therefore
only be necessary that the coating consist of a single mono-
layer with a very low surface free energy, since such a sur-
face also increases 8 as is shown by Equation (1).
Many such molecular types are specified in References 3 and 41.
However, the above simplified theory must be modified to in-
clude other important technical factors.
1.1 Practical Modifications of the Basic Theory
Solubility. The simplified theory does not account for solu-
bility of the fluid phase in the substrate or coating. This
10
-------
has been demonstrated in tests at BBRC. For example, low
energy coatings have been tested upon which certain fluoro-
chemicals (with Y-^y0 = 18 ergs/cm2) will not spread but upon
which certain silicones (with Y^y0 = 23 ergs/cm2) will spread.
This explains the need for solubility testing of candidate
coating materials in water and the practical difficulties of
deriving surface energy from contact angle measurements (dis-
cussed in Section 3 below).
Long Range Forces. Most intermolecular forces are relatively
short range(less than 10 A, or about one monolayer). However,
permanent and induced dipole forces (water is a strong dipole)
have ranges of many monolayers. This explains the need for
relatively thick coatings (greater than one micron, or
10,000 A), to block the adhesive effect of these forces. This
effect is discussed further in Section 2 below.
Roughness. The theory assumes perfectly flat surfaces. This
is never true in reality. On rough surfaces, Wenzel's equa-
tion:
cos 0" = r cos 9 (4)
where
0 ' = Contact angle observed
r = Ratio of aetual surface area to apparent (envelope)
surface area
6 = Contact angle on a smooth surface
applies. For example, should 0 be 60ฐ and r be 2.0, 0 "* will
be 0ฐ and total spreading will occur. Such phenomena have been
observed and studied at BBRC. This is the explanation for the
use of "rough" more "real-life" surfaces in the contact, angle
screening tests (Chapter 4).
1.1.1 Requirements of a Truly Hydrophobic Coating
From this brief (and in some respects superficial) examination
of surface theory, a truly hydrophobia coating must have:
Minimum specific surface energy
A thickness of several thousand angstroms
Virtually no solubility in water
11
-------
A contact angle as large as possible with a minimum
value of 60ฐ on a smooth surface
Equation (3) demonstrates why the work of adhesion is unlikely
to ever be zero. The first two terms represent a positive
value and the third term is always greater than zero (since
8 = 180ฐ has never been observed in practice - see page 145 of
Reference 3) .
1.2 Applied Theory and Water/Ice Phobicity
The theory outlined above is now directed to the specific prob-
lem of water/ice phobicity of coatings applied to rough roadway
surfaces.
Testing Considerations. The relationship between hydropho-
bicity and the corresponding property for ice has been treated
in some detail in Reference 2, pages 46-77. Specific points
to be considered in testing are:
The tensile strength of ice itself decreases with in-
creasing ice volume. This, together with the assump-
tion that water will bead up on hydrophobic coatings,
suggests the use of small ice volumes to measure the
adhesive ice/coating shear strength.
The number of factors indicated in the problem dis-
cussion in a previous section are also emphasized in
Reference 2. This confirms the conclusion already
reached that complete simulation of reality in the
laboratory is not economically feasible and that only
individual specific parameters can be treated experi-
mentally.
The surface free energy of ice is cited in Reference 2
as 109 ergs/cm2 and of water as about 75 ergs/cm2. On
this basis, ice should have lower work of adhesion.
That it does not (see discussion in Reference 2) indi-
cates the existence of long range forces discussed
above.
Some solid polymers exhibit no change in shear-release
force of ice with repeated release while other hydro-
phobic materials (having equal or lower surface
energies), such as the perfluorinated acids, show an
increase with each release, indicating coating removal.
The use of tough binders appears to be a logical
approach. In binders, the effective hydrophobic
groups can be exposed at the surface by preferential
12
-------
density effects and maintained by wear of the coating.
Experimental verification is obviously a necessity.
In the conclusion of the Reference 2 article, the
difficulty of simulating reality is again emphasized.
The partial absorption of water by the coating and
subsequent coating removal by cohesive failure during
shear testing is stated as the major problem area.
1.2.1 Desirable Chemical Types
The surface free energy of a large class of materials is given
in Reference 3. Molecular orientation is vital and the species
predominating on the coating surface control the surface
energy. Some examples are:
Predominant Species Surface Energy (ergs/cm2)
-CF3 6
-CF2H 15
-CF2- 18
-CF3 22-24
-CH2- 31
Water (surface energy about 75 ergs/cm2) cannot spread on a
lower energy surface, in general, so that such surfaces are
highly hydrophobic. This explains the action of organo-
fluorochemicals (the first three types in the table above),
and of cationic surface-active agents (exemplified by the
latter two types). As explained in the Glossary, surface
active agents have hydrocarbon "ends" rich in -CH3 and -CH^-
groups. The exact hydrophobic mechanism of organo-silicone
resins is more complex and is not solely a function of sur-
face energy. This is illustrated by data in References 17 and
18. The work of adhesion (ice in shear) is cited as being much
lower for silicone resin XZ-8-3057 than for FEP Teflon. This
is the reverse of what would be expected from surface energy
considerations (silicones generally have surface energies
ranging from 18 to 22 ergs/cm2 for dimethyl types to 35 or so
for substituted polymers), and suggests cohesive failure within
the resin. Strongly hydrophobic silicas are also known and
compromise a fourth class of potential candidates for this
application. The fifth class, a rubber-based coating, is dis-
cussed be^Low with respect to binder coatings .
13
-------
1.2.2 Binder Coatings with the Water/Ice Phobic Chemicals
Some aspects of thickness effects have been presented earlier,
namely,
Thin films are likely to be more durable from a stress
standpoint and are more economical from a materials
standpoint.
Thicker fil-ms are required to prevent long range dipole
adhesion (of water) effects and may have longer
abrasive wear life.
The use of "inert" binders is suggested by these considera-
tions . The binder serves to dilute the active ingredient
(thus saving costs in the case of the fluorochemical class
especially), holds hydrophobic materials with low pavement
adhesion in place and possibly acts as a reservoir of active
material by diffusion through the binder. Also, as discussed
in detail below, thicker films will reduce roughness and hence
wetability. Highway paints have already been developed that
have the required six-month service life (based on verbal data
from Hauser laboratories, BBRC's principal subcontractor on
this program). The extended wear life of rubber-based paints
is also confirmed by the wear data of Reference 49. In addi-
tion it is interesting to note that the one part of a car
that does not ice up is the tires, suggesting that rubber-
based paints might also be advantageous themselves. This is
also suggested by the wear data of Reference 49.
1.2.3 Roughness Influence Upon Coating Effectiveness
The situation may be visualized as in the following sketch
for coatings much thinner than surface roughness profiles.
Coating Initial
Condition
f
'Pavement'
Coating ...
6 Worn
Condition
Pavemen
14
-------
This schematic representation indicates what would be expected
after a period of wear (traffic) on a treated pavement surface.
Note that wear will proceed more rapidly at the points of
highest stress. The result will be:
Traction will be good due to exposed pavement at high
points, even if the coating itself had a lower co-
efficient of friction than the pavement.
0 The effectiveness of the coating will not be greatly
affected since most of its surface area is still in-
tact in the valleys where water would tend to collect
and freeze.
ซ Pavement crack propagation is most likely at the root
(or bottom) of surface irregularities where stress
concentrations exist. These areas will be the last
to be worn off so the sealing effect (pavement life
improvement) will be maintained.
For the thicker coatings, the valleys will remain
filled and thus the wetability due to surface rough-
ness will be reduced.
Even on extremely rough roadways, the possibility of water-to-
water (ice-to-ice) bonding at the peak of the ridges exists.
This can be evaluated only by field tests .
2.0 LITERATURE SURVEYS
Theoretical studies directly applicable to this program have
been found to be quite rare. In fact, a very recent report
(Reference 40) states that no satisfactory icephobic coatings,
as yet, exist.
Such observations as are given below are inferred from
References 1, 2, 3, 5, 7, 15, 16, 26, 31 and 36. As some of
the theoretical studies cited contain test data, the division
between theoretical and test studies is somewhat arbitrary.
An attempt by any author to arrive at generalized rules was
the criterion used in defining theoretical work. Test study
conclusions are summarized in Chapter 3.
It must be emphasized that the conditions for a truly hydro-
phobic coating (Part 1 above) are sufficient for water but
only necessary (not sufficient] conditions with regard to the
adhesion of ice. The reasons for this are discussed below.
15
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2.1 Dispersion Forces and Work of Adhesion
As cited in Chapter 1 of Reference 1, long-range dispersion
forces (sometimes called London dipoles) are the controlling
forces across interfaces (as between water or ice and a solid).
This value for water (Yฐ0 is only 22 ergs/cm2 as opposed to
the total surface energy for water (Yw) of 75 ergs/cm2. For
a solid with a dispersion force of Yง, the spreading co-
efficient (S)* is:
, , (Ref. 1)
S = -2Yw + Y* + Y* (5)
Using the values for water cited above, we have the rather
surprising conclusion that any solid where Y^ is less than
about 130 ergs/cm2 should be hydrophobic. Since Y^- < Ys**,
any solid with a total surface energy (Ys) less than 130
should be hydrophobic and (per Reference 36), this includes
virtually all organic films.
Per Reference 3, the work of adhesion (WA), is:
WA = S + Wc (6)
where Wc is the work of cohesion of the water or ice.
Equation (6) explains part of the observed adhesive ability of
ice. For example, Jellinek (Reference 2) gives the theoreti-
cal tensile strength of ice as 10,000 kg/cm2*** and actual
measurements cited as 16 to 80 kg/cm2****. Tensile strength
cannot be directly converted to work of cohesion, although
these properties should be proportional to each other. There-
fore, since these actual values of tensile strength for ice
are much larger than those for water, the work of cohesion
for ice should be much larger than that for water. This
partially explains the adhesion of ice on some surfaces, even
though S for liquid water may have a large negative value.
*Remember that if S is negative, spreading will not occur,
a finite contact angle will exist and the surface is
thus hydrophobic.
** Reference 1, Chapter 1.
*** About 1 x 109 N/m2, or 140,000 psi.
**** 230 to 1,140 psi.
16
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2.2 Hydrophilic Sites and Temperature Effects
In addition to purely practical difficulties in achieving ice
release (see Chapter 3), two other phenomena complicate
matters even with carefully prepared laboratory surfaces.
As discussed in Reference 1, Chapter 1, all known solid hydro-
phobic surfaces have residual hydrophilic sites. Whether
introduced inadvertently as in the emulsion application of
TFE or as an inherent part of the structure (such as carboxyl
groups in alkyd resins), the effect is the same and creates
some unexpected properties. These are:
Although Y^ decreases with decreasing temperature
(thus making ambient temperature contact angle
measurements conservatively low), the number of
hydrophilic sites (as measured by crystal formation
below 0 C) increases with decreasing temperature.
The amount of water adsorbed on the surface (as
measured by water adsorption between zero and 25 C)
increases with -increasing temperature.
We thus have two opposing phenomena affecting adhesional
strength and which can vary from lot to lot of material. This
might help explain the wide variation in reported ice adhesion
test values. The first effect seems most pronounced with very
hydrophobic (i.e., low surface energy) materials and explains
the strong adhesion of ice to TFE at temperatures below
258 K (-15 C) (see Reference 15 and 34, for example). The
hydrophilic site phenomenon also implies that fluids should
be more efficient than solids in reducing adhesion, since
localized sites of any sort cannot be maintained in a mobile
medium.
Finally, the increase in adsorbed water with increasing
temperature may explain the semi-fluid region between 263 K
(-10 C) and 273 K (0 C) reported by many investigators (see
References 2 and 26, for example).
2.3 Conclusions
Other theoretical work has been reviewed but has added little
to the practical solution of this problem. On the basis of
theory:
Little seems to be gained by the selection of extremely
hydrophobic materials (those with large negative
values of S, including most organics).
17
-------
Extremely hydrophobia materials may actually exhibit
high adhesion (due to the hydrophilic site effect) .
Materials containing Si-C bonds are probably not UV
stable (Reference 7) .
o A stable contact angle of water on the material, in-
dicating very low solubility, is probably more im-
portant than a very high angle.
e Adhesion tests should be conducted below 263 K (-10 C)
to avoid the semi-fluid layer region.
Any coating must be at least several hundred nanom-
eters (thousands of Angstroms) thick to block the
London dispersion forces (Reference 41, page 55).
3.0 SURFACE ENERGY AND CONTACT ANGLE
It was proposed that solid-surface dispersion energies, and
thus work of adhesion for these surfaces, could be derived
from laboratory-measured contact angles of different sub-
stances, (e.g., water and oil), on these surfaces. From
Reference 1, pages 8 and 9, the following equations can be
derived:
YSH 0 = [(1 + CฐS 9H2ฐ)/0-13]2 C7)
YS0il = [(1 + CฐS 6oil)/ฐ-34ฐ]2 (8)
= [(cos 9oil - coseH2o)/0.210]2 (9)
where
Y^ = The solid dispersion energy directly related to
work of adhesion as explained in Section 2.1
above, ergs/cm2
6 = Contact angle with water or oil as noted
It was hypothesized that Equation (9) could be used to rank
the dispersion energy of the coatings studied using contact
angle data (Chapter 4) . If the equation is valid, Equations
(7) and (8) should give identical values. This was not found
to be the case. It is suspected that solubility effects (see
18
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Section 1.1 above) and/or impurities in the commercial
materials studied (a basic program ground rule was the use
of commercially available substances) explain the disagree-
ment between Equation (7) and (8) values computed from the
contact angle data generated in this program. The reason is
that zero solubility of both water and oil in the coatings or
impurities (a requirement of the equation's theoretical
basis) is very unlikely.*
The equations are presented to permit independent evaluation
of this phenomenon from the data cited in Chapter 4 and to
thereby illustrate the harmful effect of solubility on dis-
persion energy (and thus on work of adhesion).
This is evident from the classification of materials into
oleophilic and oleophobic (or hydrophilic) groups (see
Glossary) . Virtually all materials fall into one class or
the 'other and are thus solvated by either water (and other
polar compounds like alcohols) or oil (hydrocarbons).
19
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Chapter 3
PHASE I
INTRODUCTION
This chapter presents the work performed during Phase I of
this investigation. The following aspects of this phase are
discussed below:
The literature survey
The review of theoretical studies, test programs
and property identification efforts
Material vendor contacts
Other organizations contacted
The selection of material candidates to be evaluated
in the Phase II screening tests
1.0 SEARCH SUMMARY
The results of the literature survey conducted are given in
this section. Excluded are other searches (as of vendors,
highway material data and meteorological data records) which
are described in later sections.
1.1 Search Literature
The specific sources searched are given in Table 3-1. As
indicated, a wide range of United States Government and in-
dustrial publications were reviewed. National Technical
Information Service (NTIS) was not asked to search. Prior
experience at BBRC has indicated that NTIS searches are
duplicated by other sources. As is also indicated, most of
the searches were limited to documents from 1968 to the
present in view of the very complete search of Reference 20
and the search cited in Reference 4', which thoroughly covered
most work prior to 1968. In many cases, of course, references
cited earlier works which were also reviewed.
20
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Table 3-1
EPA LITERATURE SEARCH* SUMMARY
Descriptors: Deicers- Ice Removal, Ice Adhesion, Hydrophobic/
Icephobic Materials, Highway Deicing
1. AEROSPACE RESEARCH APPLICATIONS CENTER (ARAC)
(a) Government Report Announcements
(b) Engineering Index, Compendex
2. COLORADO TECHNICAL REFERENCE CENTER (CTRC, University of
Colorado, Boulder)
(a) Engineering Index
(b) Applied Science and Technology Index
(c) British Technology Index
(d) Chemical Abstracts
(e) Highway Research Information Service (HRIS) Abstracts
(f) Bibliographic Index
(g) Highway Research Abstracts
(h) Government Reports Index
(i) International Aerospace Abstracts
(j) Monthly Catalog of U.S. Government Publications
(k) Subject Guide to Books in Print
(1) Library of Congress Catalog, Books: Subjects
3. DEFENSE DOCUMENTATION CENTER (DDC)
(a) All DOD Documents
4. NASA SCIENTIFIC AND TECHNICAL INFORMATION FACILITY
(a) NASA Documents
*Most searches were limited to the period 1968 to date in view of
the comprehensive search (over 200 applicable references) made
by Cold Regions Research and Engineering Laboratory in Icing
Occurrence, Control and Prevention, by K. L. Carey, July 1970
(AD 711 534).
21
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1.2 Search Comments
During the search, abstracts of over 500 references were re-
viewed. In general, most were concerned with aircraft or
stationary installations with auto-release, i.e., no applied
force other than gravity or air streams, of ice from the
structures being the goal. This goal accounts for the rather
pessimistic conclusions (of References 17 and 21) that
"passive ice removal techniques are not feasible". In con-
trast, it must be recognized that in the present case there
are additional forces available (traffic load, for one) which
can aid in ice removal. In addition, the concern here is only
with adhesion reduction, not elimination. Complete adhesion
elimination, in fact, would create a dangerous roadway skid
hazard.
1.3 References
All program references are given at the end of this report.
Many have been derived from sources in addition to the survey
conducted during this initial phase. For this reason, and
also because of the reorganization of material during the
preparation of this program report, cited references are not
necessarily listed in the same order as they first appear in
the text.
2.0 THEORETICAL STUDIES
Theoretical studies reported in the literature have been
summarized in Chapter 2.
3.0 TEST PROGRAMS
The test programs reported in the literature were not
especially applicable to the current program. However, some
generalizations could be inferred which were helpful in
material selection.
3.1 General Comments
In all the programs reviewed, two general features appeared
in most studies:
The coatings and substrates were made as smooth as
possible (References 2 and 31 are exceptions)
Low ice adhesive shear strength was the sole
criterion for successful coatings
22
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3.2 Common Results of Tests
In spite of the wide variation in test techniques and reported
values, certain conclusions seemed common to (or at least were
not contradicted by) most studies:
Some degree of flexibility of the coating reduces
ice adhesive strength (References 2, 12, 14, 15
and 30)
Polar sites increase adhesion, as would be expected
from the hydrophilic site theory discussed in
Chapter 2 (References 13, 16 and 27)
Nonporous surfaces are required to promote low ad-
hesion (References 15 and 21)
Fluid films give lowest adhesive force (References 17,
22, 27, 29, 31, 34 and 37)
Rough substrates give higher adhesion values
(References 2 and 31)
Monolayers of even very hydrophobic substances are
ineffective in reducing adhesion, as would be ex-
pected from the range of London dispersion forces
discussed in Chapter 2 (References 2 and 3)
3 .3 Anomalous Results
The number of anomalous results reported in the literature,
remembering that hydrophobicity is a necessary but not
sufficient condition for low ice adhesion strength, were few.
Most anomalies concerned the effect of temperature on adhesive
strength. This is really not surprising in view of the two
opposing effects cited in Chapter 2. As is also pointed out
in Chapter 24 of Reference 1, the effect of temperature on
contact angle can even be reversed depending on whether the
area of water coverage is increasing or decreasing.
With regard to material selection, in general it was found
that hydrophobicity is some guide to low ice adhesion even
though one reference (Jellinek in Reference 2) concludes
that there is no correlation of adhesion with either coating
surface energy or contact angle. The detailed problems in
material selection and the criteria used by BBRC are dis-
cussed next.
23
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4.0 MATERIAL PROPERTIES AND SELECTION CRITERIA
Identification of candidate material properties are presented
below along with tradeoff problems and the selection criteria
actually used on this program.
4.1 Hydrophobicity
The degree of hydrophobicity of the materials selected re-
quires special mention. As pointed out in Chapter 2, to
give a finite contact angle, theory requires only that the
surface energy of the coating be less than about 130 ergs/cm2.
Of the 43 polymers listed in Reference 36, the highest value
is 61 ergs/cm2. Thus, at first glance, virtually any organic
coating should be considered.
However, greater hydrophobicity also implies lower water
solubility and a breakup of impinging water into small drops,
which gives trapped air bubbles at the interface of the ice/
coating and thus reduces adhesive strength even further (see
Reference 26). We certainly wish to minimize solubility and
to maximize bubbles. Consequently, relatively higher con-
tact angles are desirable, indicating that relatively lower
surface energy materials should be selected.
4.2 Problems in Property Identification
Properties of proposed coatings under specific conditions can
be determined. Of concern here is the fact that any given
property has both desirable and undesirable consequences.
A few such tradeoff problems are illustrated below.
Phase. Solid films are less likely to be removed by traffic
and are less likely to be slippery. On the other hand,
liquids cannot maintain hydrophilic sites and they also pro-
vide more uniform coverage.
Thickness. Relatively thick layers are required to provide
desirable flexibility and to block London forces. However,
they will be more costly and will promote skidding by smooth-
ing the highway macrostructure (see Reference 6 and Reference
62 in Appendix B).
Solubility. Water soluble coatings are much safer and cheaper
to apply, but unless they are very reactive with the highway
surface or tend to form polymers, they will not remain in
place. Solvent-soluble polymer coatings have the reverse
characteristics.
24
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Biodegradability. This is desirable if the material is re-
moved from the road surface, but it could result in rapid
deterioration of the material on the surface.
Highway Materials. As discussed in detail in Reference 54,
Appendix A, the diversity of highway surfaces, (e.g., con-
crete is porous and alkaline while asphalt surfaces are non-
porous and acidic or neutral), makes the existence of an all-
purpose coating appear unlikely. Further, the hydrocarbon
(and thus somewhat oleophilic) nature of asphalt indicates
the need for solvent application, in contrast to the proce-
dures possible for the easier-to-treat concrete roads. Un-
fortunately, the latter comprise only about six to seven
percent of the total miles of surface (verbal from the
Colorado Department of Highways).
Cost. An inexpensive material may require a very expensive
solvent for application. While such considerations are
properly a part of the Phase III application study, it would
be futile to even screen a material that requires a $20 per
kilogram ($9 per pound) solvent.
The above tradeoff problems complicate material selection and
make postulation of "ideal" coating properties virtually
impossible,
4.3 Gene r a1 Selection Cri t e r ia
In spite of the difficulties cited in Section 4.2 above,
selections for the screening tests had to be made. Since
this was a somewhat arbitrary area, all materials considered
are given in Table 3-2 to facilitate independent review.
Selection criteria were:
Fluidity. Any material existing and remaining in a fluid
state after application was rejected. Rapid removal by
traffic and skid promotion were believed to govern here.
Cost and Solubility. Any extremely expensive material or any
material requiring an expensive organic solvent was rejected
unless it was believed that valuable technical information,
possibly for future programs, might be gained.
Other Factors. High toxicity for either the as-received or
dried-film condition (judged from OSHA standards), vendor
recommendation, likely low surface energy and prior usage in
related applications were considered.
25
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Table 3-2
HYDROPHOBIC HIGHWAY MATERIALS
Class: Cationic Surface-Active Agents
MATERIAL
Trade Name
All quit
H-226
Allquat
264
Chealcal
39 High
Cone
Chemical
395 High
Cone
Cera nine
HCA gran-
ules
Cartare-
tln-F
Viscospln-
8
Ceranine
PKS '
Cartarex
FL
Chemfll
Car Gloss
Arosurf
TA-100
Softener
x"
Hlpoche*
Aquapruf"
Chealcal Name
Of me thy] D1
terป-
nonlum chlor-
ide
Olnsttiyl 01-
fatty ammon-
ium chloride
Fatty amide
Polyanlde
Anine
Poly-ethoxy
fatty inlda-
zoline
Blend of:
Honlonic
surface
Waxes
Cationic
fatty ni-
trogen
complex
Dimethyl-
ta!]^
arnnontun
chloride
Alykl-
Inldizollne
Derivative
Qua ternary
Hethol Anlde
Other
Cationic
"Compound"
Weakly
Cationic
Softener
Weakly
Cationic
Softener
Optical
Quencher
Chensheen"
Vendor/Contact
General Hills Chemical, Inc.
Minneapolis, Minnesota
(612) 540-2451
Al deMuerlsse. Marketing
General Mills, Chemical, Inc.
Hinneapol's, Minnesota
(612) 540-2461
Al deMuorlsse, Marketing
Sandoz Colon & Cheatfcals
Hanover, (few Jersey
(201) 386-7690
Haroon Brown t Tech. Service
Sandoz Colors & Chemicals
Hanover, ifew Jersey
(201) 386-7690
Harmon Brown, Tech. Service
Sandoz Colors & ChenlcaU
Hanover, Hew Jersey
(201) 386-7690
Hiroon Brown, Tech. Service
Sandoi Colors 8 Chenlcals
Hanover, New Jersey
(201) 386-f690
Harnon Brown, Tech. Service
Sandoz Colors & Chenlcals
Hanover. New Jersey
(201) 386-7690
Hiroon Brown, Tech. Service
Sandoi Colors & Chemicals
Hanover. lซw Jersey
(201) 386-7690
Harmon Brown. Tech. Service
Sandoi Colors & Chemicals
Hanover. Hew Jersey
(201) 386-7690
Harmon Brown, Tech. Service
Chenflt Corporation
Troy, Michigan
Ray Charles, Product Oevlpat
Onyx Chenlcal
Jersey City, New Jersey
Hlghpoint Chemical Corp
Hlghpolnt. North Carolina
;l;_Stevens
J. t. Stevens Coopany, Inc.
iarfteld, Kew Jersey
;20I) 772-7100
fete Drexler
FORK
Basic
Solid
Solid
Waxy
Solid
Solid
Solid
Liquid
Liquid
Solid
Liquid
Solid-
Liquid
Mixture
Aquipruf
As Purchased
Paste {7St
in solids
aqueous Iso-
proptnol )
Seal -fluid
(75X solids
in aqueous
Isopropanot)
Solid
White Collo-
dlal disper-
sion
Solid
Liquid
Liquid
Solid
Liquid
liquid
has not been p
Solubility Data
Soluble In al-
cohol, forms
HjO dispersion
Soluble In al-
COhol . Forms
Hฃ0 dispersion
Soluble In HgO
Forms H,0 dts-
perslonฃ
Soluble In
boiling Kฃ0
Soluble In Hฃ0
Soluble in H.O,
acid base z
Soluble in
boiling H2Q
H20 soluble
Hater soluble
oduced for severa
Application Hethods
Spray, Inversion
Spray, Immersion
Spray, Inuerslon
Inerston
Inversion
Inversion
Pad, exhaust, spray
Dip, spray
Spray
years
Surface Energy
No Information
Ho Information
Ko Information
Ho Information
No Information
Ko Information
35. 1 ergs/cnฃ
for O.H H,0
solution *
Ko information
NO Information
NO Information
Aval lability
Poor in mega*
kilo lots
at present
Poor In mega-
kilo lots
at present
Good
Good
Good
Good
Good
Good
Good
Good
Toxic Riling
Very low
Very low
Very low for
skin contact
No Informa-
tion
Very low for
skin contact
No Informa-
tion
No Informa-
tion (blode-
grades)
No Informa-
tion
No Informa-
tion
No Informa-
tion (blode-
grades)
LTV Stability
No informa-
tion
NO Informa-
tion
Ho Informa-
tion
No Informa-
tion
Ho informa-
tion
Ho Informa-
tion
Ho Informa-
tion
No Informa-
tion
Ho Informa-
tion
COST
Noted
44
26
121
ฃ6
146
50-56
134
120
396
ฃ00-300
BBRC Cements
use as antlstat
Implies water
absorption (not
good)
Currently used
to hydrophobe
car paint
Same as All -
quats and vis*
cospln 8
Unable to locate
vendor
Vendor Consents
Work has been done
at Texas ASH on soil
stabilization using
this material
factant for viscose;
has also been used
in asphalt to hy-
droohobe surface
Used to reduce flu-
orescence In paper
making
5/10/74! not
available
Test Decision
Test
Test if dif-
ferent than
K-226
Test
Test If dif-
ferent than
39
Reject only
weakly cationic
Test
Test:
Reject, weakly
cationic
Reject; stays
fluid
Test
Do not test
Reject; not
available
to
Cft
-------
Table 3-2 HYDROPHOBIC HIGHWAY MATERIALS (Continued)
Class: Organo-Silicones
Trade rune
Dow-Corning
92-009
1) Anti-
static
179
2) Wipe
3} Antl-
FOg
Caul I Ing
Compound
1684
Formula
125
SC-3700
2-6079
DC772
Drl-sll
73H-0
repellent
Glldalr
HI 903
MATERIAL
Chenlcal Kane
SMtcone
Silicon*
Rubber
Orgino
Slllcones
Z-4141
series
sllanes
Fatty tnilne,
Gtycol a\x
Sill cone
varnish
SIM cone
SIM cone
Rubber
Polyslloxine
base
Hethyl-
slllcone
Sllazane
Hexaiwthyl-
dtsllazane
Sodium nethyl
slllconate
C02 reactive
Sill cone H?0
reictlve
Slllcone
Otner
XI-8-3057
EC- 1931
DC 732
clear
Vendor/Contact
>w Corning
Midland, Michigan
(517) 636-895S
Daryl Dlckson, Ext. 8594
Oow Corning
Midland, Michigan
(517) 636-8955
Daryl Dlckson, Ext. 8594
Union Carbide
Technical Division
Tarry town, Hex York
J. A. Schofleld
Dow Corning
Midland, Michigan
(SI 7) 636-8955. Ext. 9484
Ward Collins. Tech Serv Div
Merlx Chemical Company
Chicago. Illinois
(312) 221-8242
Dave Sonneman
3M Cooyany
Minneapolis. Minnesota
(612) 733-9710/4619
John Norwood (Varnish Prod)
(referred to Fred Schwabe
Tech Elect Prod)
3H Company
Minneapolis, Minnesota
(612) 733-1110
L. Shaver (Coew. Chemicals)
Oow Corning
Midland. Michigan
(312) 671*3100
Transcontinental Research
and Development
Tucson. Arizona
(602) 194-346*
Tom Wallace
General Electric
Schenectady. New York
(518) 237-3330
Scott Hurley (technical)
General Electric
Schenectady. New York
(518) 237-3330
Scott Hurley (technical)
Oow Coming
Midland, Michigan
(517) 636-8594, 8597, 8374
Lou Arends
Mr. Kendenson
Dow Corning
Midland, Michigan
(SI 7} 636-8000
Ray Humphrey
Dow Corning
Midland. Michigan
(517) 636-8000
Ray Humphrey
XIH Products, Incorporated
Westhlake, Ohio
(216) 871-4737
Harold Wertnan
Basic
No long*
Solid
Solid
11 !r
21 a-
3) iq-
1d
Liquid
Solid
Liquid
Liquid
Solid
Solid
Sill-
cone
fluid
FORH
As Purchased
f available per
33S by weight
dispersion
All three
are liquids
Liquid In
solution
Solvent
solution
Liquid
chemical
Liquid
chenlcal
30 percent
solids In
liquid
dispersion
Solvent
solution
Sprayable
solution
Solubility Data
Daryl Oickenson
Soluble; VHP
naphtha
Not known by
Hard Collins
All three H,9
soluble 2
Soluble In VHP
Supplied as
water solution
Mineral spirits
Benzere, tolvene,
hexane, ?c/'
Benzene, tolvene
hexane, CC14
H20 dispersion
Mineral spirits
or stoddard sol-
vent
Application Methods
Spray, paint, etc.
Spray, paint, etc.
2) Wipe on
3} Mi pe on
Spray; dilute 44:1
Dilute fron 70S
concentration and
Spr-sy
Dilute and spray
Dilute and spray
Dilute to SS and
spray
Dilute and spray
Spray
Surface Energy
Not known
Not known
No information
No inf creation
No information
No Information
No information
No Information
No information
Availability
Good
Ko informa-
tion
Good
Good
Good
Good
Good
Good
Poor; sold
only In 16
ounce spray
cans
Toxic Rating
LOW
No 'Informa-
tion
lion
Low
Low
Low
Low
No informa-
tion
No informa-
tion
No Informa-
tion
UV Stability
Poor .
Claimed to
be high
No informa-
tion
tlon
No informa-
tion
No Informa-
tion
Ko Informa-
tion
No Infona-
tton
No Informa-
tion
No Informa-
tion
Ko Informs*
tlon
COST
Noted
1500 (331
dispersion)
No Informa-
tion
tlon
300 (for
concentrate)
43.85/Kg
(70X conccn-
Irate)
(22/Kg
(1001 con-
centrate)
*iooo (lorn
concentrate)
66-77
(301 concen-
trate)
500 (60X
concentrate)
EBRC Convents
lals; not useful
for hydro, road
coating
To be studied as
cheaper version
of 92-009
rustic solution.
lash Point 65*C
Vendor Comnents
U.C. has experimented
and cannot develop any
slllcone compound that
Is not slippery.
Z414I will make glass
hydrophoblc when ap-
plied; received no ad-
ditional information
froM Dickson
Not 3H product; suggest-
ed we contact prlrary
Suppliers of silicons
varnish (Dow Coming
and General Electric)
EC-1981 Is an experi-
mental stHcone com-
pound; It is not being
marketed at present
Has been lab tested by
Arizona H.D.; used In
new road nfx, building
foundations, and soil
stabilization; self
cures to solid
Sili cone varnishes
not recomcnded
Reactive with water and
raethanol
Humphrey has worked with
the Michigan H.D. on
various p rob lets; DC-722
will Into road surface
to depth of 2-4 en.
Reported used with
Sllanox 101 to hydro-
phobe sand. 400 (101)
T01 (73)
Vendor states material
is very slippery. Not
applicable.
Test Decision
Reject; not
available
Test
Reject
Reject; not
available
Reject; remains
water soluble
Reject
Reject; not
available
Test
Test
Reject; varnishes
require high
temperature cure
and are brittle
Test one of
these
Test
Test
Reject; renal ns
fluid
to
-------
Table 3-2 HYDROPHOBIC HIGHWAY MATERIALS (Continued)
Class: Rubber Base Coatings
MATERIAL
Trade Him
Rubber base
TT-P-85, IT
Proton 376
Arolon S85
Arc thane
190
Chemical Nwe
Silicons.
rubber
Silicon*
rubber
paints per Fed 5
P-110, and TT-P
Paint per
Fed Spec
TT-P-1150,
Type II
Saf flower
Alkyd resin
Modified
Saf flower
Alkyd
Ure thane
Other
pecs
IIS
Vendor/Contact
General Electric Construction
Sillcone Department
New York, New York
(51 8) 237-3330
Vic Jordan; referred to
Rich Gibbons
Pecora, Incorporated
Philadelphia, Pennsylvania
(215) 247-8342
Garland, Texas
(214) 278-8158
Marketing Division, refer-
red to Don King, Texas
Various
Goodyear Chealcals
Akron, Ohio
(216) 794-4400
Cave Bogrwr, Chcntst
Ashland Chemical
Kanses Ctty office
(816) ฃ21-7177
Jerry Perrlne
Ashland Chemical
Kansas City office
(816) 221-717/
Jerry Perrlne
Ashland Cheolcal
Kansas City office
(816) 221-7177
Jerry PerHne
FORM
Basic
See
com-
ments
See
com-
ments
Per Fed
Solid
Solid
Fluid
As Purchased
Specification
HjO solution
(JOS solids)
sTon (42X
solids)
Mineral
spirits (50*
solids)
Solubility Data
Per Federal
Specification
H20
Mineral spirits
Application Methods
Spray, paint
Spray, paint
Surface Energy
Unknown
Unknown
Unknown
Unknown
Availability
Can be formu-
lated by two
companies
Good
Good
Good
Toxic Rating
Low; meets EPA
solvent re-
quirements
Low
Low
Low
UV Stability
Good
Good
Good
Good
COST
-------
Table 3-2 HYDROPHOBIC HIGHWAY MATERIALS (Continued)
Class: Inorganic
Trade Name
101
HATERIA
Chemical Name
silica
Other
Cabot Corporation
125 High Street
Boston, Massachusetts 02110
Technical Center
{617} 663-3455
BUI Cfrelda
Basic
P'0.05
dry
powder
As Purchased
Dry powder or
powder/resin
system
Solubility Data
Insoluble
Application tethods
Plane spray or in
binder ,
0.03 lbs/1000 ft*
Surface Energy
Ho data yet;
like CH3
Aval lability
(by be Unit-
ed In mega*
kilo lots
Toxic Rating
Very low
UV Stability
Not known
COST
*/kg or as
Noted
700
BBRC Consents
Vendor Comments
Sllanox now mixed directly
Into concrete to Improve
H;0 resistance of new and
resurfaced roads.
Test Decision
Test
Other Materials
MATERIAL
Trade Name
Cartarex FL
UCAR Runway
Delcer
PCL-300
and PCL-
700
"0". "N"
"Ml"
Ethyl Sili-
cate cond.
E.S. E.S.
40
ISOLV
Xylan
1010
Xylan
2014 and
2052
DAP Caulk-
ing mter-
fals
Chemical Name
Glycol base
Polycapro-
lactone
Honoalumlnum
phosphate
(S,02/Na20)
silicates
Tetraeth/1
orthosllicate
Proprietary
fluid delcer
Phenylene
dlanine
Polys iloxane.
fluoroearbon,
polyester.
polyurethane
polyvinyl
fluoride
fluorinated
epoxles
Acrylo-atnlde
Conplex acryl
TFE
Hot known
Other
Crystal-
line
thermo-
plastic
resin
-anfde with
Not known
Vendor/Contact
Sandoi Colors * Chemicals
Hanover. New Jersey
(201) 386-7690
Harmon Brown
Union Carbide
Func. Chemical Department
New York, New York
(ฃ12) 551-5114
fi. Kennedy
Union Carbide
Func, Chenlcal Department
New York, New York
(212) 551-3287
Chicago (312) 822-7163
0. A. Schofleld
Stauffer Chemical Company
Industrial Chemical Division
New York, New York
(212) 421-5000
Jack Blua, Los AngeleS
Jack KcLaughlln, New York
Philadelphia Quartz Company
Valley Forge, Pennsylvania
(215) 637-3500
Jerry Bernstein
Union Carbide
Chicago, Illinois
(312) 822-7104
Cliff Schwahn
KalSf Agricultural Chenlcals
Savannah. Georgia
(912) 964-4311
f. E. Gorton
Naval Civil Engineering Lab
Port Hueneme, California
(805) 982-467g
Or, Alunfcaugh
Naval Civil Engineering Lab
Port Hueneme, California
(805) 982-4657
Dr. Peter Hearst
Kaval Research Lib
Washington, 0. C.
(202) 767-2S29
J. R. Griffith, Research
Hhltford Corporation
Hestchester, Pennsylvania
(215) 436.0600
Ton Sloan
UMtford Corporation
Vestchester, Pennsylvania
(215) 436-0600
Ton Sloan
DAP, Incorporated
Dayton. Ohio
(513) 253-7)51
Halt Abreth, Research Eng.
FORM
iasic
.Iquid
Liquid
Solid
Liquid
Liquid
Liquid
Fluid
and sol-
uble
compo-
nents
Solid
.1 quids
lolld
films
Solid
Solid
As Purchased
Liquid
Liquid
Solid: PCL300
f lakes; Pa
700 pelttts
Liquid
Liquid
Liquid
Fluid
Solid
Sane
Solvent
Suspension
Solvent
suspension
Solubility Data
Soluble In Hฃ0
Soluble In HjO,
ether, alcohols
Soluble In aro-
matic H.C. and
some chlorinated
solvents
Soluble In HjO
Soluble In Hฃ0
Soluble In water
Soluble In H20
Soluble In Hฃ0
See addendum to
reference 17
Dimethyl*
fomamlde
Dlnethyl*
formanlde
Application Methods
Immersion
Spray
Mix with other
Chemicals
Mix with other
chemicals
Spray
Spray; preheat to
ISO'F
ROOD temperature
cur*
Surface Energy
No information
No Information
No Information
No Information
No Information
No Information
No information
No Information
Should be
very low
Probably low
Availability
Good
Good
Good
Good
Good
Good
Not now avail-
able (5/10/74)
Good
Poor at
present
Good
Toxic Rating
No informa-
tion
No Informs-
tion
Slight
No Informa-
tion
No Informa-
tion
100 ppm per
OSHA for
ethyl silicate
Low and biode-
gradable
High
No Informa-
tion
No Informa-
tion
UV Stability
No Informa-
tion
No Informa-
tion
No Informa-
tion
No informa-
tion
No Informa-
tion
No informa-
tion
No informa-
tion
No informa-
tion
No Informa-
tion
COST
Noted
230
"100
=100
170
110
120
d,,3?.,,.
able)
1000
Very high
at pre-
sent
"2000
o2000
BBRC Contents
Used as a binder w/
ceramics and glass:
cures w/baslc con-
pounds
Not hydrophoblc
Contact Mr, Griffith
In March
Coatings quite
slick but not test-
ed against rubber
Old not seen at
all willing to sup-
ply samples
Vendor Coments
Used for the reduction of
fluorescence In paper-
making
Used as thin film. Not
Suitable for seal-pern.
coating. U.C. has not
pursued road coatings
because of need for
periodic application
Siodegrades
"D" colloidal control;
N* binder for cements,
leak sealer; "KIT fast
setting gel, cures with
acidic materials
Reacts with acid, ethanol,
water to form gel , then
H20 frosTilr to give silica
Hill advise E3RC If be-
comes available
rhirty-mlnute cure at
280*F required
Vendor cemented material
probably not suitable
without other binders
Feels that the basic paint
vehicle approach we're
taking is correct.
5/29/74.
Test
Decision
Reject;
remains
fluid
Reject;
remains
fluid
Reject;
like
nylons,
absorbs
Test
Test
Do not
test; too
toxic
Reject;
not avail-
able
Reject;
too hazard-
ous per
OSHA
Reject;
see text
Test
Reject;
high teirp
cure reqd
Test
Reject
to
to
-------
5.0 CONTACTS
This section presents the contacts made with vendors and
other outside experts in various fields and also briefly
describes the contact/materials work sheets included as
Table 3-2. This table is included primarily to illustrate
the number of contacts made and the selection procedure.
5.1 Vendor Contacts
The work sheets included as Table 3-2 illustrate the value of
these contacts. In many cases vendors made specific recommen-
dations and a few cited applications for cases similar to
the problem here. While the recommendations of a few vendors
were not taken (e.g., 3M's opinion that Scotchgard would not
work), vendor contact proved to be the most valuable source
of practical data found.
A few comments concerning materials listed on the work sheets
are included here:
The Onyx Corporation materials are the same as others
and the High Point Chemical material could not be
located.
In addition to materials suggested from the litera-
ture, other materials were included for at least
preliminary consideration. These included vendor-
suggeste.d materials, materials used by BBRC previously,
and consultant-suggested materials.
Note that the only fluids selected to be screened
were those which either solidify or could be expected
to strongly react with the highway surface.
Some materials have been used in highway mixes or
for soil stabilization although none have, to date,
been applied to roadway surfaces.
9 Rather than pushing products, some vendors (note
Entries 3, 10 and 15 on page 27) stated that some of
their products were not recommended. It must be
pointed out that 3M also did not feel their Scotchgard
material would work, even though we believed they
should be screened.
Note also that the plastic films on page 29 (ninth
entry, Other Materials) which were suggested by some
sources, either proved very high in ice adhesion or
similar compounds were screened in this study.
30
-------
In most cases, comments In the right-hand column in-
dicate the reason for rejection.
The detailed final list of materials selected for screening
is presented in Table 4-1 of Chapter 4. A summary list by
categories plus comments on mixtures and combinations of
materials is given in Section 6 of this chapter.
5.2 Other Contacts
Other major contacts are summarized in Table 3-3. The three
most important areas are discussed in somewhat more detail in
this section.
5.2.1 Hauser Laboratories
Mauser Laboratories was requested to summarize roadway materi-
als' properties and to present the state-of-the-art in high-
way marking paint. Their complete report is included as
Reference 54 in Appendix A. Some of the more important
aspects of this report have been given in Section 4.2 of this
chapter.
It is noted, from the Hauser report, that concrete roadways
present a much easier application and coating retention prob-
lem due to the void content of the concrete and its somewhat
greater roughness than asphalt. Good adhesion to asphalt
may necessitate the use of organic solvents which partially
attack the binder. This conclusion agrees with that ex-
pressed by the Colorado Department of Highways (Appendix B).
Note also the inclusion of the friction coefficient curves
used as a guideline for the screening friction tests. Finally,
note the typical paint application rate of 0.39 ฃ/m2 (equal
to 105 feet2 per gallon) to give reasonable life. The original
thought of using such paints as binders required re-evaluation
in view of this rather low and therefore costly coverage rate.
5.2.2 Colorado Department of Highways (CDH)
Ihe original contact report with CDH is given as Reference 62
in Appendix B. Of special interest are:
The availability of accident records with prevailing
weather conditions for most areas of the state.
The availability of full scale and portable road skid
test apparatus.
31
-------
Table 3-3
CONTACTS OTHER THAN VENDORS
Organization
Colorado Department of
Highways, Denver,
Colorado
Naval Research Laboratory,
Washington, D. C.
Deb ell and Richardson,
Enfield, Connecticut
NASA Lewis Research
Center, Cleveland, Ohio
U. S. Army Cold Regions
Research and Engineering
Laboratory, Hanover, New
Hampshire
National Oceanic and Atmos-
pheric Administration
(NOAA), Boulder, Colorado
Boulder Municipal Airport
National Center for Atmos-
pheric Research (NCAR) ,
Boulder, Colorado
Hauser Laboratories,
Boulder, Colorado
Personnel
B. B. Gerhardt
B. A. Brakey
J. R. Griffith
E. S. Childs
Vernon Gray
Technical Library
Receptionist
Receptionist
D. Baumhefner
Dr. Ray L. Hauser
Purpose/Results
Obtain traffic density map of test sites.
Obtain Colorado State Solvent Pollution rules.
Obtain data on in-situ friction testing of roads.
Obtain agreement for cooperation during road tests.
Contact Accident Data Center personnel.
Obtain roadway surface roughness data.
Obtain agreement to coat test samples with experimental
fluoroepoxy.
Try to obtain more data (specific compositions) on water-
borne coatings. No luck. Index only sent.
Check report (from ARAC survey) that NLRC made road
tests on hydrophobic materials during WW II. Report
incorrect.
Obtain copies of References 29, 30 and 31 from EPA
Report R2-72-125.
Inquire regarding local weather recording facilities.
No longer record such data.
Inquire regarding local weather recording facilities.
No data or instrumentation.
Inquire regarding local weather recording facilities.
NCAR records climatological data only when their needs
require .
Obtain report (Appendix A) on roadway materials '
properties and current highway prints.
oo
-------
Their opinion of normal coating coverage rates of
0.09 to 0.18 ฃ/m2 (0..02 to 0.04 gallons per square
yard) which are quite close to the coverage rate
cited in Reference 4.
The cited macrostrueture roughness (which controls
high speed skid resistance) of about 10~3m (40 mils)
arithmetic mean square (ams) implies that if rather
thick coatings are needed for wear life, they can be
used without covering the peaks (in agreement with
Reference 6).
Even the microstructure, controlling low speed skid
resistance per CDH, has a roughness of about one-
tenth of that above (Reference 6). This still permits
a lO'^m (4 mil) coating without covering the tire/road
contact asperities.
5.2.3 Weather Recording
As noted in Table 3-3, use of outside sources to obtain local
meteorological data during the road test phase was not possi-
ble. For budgetary reasons, sophisticated weather recording
equipment also could not be employed. Instead, as is dis-
cussed in Chapter 6, intermittent measurements were made of
air and road surface temperatures along with estimates of wind
speed, precipitation, etc.
6.0 PHASE II MATERIAL'S LIST
Listed in this section by chemical/physical class (see Section
1.2.1'of Chapter 2), are the 35 materials selected for
Phase II screening. By screening is meant any combination of
the tests used (see Chapter 4) to indicate promise of a
material or to eliminate one from further consideration. To
avoid duplication of much of the data presented in Chapter 4,
and in Table 3-2 of Section 4.3 above, only the class, materi-
al and vendor are given here. A few brief comments on
material combination philosophy are also given.
6.1 Materials
6.1.1 Cationic Surface Active Agents
Aliquat H-226 (General Mills)
Aliquat 264 (General Mills)
39 High Concentrate (Sandoz)
33
-------
39S High Concentrate (Sandoz)
9 Cartaretin-F (Sandoz)
Viscospin-B (Sandoz)
Chemsheen (Chemfil Corporation)
6.1.2 Fluorochemicals
Scotchgard FC-321 (3M)
Scotchgard FC-210 (3M)
0 Nyebar F (W. F. Nye, Incorporated)
Fluoroepoxy (NRL)
Xylan 2052 (Whitford Corporation)
6.1.3 Silicone Base
Frekote 33 (Frekote, Incorporated)
DC 92-009 (Dow-Corning)
Formula 125 (Transcon R$D)
DC 772 (Dow-Corning)
DRI-SIL 73 (Dow-Corning)
SS-4044 (General Electric)
DC 732 (Dow-Corning)
RTV-11 (General Electric)
G31, 2X (BBRC)
G31, Thin (BBRC)
6.1.4 Paints and Paint Base Binders
Federal Specification TT-P-115D (Goodyear)
Federal Specification TT-P-115D without Ti02 pig-
ment (Goodyear)
34
-------
Federal Specification TT-P-85D (Kwal Paint)
Arothane 190M50 (Ashland Chemical)
ซ Arolon 376 (Ashland Chemical)
Arolon 585 (Ashland Chemical)
6.1.5 Hydrophobic Silica
Silanox 101 (Cabot Corporation)
6.1.6 Other
Silicates "D", "N", "RO"; possible binders
(Philadelphia Quartz)
Monoaluminum Phosphate; possible binder
Z-6079; possible hydrophobe (Dow-Corning)
Petroset AT (Phillips Petroleum Company)
Note that the above listing includes some materials that were
not even suspected of being hydrophobic and more than twice
the number of items originally planned for screening. The
two BBRC formulations developed from other work were selec-
ted for only cursory screening.
6.2 Material Combination Philosophy
It was recognized that some very hydrophobic materials, as
judged from the literature, had other properties such as lack
of abrasion resistance (e.g., DC92-009 and DC732), or zero
cohesive strength (e.g., Silanox 101, a dry powder), which
required the use of binders. Thus, the emphasis on binders
was believed to be a necessary requirement in view of the
ultimate program goal --a successful ooating.
Also, it appeared unlikely that any single commercial material
could have all the needed characteristics (hydrophobicity,
impermeability to water, toughness, abrasion resistance,
adequate friction coefficient, etc.). From the start it seemed
evident that a composite formulation would be required.
35
-------
Chapter 4
PHASE II SCREENING TESTS
This chapter presents the data and observations for both pure
(single component) materials and formulated (multicomponent)
coatings acquired during the screening (basic property deter-
mination) tests.
As stated in the Intent of Report (see Recommendations and
Summary, Chapter 1), an attempt to present all'data obtained,
whether positive or negative, is the basic rationale here.
Organization of the data has proved to be a major problem.
This is due to both the amount of material to be presented
and, because of the receipt of test materials over an eight-
month period, an inability to run tests on all materials in
a sequential step-by-step fashion. Accordingly, the data
are organized by major category and chronologically within
each category. Observations, especially on degradation
phenomena, and computations are interjected as necessary.
Finally, the basic goal of a coating that is applicable to
roadway surfaces with standard spray equipment and which em-
ploys commercially-available material must be kept in mind.
The real-life target of this investigation strongly affected
the test methods employed.
1.0 INFRARED ANALYSIS AND OTHER MATERIAL CHARACTERISTICS
Infrared spectra were run on most materials using either a
Perkin-Elmer Model 700 or a Beckman Model 20AX spectrometer.
These data, were required for molecular identification and to
serve as a quality control guideline. All spectra were run
on the dried solids to remove possibly conflicting absorption
bands due to solvents or diluents. In some cases, the as-
received materials were also run to determine the solvents
employed. Spectra could not be obtained from the Silanox 101
(because of scatter from the sample), or from the fluoroepoxy
supplied by NRL (because of the substrate on which the sample
was supplied). The formulations of the two BBRC coatings as
well as those of all other formulated coatings are defined in
Chapter 5.
36
-------
These data are presented in Table 4-1. Also included in this
table are other material characteristics derived during the
Phase II work and not properly belonging in other major cate-
gories. The other solvents listed were determined by experi-
ment. The toxicity ratings were inferred from the chemical
natures of the materials and solvents, using OSHA recommenda-
tions. The as-supplied pH and non-volatile solid content
were determined by test at BBRC. The tack-free drying rate
was also determined experimentally at ambient temperature.
2.0 SURFACE ENERGY AND WETTING CHARACTERISTICS
The data, observations and some typical photographs accumu-
lated during this extensive effort are presented in this
section. The need for this basic data has been discussed in
Chapter 2.
2.1 General Approach
It was originally planned to use filter paper as an absorptive,
"rough" substrate for this work and some of the earlier data
were so obtained. However, it was found that even applica-
tions of the materials were quite difficult and contact angle
measurements nearly impossible due to the tendency of the
paper to curl. Therefore, most of the work was performed on
AISI 52100 steel polished to about a 10~7m rms (four micro-
inch) finish. As will be shown below, this also (a) permitted
evaluation of spraying techniques, (b) permitted easy evalua-
tion by visual observation of a material's tendency to self-
level and/or separate, (c) provided a hard substrate for quali-
tative hardness checks, and (d) provided a very sensitive
means of detecting water penetration of the film (since 52100
rusts quite easily).
In most cases, the materials and formulations (diluted to
sprayable consistency) were applied to the discs, ambient
temperature cured for two to four hours, checked for oil
and water contact angles, exposed to 100 percent relative
humidity (or soaked in water per the tabular data sheets)
and rechecked.
Approximately five microliter-sized drops of distilled water
and a highly purified hydrocarbon oil (Apiezon C) were applied
to the horizontal surfaces of the discs. Contact angles of
these materials were then measured using a Bausch and Lomb
stereo microscope with a Unitron Model PTV Goniometer eye-
piece .
37
-------
Table 4-1
INFRARED ANALYSES AND OTHER MATERIAL CHARACTERISTICS
Material
Aliquat H-226
Aliquat 264
39HC
395 HC
Cartaretin-F
Viscospin-B
Oiemsheen
Frekote 33
FC-321
FC-210 '
Nyebar F
DC92-009
Formula 125
Z-6079
DC772
Dri-Sil 73
TT-P-11SD,
Ty. it
Mod TT-P-11SD
(No Tl02)
TT-P-8SD
Silanox 101
Monoaluninum
Phosphate
Silicates
NRL Fluoro-
epoxy
Xylan 2052
SS-4044
DC732
KTV11
Aro thane
190MSO
Arolcn 376
Arolon 585
Petroset AT
G31, 2X
C31 Thin
Vendor or
Supplier
General Mills
General Mills
Sandoz Chela
Sandoz Oiem
Sandoz Chem
Sandoz Giein
Chemfil Corp
Frekote, Inc.
3M
3M
W. F. tire, Inc
Dow-Corning
Transcon RSD
Daw-Coming
Dow-Corning
DDw-Cornirfg
Good/ear Chem
Goodyear Chen
Kwal Paints
(Denver)
Cabot Corp
Stauffer Qiem
Philadelphia
Quartz
Naval Research
Laboratory
Khitford Corp
General Elec
Dow-Corning
General Elec
Ashland Chem
Ashland Chem
Ashland Chem
Phillips
Petroleum Co
BBRC
BBRC
Infrared Analysis
High Hoi. Wt. Linear
Hydrocarbon/Amide
Sana as H-226 with
Ketone groups
Aliphatic Amide with
organic acid salt
Sate as 39HC with
ether groups
Pure Polyamide
Similar to 39S
Aliphatic Amide/
Ether/Acid Salt nix
Hydroxyl Rich Sili-
cate/Silicone
Fluoroacrylate Ester
with Organic Acid
Salt
Fluoroacrylate/ Amide
with Sulfonate
Fluorocarbon/Ether/
Acrylate 5 Acid Salt
Polymethyl Silicone
Methyl Silicone and
Kydroxyl Rich Carbon-
ate
Hexamethyl Disilazane
Same as Formula 125
Reactive Methyl Sil.
5 Hydroxyl Rich Ale.
See Fed Spec , Spectra
on file
See Fed Spec Spectra
on file
Proprietary
Spectra not possible;
is a silanized silica
Spectra on file
Spectra on file
Spectra not possible
Fluoronated Benzyl
Acryl Amide
Dimethyl Silicone,
Adhesive type
Trifunctional, adhe-
sive type silicone
Polydimethyl Silicone
w/Pigment and Carbon-
ate
Alkyd Type Ester/Ure-
thane Copolymer
Modified Saf flower
Resin
Modified Saf flower
Resin
Styrene-Butadiene
Copolyner w/sulfon-
ated Hydrocarbon
Proprietary
Proprietary-
Solvent^) as
Supplied
Paste with
Isopropanol
Emulsion with
isopropanol
None
Solution with
water/alcohol
Water
Water
Water
P-Dioxane, Chlo-
ro thane
Chloro thane
Water Emilsion
Chloro thane
Naphtha
Hater
Pure Material
Water
Mineral Spirits
Mixture
Mixture
Mixture
None
Water
Water
Hone
DuDethylformamide
Freon TF
Ether/IBHttylene//
Ale. mix
None
None
Naphtha
Water Butyl Alco-
hol; Butoxy Eth-
anol
Water
Water
Emulsion
Freon TF
Freon TF
Other
Solvents
and/or
Diluents
Water
Alcohols
Water
Alcohols
Water
Alcohols
Water
Alcohols
Water
Alcohols
Xylene
Hexane
VHP Naphtha
TOP Naphtha
VHP Naphtha
Hexane
Hydrocar-
bons
Hexane, VHP
Naphtha
VHP Naphtha
VHP Naphtha
VMP Naphtha
No solvents,
will mix
VHP Naphtha
VHP Naphtha
Alcohols
VMP Naphtha
Alcohols
VMP Naphtha
Alcohols
VMP Naphtha
Alcohol
Toxicity
as
Supplied
Low
Low
Lew
Low
Low
Low
Low
Rather high
due to sol-
vent
Same as
Chloro thane
Low
Same as
Chlorothane
Low
Low but
bum hazard
due to pH
High
Low but
bum hazard
Low
Low
Low
High (long
term); 0.5*
percent leat
Low
Low but
acid hazard
Low
lev
High due to
solvent
Typical of
solvents
Low
Low
Low
Low
Low
Low
Low
Low
pH as
Supplied
8
8
8
6
8
8
9
Non-
Aqueous
Non-
Aqueous
7
Non-
Aqueous
Non-
Aqueous
12
Non-
Aqueous
12
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
2
10
Solid
film
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
Non-
Aqueous
7
7
7
7
7
Nonvolatile
Solids
Content
(kg/t)
Not measured
Not measured
Not treasured
Not neasured
0.38
Not measured
tot measured
0.006
0.30
0.39
0.030
0.28
0.66
Could not
measure
0.71
0.66
0.85
0.81
1.02
Dry powder
0.046
Not measured
Not measured
Received as
solid film
0.40
0.103
0.98
1.13
0.57
0.57
0.55
0.63
0.26
0.62
Drying Rate-
(Tack Free)
Days
Days
Solvent Evap
time
Solvent Evap
time
ป1 hour
Days
Days
10 Bin.
=30 Bin.
=1 hour
1 min.
'30 min.
=1 hour
=1 hour
Function of
Relative
Husidity
30 min max
per Fed Spec
30 min max
per Fed Spec
40 min max
per Fed Spec
Water Evap
Osx
Water Evap
tine
ป3 hours
10 min
10 min
ซlhour
30 Bin
2 hours
10 min
Days
=45 min
al.5 hours
Other Comments
Remains as a
waxy fila
Remains semi-
fluid
Remains semi-
fluid
Remains as a fluid/
solid mix
Evaporates too fast
to be useful
Complete cure re-
quires days
Requires catalyst
Requires catalyst
Requires catalyst *
38
-------
2.2
Numerical Data
The numerical contact angle data are presented in Tables 4-2
through 4-6. Table 4-2 compares data from the literature with
measurements at BBRC as a check on the technique used here.
The agreement is seen to be quite good where comparisons could
be made.
Table 4-2
CONTACT ANGLES OF WATER ON VARIOUS SUBSTRATES
Material
Stainless Steel Mirror
Teflon
Aluminum
Glass
Control Plate
(High Nickel Steel)
Plate A2
(High Nickel Steel)
Disk 64
(High Nickel Steel)
High Nickel Steel Disk
Literature Data
Contact
Angles
(Degrees)
11
97
68
34
Reference
43
44
44
44
BBRC Data
Contact
Angles
(Degrees)
11
29/30/28
37/38
37/37
36/38
42/40
Date
5/16/74
6/25/74
5/16/74
5/16/74
5/16/74
5/16/74
Table 4-3 is essentially a compilation of failed attempts to
utilize various materials having specific advantages, such as
low cost or low inherent pollution during application (e.g.,
water-based systems). The difficulty in curing these systems
at ambient temperature to a hydrophobic condition is evident.
Chemical compatibility problems are also evident.
Tables 4-4, 4-5 and 4-6 give the numerical contact angle data
for basic materials, binders and formulations under various
conditions. Note especially the poor results for most of the
cationic surface active agents. While a monolayer of one of
39
-------
Table 4-3
MATERIALS OR FORMULATIONS REJECTED FOR FURTHER CONSIDERATION
Material
39 HC liquid
RU Silicate
Scotchgard 210
Triton X 100 + 50/50 H20 Silicate
Silicate RU + Kferix
FC 431 + 50/50 H20 Silicate
DC772 + Silicate + Teepol
Dri-sil 73 + Silicate + Teepol
92-009 + Silicate + Teepol
DC772 + Formula 125
Cartaretin F4 + Silicate + Teepol
Frekote 33 + Silicate + Teepol
39S + Silicate + Teepol
Scotchgard 210 + Silicate + Teepol
Formula 125 + Silicate + Teepol
Dri-sil 73 + Silicate + Teepol
Z-6079 + Silicate t Teepol
39S + Silicate
Cartaretin F4 + Silicate
Frekote 33 + Silicate
Scotchgard 210 + Silicate
Formula 12S + Silicate
DC772 + Silicate
Dri-sil 73'+ Silicate
92-009 + Silicate
DC772 + 39S + Silicate
DC772 + Cartaretin F4 * Silicate
DC772 + Scotchgard 210 + Silicate
DC772 + Formula 125 + Silicate
Z-6079
Dri-sil + FC321
Dri-sil + 92-009
SWB42V2
Aro 585
Dri-sil + 92-009 + Catalyst
Dri-sil + Versamid 125 + Catalyst
TTP-115D + Dri-sil 73
TTP-115D + Viscospin B
Dri-sil + V12S
Dri-sil 73 + 92-009 V125 + Catalyst
Dri-sil 73 + 92-009 + V125
Dri-sil 73 + VMP + XI-2104
Petroset + Dri-sil 73
Petroset + Silicate RU
Petroset
Petroset + H20
Petroset + monoaluminum phosphate
Petroset + FC210
Formula 125
190M + VMP + FC321
ARO 376
DC772/F125; seven mixtures/wetting agents
Dri-sil + catalyst XI-2551
TT-P-85D + 92-009
TT-P-85D + DC732
Reason for Rejecting
Very corrosive to steel
Washes off in H20
Corrosion; poor wetting
Not miscible
0ฐ *
Not miscible
Washes off in H.,0
Not miscible
Not miscible
Washes off in H20
Reacts with silicate
Not miscible
0ฐ *
0ฐ *
0ฐ J
Not miscible
Not miscible
0ฐ *
Sets off silicate
Not miscible
0ฐ *
0ฐ J
Washes off
Not miscible
Not miscible
0ฐ J
Reacts
Reacts
Washes off
Too volatile
Reacts
Much too soft
Heavy corrosion of steel
Corrosion
Tacky
Sticky
Out, unless Dri-sil can be cured
Separated badly
Runny
Separated; runny
Sticky
Catalyst settled out
Not miscible
Sets off rubber
O'i
0ฐ.*
0ฐ J
0ฐ}:
0ฐJ
Stays tacky too long
Film destroyed by five hour soak in H20
ALL washed off by water
Did not cure
Reacts
Reacts
Date
5-1-74
5-1-74
5-1-74
S-2-74
5-2-74
5-2-74
5-2-74
5-2-74
5-2-74
5-2-74
5-2-74
S-2-74
5-2-74
5-2-74
5-2-74
5-2-74
5-2-74
5-3-74
S-3-74
5-3-74
5-3-74
5-3-74-
5-3-74
5-3-74
5-3-74
5-3-74
5-3-74
5-3-74
5-3-74
5-6-74
5-7-74
5-7-74
6-2-74
6-2-74
6-12-74
6-12-74
6-12-74
6-12-74
6-12-74
6-12-74
6-12-74
6-19-74
6-28-74
6-28-74
6-28-74
6-28-74
6-28-74
6-28-74
7-1-74
7-29-74
6-2-74
5-15-74
7-26-74
8-12-74
8-12-74
= Contact Angle
40
-------
Table 4-4
CONTACT ANGLES OF OIL AND WATER ON PROSPECTIVE MATERIALS
MATERIALS
Aliquat H22-C
Aliquat 264
39 HC
39S
Cartaretin F-4
Viscospin B
Frekote 33
FC-321
FC-210
Nyebar F
DC 92-009
Formula 125
Z -6079
DC 732
Dri-sil +
Silanox 101
RU-Silicate
G-31, 2X
G-31, Thin
Dri-sil +
92-009
Cartaretin F-8
DC 732
Xylan 2052
(24 -hour
air cure)
TEST FLUIDS
Oil
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
hater
X
X
X
X
X
X
X
X
X
,x
X
X
X
X
X
X
X
X
X
X
DATE
4-29-74 to
5-1-74
4-29-74 to
S-l-74
4-29-74 to
5-1-74
4-29-74 to
5-1-74
4-29-74 to
5-1-74
4-29-74 to
S-3-74
4-29-74 to
5-3-74
4-29-74
to
5-4-74
4-29-74 to
5-13-74
4-29-74 to
5-1-74
4-29-74 to
5-2-74
4-29-74 to
5-1-74
4-29-74 to
5-1-74
4-29-74 to
5-13-74
S-l-74 to
5-3-74
5-1-74 to
5-3-74
5-4-74
5-16-74
7-11-74
7-22-74
7-22-74
7-22-74
7-22-74
9-20-74
CONTACT ANGLES (DEGREES)
Substrate Materials
Paper
13,38,37
51,55
13,9
18,50
9,22
59,66
21,34
60,90
5,0
7,9
103,125
90,98
103,125
90,98
106,121
141,98
106,93
103,10!)
89,111
97,97
88,124
71,99
108,129
69,77
72,62
60,77
142,129
42,75
90
70
119
69
Steel
29,72
41
56,70 '
69
56
87,86,98
39
94,96,103,100,99
72
94,96,103,100,99
72
103,103,108,91,103,108,
89
81,107,99,55
86,79
100,99
81
103,96,103
62
95,93
49
7,6
45
105,109,117,107,119,100
43,47
100,97,113,93
73
98,103,102,95
72
78,87
94
95,98,94,90,93,93
100,99,101
108,108,109,111,111,110
105,105,105
105,104,103
69,79,63,59
OBSERVATIONS
Wet in all cases; data not usable for surface energy
Wet in all cases; data not usable for surface energy
Wet in all cases; data not usable for surface energy
Wet in all cases; data not usable for surface energy
Wet in all cases; data not usable for surface energy
(94ฐ, 96ฐ)*
Problems of even application
Thin film giving erratic results
Thicker films on steel look good
Uneven film evident
Too volatile
Uneven film on nonporous surfaces vary evident
Low energy but variable. (105ฐ, 109ฐ)*
No good until some way is found to accelerate cure
Complete cure doubtful. (93ฐ, 100ฐ1*
Complete cure doubtful. (95ฐ, 98ฐ)*
Need more data
Without isopropanol
Without isopropanol
Without isopropanol
With isopropanol, pour on
Five minutes exposure to water destroyed film
* After 24 hours at 100 per cent relative humidity, contact angle measurements of water on ice gave indicated values.
41
-------
Table 4-5
CONTACT ANGLES OF OIL AND WATER ON PROSPECTIVE BINDER MATERIALS
BINDER
MATERIALS
SWB 42V2
TT-P-115D
4044 Primer
Aro-190-
M-SO
Aro 376
Aro 585
Modified
TT-P-11SD
Petroset
Sodium Sili-
cate RU
Dri-Sil 73
TEST FLUIDS
Oil
X
X
X
X
X
X
X
X
X
X
X
Water
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DATE
5-31-74
5-31-74
5-31-74
6-2-74
6-2-74
5-31-74
6-2-74
6-2-74
5-31-74
6-2-74
S-31-74
6-2-74
7-22-74
7-22-74
7-22-74
4-29-74 to
5-1-74
4-29-74 to
S-2-74
CONTACT ANGLES (DEGREES)
Substrate Materials
Paper
0,0,48
10,19,41
84,114
56,61
Steel
25,20
10,16
87,86
10,11
92,91
51,49
90,90
86,85
83,89
14,12
90,87
29,19
80,81
15,16
82,82
75,73
15,17
62,65
100,87,80
82,84,83,82,83,84
88,90,90,92,89,89
16
95,88,85
35
OBSERVATIONS
After 24 hr 1001 RH
After five hrs underwater
After 24 hrs 100% RH
After five hrs underwater
After 24 hrs 1001 RH
After 24 hrs 1001 RH
Poured on
Sprayed on
Five discs with different concentrations. None indi-
cated any degree of tLO repellency
Soaked into paper
to
-------
Table 4-6
CONTACT ANGLES OF OIL AND WATER
ON PROTECTIVE COATING FORMULATIONS
COATING FORMULATIONS,
Manoalimnuro Phosphate + F 125
Sodiun Silicate, H20, Teepol
+ Scotchgard FC210
+ 39S liquid
+ F 125
+ Iferix
+ DC772
* 92-009
Sodiun Silicate, HjO
* 39S
+ Scotchgard
ป F 125
+ DC 772
DC 772 + 39S
+ F 125
Dri-Sil 73 + 92-009
Dri-Sil t Silanox Ml
Dri-Sil 73 + RTV 11
Dri-Sil 73 + KTV11 + Therm 12
* V-125 CVersamid-125)
* Viscospin B
Dr'i-Sil 73 + RTV11 * Cat +
Viscospin fi
Dri-Sil 73 + RTV11 + Cat +
V-125
Dri-Sil 73 * 92-009
Dri-Sil 73 + V-125
Dri-Sil 73 + 92-009 + V-125
Dri-Sil 73 + Catalyst
Dri-Sil 73 + 92-009 + Catalyst
Dri-Sil 73 + V-125 * Catalyst
Dri-Sil 73 * VMP * DC732 +
Isopropanol
Dri-Sil 73 + 92-009 * V-125 *
Catalyst
TEST FLUIDS.
Oil
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Water
X
X
X
X
X
X
X
X
x'
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DATE"
S-2-74
S-2-74
S-2-74
5-2-74
5-3-74
5-3-74
5-3-74
5-3-74
5-3-74
5-3-74
S-2-74
5-2-74
S-2-74
S-6-74 to
5-13-74
5-20-74
5-20-74
5-22-74
S-22-74
5-22-74
5-22-74
S-22-74
5-22-74
5-22-74
5-24-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-12-74
6-13-74
6-12-74
6-13-74
7-22-74
6-12-74
6-13-74
CONTACT ANGLES (DEGREES)
Substrate Materials
Paper'
Steel
37
19,19
0,7
0
0
0
6
0
0
0
60
0
26
78,87
100,129,117
47
100,100,99,98
63,63,65
101,99,100
68,68
98,98,98,101,101
98,99,98,99
60,61,56,57
98,106
97,97
106,103,102
105,105,107
63,62,75,85,79,66
98,106,106
99,99,98
46,42,48
96,98,99
71,73,50,66
100,93,8
44,36
82,63,78
38,50,44
91,83,89
63,56
103,110,98
73,90,61
99,90,99
74,60
85,91,85
40,41,41
85,89,90
68,68,73
104,109,97
60,54
66,78,88
36,41,38
86,86,95
55,49
104,103,103
108,98,100
60,62,80
100,101,103
56,63
OBSERVATIONS
H20 completely dissolved coating
Washes off in seconds
Sticky; put in 100$ BH to cure. Contact
angles measured after cure.
Cured 2 hrs 6 100 C
Cured 2 hrs ซ 100 C
Room temperature cure
Room tenperature cure
Very Slow Curing
Very Slow Curing
V-125 not completely dissolved
)After overnight 1^0 soak
}Still runny
}After overnight HjO Soak
)After overnight It-O soak
}After overnight IkO soak
}After overnight li^O soak
}After overnight H^O soak
43
-------
Table 4-6
CONTACT ANGLES OF OIL AND WATER
ON PROTECTIVE COATING FORMULATIONS (Continued)
COATING FORMULATIONS
Dri-Sil 73 + V-125 * Catalyst
FC321 + 4044
TT-P-115D + Dri-Sil 73
TT-P-115D + 92-009
50/50 Xylene
TT-P-11SD + Viscospin- B
TT-P-115D t 92-009
TT-P-115D + 4044
TT-P-115D + Frekote (Straight)
TT-P-115D + DC732
Cartaretin F4 * F-125
Cartaretin F4 + F-12S
+ Cellosolve acetate
Cartaretin F4 + DC732
Cartaretin F4 + DC732 +
Cellosolve acetate
Cartaretin F4 + F-125 +
Isopropanol
Cartaretin F4 * DC732 + Isopro-
panol
Cartaretin F4 + F-125 + Isopro-
panol
190MSO + Dri-Sil 73
190^EO * 92-009
190M50 + 4044
190MSO * Frekote (straight)
Cartaretin F4 * ARO 376
Modified TT-P-llSD + 4044
TLST FLUIDS
Oil
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Water
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DATE
6-12-74
6-13-74
5-5-74 to
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
7-22-74
6-12-74
6-13-74
7-22-74
5-14-74
5-14-74
5-14-74
5-14-74
5-14-74
5-14-74
5-16-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
6-12-74
6-13-74
7-22-74
7-22-74
CONTACT ANGlkS (UtGRRS)
Substrate Materials
Paper
Steel
66,78,88
36,41,38
86,86,95
55,49
108,91,113
107,97,93
34,40,38
74,102,93
34,35
91,100,102
62,43,64
113,111,113
33,37
11,17,18
55,50,20
21,20,23
24,27
110,107,110
74,85-,83
108,108,105
55,61
90,90,93
45,47,40
84,88,91
39,43
105,103,103,115,113,
113
105,104,104
90,90,87
44,38,40
96,85,97
30,31
119,119,116,115,115,
114,119
119,117,115
87,87
89,86
0
0
97,90
0
94
93,97,95
48,42,43
96,97,90
40,36
100,103,102
76,68,60
98,110,95
50,36,36
93,95,92
49,50,49
83,80,85
36,25
94,92,91
59,57,50
93,92,95
45,44
93,91,90
111,107,107,109,111,
110
106,105,104
OBSERVATIONS
JAfter overnight H20 soak
lAfter overnight H20 soak
After overnight H^O soak
lAfter overnight H20 soak
JAfter overnight H20 soak
)After overnight H-O soak
lAfter overnight H,0 soak
Washes off in one minute
}After overnight H,0 soak
)After overnight H20 soak
)After overnight H,0 soak
}After overnight H20 soak
No data
44
-------
these materials might exhibit hydrophobicity due to molecular
orientation (see Chapter 2, Section 1.2.1), a layer of finite
thickness (required to exhibit any wear life whatever), is
definitely hydrophilic. Note that contact angle data employed
to detect changes during a given screening test are given in
later portions of this chapter.
Finally, it was mentioned in Chapter 2, Section 3, that con-
trary to theory, contact angle data could not be used to
estimate solid dispersion energy. Using the data for
DC92-009* on steel, where the water contact angle was about
100 degrees and the oil contact angle was 62 degrees, we com-
pute from Chapter 2, Section 3, formulas 7 and 8:
Yd =40 ergs/cm2
2
Yf = 19 ergs/cm2
oil
These should be the same. Whether impurities in the film (we
must deal with commercial products) are responsible is not
known. More likely, the "maximum contact angle" phenomenon
discussed in Chapter 9 of Reference 3 is responsible. After
this discovery, the water contact angle alone was used to rank
coating hydrophobicity.
2.3 Photos
Figures 4-1, 4-2, 4-3 and 4-4 illustrate some of the above
discussion.
Figure 4-1 shows:
4-la: Five formulations of Petroset AT on discs (straight,
50/50 diluted with water, 30/70 diluted with
water, 30/70 diluted with water plus monoaluminum
phosphate and with FC-210). Note differences in
appearance.
4-lb: The test setup for measuring contact angles.
* This material, like many other silicones, does not depend
on surface active "ends" to orient on a surface and become
hydrophobic. Rather, the molecule is surrounded by -CH3
groups and is thus inherently hydrophobic.
45
-------
(a)
(b)
Figure 4-1 Steel Test Discs and Contact-Angle-Measurement
Apparatus
46
-------
Figure 4-2 shows:
4-2a: A water droplet on untreated stainless steel (14X) .
4-2b: A water droplet on Frekote 33 with the goniometer
scale visible (16X).
4-2c: A water droplet on modified TT-P-115D paint (14X).
Figure 4-3 shows:
4-3a: A water droplet on DC92-009 (14X). Note the
refraction. The angle really is greater than 90
degrees.
4-3b: Water droplets on DC92-009 (7X) as used for tripli-
cate measurements.
4-3c: A water droplet on Petroset AT (14X).
Figure 4-4 shows:
4-4a: Badly degraded Cartaretin F-4 after the first
freeze/thaw cycle during ice adhesion testing.
4-4b: A typical array of binders (SWB 42V2, TT-P-115D,
Arothane 190M50, Arolon 376, Arolon 585 and SS 4044)
after high humidity exposure. Note rusting indica-
tive of water vapor penetration.
4-4c: A typical array of materials after water soaking.
Note corrosion, peeling and bubbling indicative of
low hydrophobicity.
4-4d: A group for plates coated for the first series
of ice adhesion tests.
2.4 Conclusion
Space does not permit discussion of the mass- of data pre-
sented above. It is sufficient to state that the data are avail-
able for detailed examination, that water (and oil) contact
angle measurements permitted rapid screening of a very large
number of materials and formulations and that the steel discs
proved to be a valuable indicator of coating water resistance.
47
-------
(a)
(b)
(c)
Figure 4-2 Water Droplets on Various Materials for Contact
Angle Measurements
48
-------
(a)
(b)
(c)
Figure 4-3 Water Droplets on Various Materials for Contact
Angle Measurements
49
-------
Ul
O
WASHED 1/2 OF I DEGRADED"F-4
JPLATE-NO RUST I
(a)
V
AFTER WATER SOAK 1
(c)
(b)
IPllll
PC'.
^^^^^j^jjl
(d)
Figure 4-4 Test Discs and Plates Used for Evaluation of Various Materials-
-------
3.0 COMMENTS ON OTHER TESTS
Following the tests and observations described above, the
following decisions were made:
Since sufficient data (solids content, preferable
solvents for application and the results of various
spray techniques) were now available to compute the
solid film to be expected from a given quantity of
formula, all subsequent tests were performed on.sprayed
films having a thickness of about lO'^m (0.004-inch).
From Chapter 3, Section 5.2.2, this is about the maxi-
mum thickness that could be employed without the
danger of decreasing lowspeed highway friction co-
efficients .
Many of the materials were discarded from further
consideration. This included most of the cationic
surface active agents, most of the water-based
materials arid some of the fluorochemicals.
4.0 ICE ADHESION SCREENING TESTS
The four series of laboratory ice adhesion screening tests are
described in this section. The data are from References 55,
56, 57 and 58 included in their entirety in Appendix A. These
basic property data were required to rank the various materials
and combinations for suitability as ice release agents and
for cohesive strength during release.
4.1 Test Procedure
For series 1 and 2, the coatings were applied as specified
in 3.0 above to steel plates (5 cm by 10 cm by 0.63 cm)
having an rms surface roughness of about 1.3 by 10~6m (50
microinch). For these two series, the plates were subjected
to four hours at 100 percent relative humidity and the water
contact angles were checked before testing. In series 3,
asphalt and concrete cores were tested to obtain reference
values. In series 4, a few formulations were sprayed on cores
and tested.
In all cases, the procedure was the same as is completely
specified in Reference 55 (Appendix A). The high shear rate
used (0.5 cm/sec) was selected as being more representative
of highway speed than lower rates. However, such high rates
give maximum values of adhesion (Reference 31) and thus may
51
-------
be pessimistic. The test temperature of -12 C was selec-
ted to avoid the hypothesized "liquid-like" interface
(Reference 26) between -10 C and 0 C.
4.2 Numerical Data
The numerical data are summarized in Table 4-7. The indivi-
dual release values (three trials of two releases per trial)
are given in the second column. Actual coating thicknesses
are listed in the third column. For rapid comparison, the
average shear strength and the range are given in the fourth
and fifth columns. Contact angle data are given in the next
three columns and the last two report qualitative observations.
In series one and two, most coatings gave some reduction in
adhesion but few were outstanding.
In series three, cores were taken from Highway 36 (see
Chapter 6 for locations of sites) .
In series four, a few coatings were sprayed on cores and
tested. The results were surprising and somewhat contradic-
tory to series one and two. This emphasizes the recommendation
that coating optimization should use only core samples as
substrates. Further laboratory tests on such cores were not
possible due to scheduling (series four was run in mid-
October) and budget constraints.
4.3 Photos
Figure 4-5 shows:
4-5a.ง The series four core samples before and after
4-5b: adhesion testing. Note that the TT-P-115D/DC 732
(center of each photo) was obviously sprayed on
too heavily (compare with'Figure 4-lld in
Section 6 of this chapter) thus accounting for
its poor performance.
4-5c: Ice adhesion cold cabinet/pull apparatus at
Hauser Laboratories.
4-5d: Close-up of the Teflon ring ice holder/sample
plate configuration.
4.4 Conclusion
Ice adhesion testing revealed very wide differences between
shear forces for the various coa-tings . Testing on steel
52
-------
Table 4-7
ICE ADHESION SCREENING TEST RESULTS
MATERIAL
Nsne (STEEL PLATE)
CARTARETIN F-4
DRI-SIL 73/RIV 11
FC- 321
DRI-SIL m SILANOX 101
WESARF
NRL COATING
FREXOTE 33
FC210 HITHDUT FC-43
C31 - 2X
DC 92-005
ER1 - S!L 73
FC2IO WITH FC 43
DRI - S1L 73/92009
G 31 - THIN
ADHESICH STRENGTH
kg/a?
7. 24/S , K/7 .03/8, 1S/7.4S/6 .15
FILM
THICKNESS
FIEST TEST SB
AVERAGE STOJKTH
fc^CO
X
IIES [MAUSER REPOR
7.28
RWGE
W
R
74-225)
2.53
COATING REMOVED BY FIRST FREEZE/THMf CYCLE
6 . 68/6 . 96/8 . 93/7 . 03/7 . 31/4 . 78
4.50/3.94/2.39/2.88/2.81/2.67
17.9/12.8/14.8/24.6/7.10/7.59
4. IS/6. 75/3.87/4.57/4. 1S/3.87
7. 31/S.62/2. 32/4.57/5.20/6.26
6.68/S.06/3.5I/4.43/5. 34/3.37
4.99/7. 31/5.13/6.26/4. 29/3.6S
3.51/2.46/2.88/2.81/2.04/1.26
1.55/1.55/1.05/1.26/0.91/0.93
9 .28/ 7T 24/9 .35/8 .58/5 . 27/S . 20
6.1S/4.08/4.43/2.81/4.64/6.26
13.0/11.5/7.73/5.83/7,52/7.87
5 .SS/4 . 36/3. S2/3 . 37/3 . 73/3 . 02
0.0025
0.005
0.010
0.0007S
0.010
0.0002S
0.010
0.010
0.0037
0.0025
0.0005
0.010
0.0025
6.94
3.20
14.1
4. 55
5.21
4.81
5.27
2.49
1.22
7.49
4.73
8.91
3.92
4.15
2.11
17. S
2.88
4.99
3.16
3.65
2.2S
0.63
4.15
3.44
7.17
2. S3
SEOCND TEST SERIES (MAUSER REPORT 74-319)
WINE (STEEL PLATE)
TT-P-11SD, TYPE II
TT-P-11SD/DC 732
TT-P-11SIV4044
TT-P-U5B/K92 - 009
TT-P-115B/FC - 321
M3DIFIED TT-P-1150D TY II
MM1 TTP-11SIVIC 732
HDD. TT-P-11SD/4044
TT-P-llSD/nOOTB 33
TT-P-8SD
TT-P-8SD/4044
EC 732
190MSO
ISOMO/FKEHnE 33
190MSO/4044
OCW. C
4.69/8.51/6.45/8.16/9.27/8.44
7.17/7.94/5.S1/4. 19/8. 15/8. 29
5.22/8.65/14.9/13.2/3.30/3.80
S.93/4 .58/9. 56/10.1/9. UO/S. 94
4.62/4,52/7.87/5.83/6.16/4.94
4.12/3.42/7.46/4.13/7.31/6.92
9.28/6.19/8.08/7.87/11.7/12.0
1,02/0.87/2.45/4.19/1.11/2.90
6.82/8.93/11.2/10.1/10.9/13.0
6.21/6.89/8.22/7.31/7.10/7.52
3.S2/3.76/6.87/9.07/10.E/9.77
7.17/5.80/9.77/7.73/9.28/9.07
0.86/0.18/0.82/0.91/0.89/0.73
4.84/J.6S/4.S1/8.01/4.1S/8.22
4.15/3.97/7.24/4.87/8.01/7.24
4. 44/5. 71/3.99/6. 57/4. 15/4. 76
3.39/S.37/6.03/6.0S/7.66/6.62
0.018
0.010
0.010
0.012
0.025
0.0075
0.016
0.0075
0.010
0.010
0.0075
TACKY- NDT
&ASURED
0.005
O.OOZ5
0.0075
0.0005
7.S8
6.88
8.69
7.52
5.66
5.49
9.19
2.09
10.2
7.21
7.26
8.08
0.73
5.56
5.91
4.94
5.8S
4.59
4.11
11.7
5.54
3.35
4.04
S.83
J.32
6.19
2.01
6.25
3.48
0.73
4.58
3.27
2.58
4. 27
CCHTACT AH3LES - DEGREES
AS APPLIED
IH20/OIL)
REF. 55)
5(1/45
80/40
99/
113/37
117/47
103/76
90/40
97/78
9S/
98/60
94/70
97/33
81/79
SB/41
92/72
tef. 56)
56,65,63
86,86,92
106.108,105
96,106,106
102,106,106
118,118,118
75,83,65
119,117,120
104,110,106
93.100,95
100,100,99
104,106,110
101,102,103
78,86,86
76,80,73
91,82,86
99,99,104
AFTER 4 KR.
11001 R.H.
(H20)
83
105
103
97
es
97
93
97
91
SO
S3
92
AFTER
ADKESICN
TEST (H20)
95,93,92
103,110,111
117,117,116
98,93,101
52,88,87
106,105,106
38,101,102
95,93,99
104,100,96
104,93,92
91,75,83
101,101,101
103,95,99
*81,83,8S
*77,86,8S
*114,120.109
105,105,102
107,105,105
109,111,104
78,70,77
111,112,112
104,102,104
'108ป110,104
97,95,99
103,106,107
109,105,106
86.83,84
77,86,86
93,89,90
98,101,101
THIRD TEST SERIES (K4USER REPORT 74-343) (REF. 57)
Referent Data
CONCRETE:
ASPHALTIC PAVEMENT:
12.95
13.45
3.48
5.09
FOURTH TEST SERIES (HAUSER REPORT 74-38
H3D. TT-P-11SD/DC 732
CN ASPHALT:
CN CONCRETE:
PETRDSET AT
CM ASPHALT:
CM CONCRETE:
tRI-SIL 73/DC 732
ON ASPHALT:
G 31 - THIN
CN ASPHALT:
7.4/9. 3/9. S/10. 7/11. 0/9. 5
8.0/6. 2/5 .3/5.9/13.0/7.4
13.3/8.8/9.1/11.2/10.4/10.7
9.5/10.2/9.1/7.4/14.3/10.0
4. 8/4. S/4. 7/3.4/6.3/7.4
10. 3/8.5/5. 6/10. 3/8. 5/9.4
NOTKTOM
BUT THICK
WT ROW
Birr THICK
NOBUL
N3HKL
tiOfWL
JCKttL
9.6
7.6
10.6
10.1
5.2
8.8
3.6
7.7
4.5
6.9
4.0
4.7
) (REF. SB)
cmiiNC
ROCVAL
BY ICE
COMPLETE
IN SPOTS
JJ] L
901 COMPLETE
ML
NIL
NIL
NIL BUTKARKhD
NIL
NIL
5t RDWED
NIL BUT MARKED
NIL BUT iURKED
NIL
NIL
SOt REMOVAL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
NIL
CCATire OONDITICN
AFTER AIHES ION
TEST
SOFT, POORATKESICN
HARil, GOOD ADHESION
BRITTLE,
POOR ATKESICN
TOUCH, COCO AEIIES10N
COATING UWWKED
HARD,
EXCELLENT ADHLS10N
HARD,
0000 AEHLSIGN
TCOQi, CCOD
AHESIGH, SLIPPERY
TOXH.tiOOD ADHESION
HARD, GOOD AJlltSlCU
TOUH,
POK AIMLSim
SOFT, POCR AOIE5KN
TOUCH, GOOD
AHESICH, SLIKtRY
TOIXH
SOFT A.1ฎ FLAKY
TOU3I
SOFT
VXRY TOUH
TOUCH
SLIGHTLY SOFT
SLIQITLV SOFT
VERYTOUJI
VERY TOUCH
TCUH
WCKY
TOUCH
TOUH
VERY TOUCH
SOFT, SLIPPERY
201
20t
NIL
MIL
NIL
NIL
Wetting by Hฃ0 During,Measurซซnt
53
-------
Ol
(c)
(d)
Figure 4-5 Ice Adhesion Core Samples and Test Apparatus
-------
substrates gave wider differences between the coatings and
may thus be more representative of the coatings themselves.
However, from limited tests on asphalt and concrete surfaces,
ttae use of a steel (or any nonporous) substrate appears to
give optimistic values in this application.
Coatings with the worst (highest adhesion) performance (like
Cartaretin F-4 and Silanox 101) have also been shown to be
oleophilic and a serious threat to asphaltic surfaces (see
Section 6 below).
Finally, in agreement with Reference 2, no strong correlation
was found between ice adhesion and water contact angle.
5.0 HIGHWAY WEAR TESTS
The results of the highway surface wear tests are presented
in this section. These data were required to estimate the
coatings' wear lives as required by the basic contract's
cost/effectiveness goal of a once-per-season application.
5.1 Procedure
Highway wear tests were performed on the most promising formu-
lations at this point in time to obtain realistic traffic life
estimates. The location of the tests, the strip pattern
and configuration and spacing, are defined in Appendix C,
Figures C-2 and C-3.
It should be noted that air-type spray techniques were used
in applying the stripes. This is known to give poorer ad-
hesion and penetration than the airless spray technique finally
adapted for the full scale highway tests (see Chapter 6).
5.2 Data and Results
All data are presented in Table 4-8 for the first 35-day ob-
servation period.
Note that:
Wear was moderate (20 - 30 percent wear).
From skid values, all coatings were still effectively
present after 200,000 vehicle passes.
Both Arothane formulations exhibited unsatisfactory
(low) skid values.
TT-P-115D/DC 732 held up well on concrete.
55
-------
Table 4-8
HIGHWAY WEAR TESTS - CITY OF BOULDER
MATERIAL
TT-P-11SD, TY.II
TT-P-11SD/4044
TT-P-115D/92-009
MODIFIED TT-P/FC - 321
MODIFIED TT-P/DC 732
MODIFIED TT-P/92-009
MODIFIED TT-P/4044
AROTHANE 190MSO/4044
AROTHANE ISOMSO/FKEKOTIE
PETROSETAT
HDD. TT-P/4044
MOO. TT-P/DC 732
AROTHANE 190MSO/4044
PETROSET AT
SUBSTRATE
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
ASPHALT
CONCRETE
CtWCREIE
CONCRETE
CONCRETE
APPLICATION
APPLICATION/
OBSERVATIONS
1. ALL MATERIALS EASILY
SPRAYED KITH SLIGHT
PLUGGING OF DC732
MIXES.
2. ASPHALT VERY COM-
PACTED SO PENETRA-
TION NOT GOOD.
3. CONCRETE VERY
WEATHERED.
4. PETROSET AT PENE-
TRATION SLOW.
INSPECTION DATA
SKID VALUES
ASTM ฃ303
60/59/59/59
54/55/54/55
59/S8/58/S9
62/61/60/60
68/68/66/68
60/62/60/61
62/61/62/62
45/45/43/43
40/40/38/38
57/S7/S3/56
TOO
RfflKH
TO
MEASURE
WETTING*
OBSERVATIONS
(Kith HjO)
SOME
BEADING
SOME
BEADING
SONE
BEADING
SOME
BEADING
sac
BEADING
NO OBVIOUS
BEADING
SOM5
BEADING
SOME
BEADING
NO OBVIOUS
BEADING
NO OBVIOUS
BEADING
BEADING
NOT OBVIOUS
GOOD BEADING
BEADING
NOT OBOTniK
BEADING
NOT OBVIOUS
WEAR
ESTIMATES
(Vol. t)
30
20
30
30
30
30
20
20
20
20 (?)-
10
5
20
20 (?)-
PENETRATION MADE HEAR
ESTIMATE DIFFICULT
PENETRATION MADE WEAR
ESTIMATE DIFFICULT
STRIPE
NUMBER
(SEE PHOTOS)
Al
A2
A3
A4
A5
A6
A7
A8
A9
A10
a
C2
C3
C4
CONCLUDE
FROM SKID DATA AND
VISUAL OBSERVATION,
ALL COATINGS ARE
STILL EFFECTIVELY
PRESENT. NO DEGRA-
DATION HERE FOR
MATERIALS SHOmNG
ASPHALT DEGRADATION
IN FRICTION TESTS.
LOCATION: ARAPAHOE BETWEEN FOLSCM AND 28th STREETS
OUTSIDE, EAST BOUND LANE AND (FOR CONCRETE) PARKING LOT ENTRANCE
DATE: 8/1/74
AREA: 10cm WIDE STRIPES ACROSS LAKE AND ACROSS ENTRANCE PAD
RATE: TO GIVE 0.010 CM THICK FIIM
METHOD: "JET-PACK", SPRAY CANS, SURFACE NOT SWEPT Ojl CLEANED
TEMPERATURES: ASPHALT 33C / CONCRETE 28C
INTERIM PERIOD
EST. RAIN FAIL: ISon
TEMPERATURES: MOSTLY 27C*
TRAFFIC: ASPHALT: 204000 VEHICLE
CONCRETE : 20000 VEHICLE
PASSES
PASSES
INSPECTION
DATE: 9/4/74 REFERENCE
TEMPERATURE OF ASPHALT: 20C SKID VALUES
65/65/66/64
WETTING (BEADING) OBSERVATIONS PROBABLY PESSIMISTIC DUE TO
ACCUMULATED DIRT ON THESE REAL SURFACES
56
-------
5.3 Photos
Figure 4-6 shows four photos during strip application on
8/1/74, 4-6a, 4-6b for the asphalt and 4-6c and 4-6d on the
concrete entrance slab.
Figure 4-7 shows the asphalt stripes at the end of 35 days.
Note the .non-wetting following skid testing (rectangular areas)
in stripes A8, A9 and A10.
Figure '4-8 shows the asphalt stripes following an additional
40-day period. The paint formulation stripes are still about
50 percent present.
5.4 Conclusion
Long-term wear was least for the paint formulations. While
the wear rate was somewhat higher than hoped, the results were
encouraging in view of the non-optimum application technique
and the type of traffic flow (considerable stop-start move-
ment) at this location.
A complete environmental impact summary is given in Chapter 5.
However, from these wear data, the amount of solid wear
products can be estimated.
From Reference 6 and the definition of a "standard"
tire from ASTM E 249-66, the volumetric wear rate for
rubber - 3 x 10~5cm3 of rubber/m travel. For
2 x 10s vehicle passes (see data above) or 8 x 105
tire passes, we have 24 cm3 of rubber lost/m travel.
Assuming asphalt wear is about the same, the amount
of rubber/asphalt debris in a one-meter length of
the test section after 200,000 vehicle passes =* 50 cm3.
For a coating thickness of 0.01 cm, we have about
300 cm3 of material in a one-meter lane length. From
the data for an average wear of 25 percent, the solid
coating removed after 200,000 vehicle passes - 75 cm3.
We conclude that the amount of solid debris from the coating
is not much greater than that from normal rubber/asphalt
highway wear.
6.0 FRICTION AND DEGRADATION TESTS
Over a four-month period, a large number of materials and
formulations were applied to asphalt and concrete surfaces
57
-------
en
oo
i?
(a)
(b)
Figure 4-6 Application of Prospective Materials for Phase II Wear Tests
-------
MATERIALS
MATERIALS
AlO
Figure 4-7 Results of Phase II Wear Tests on Asphalt
After 35 Days
59
-------
(a)
(b)
Figure 4-8 Results of Phase II Wear Tests on Asphalt
After 75 Days
60
-------
on BBRC premises. While the primary goal was the determina-
tion of coating friction characteristics on real surfaces,
very useful data on coating and/or substrate degradation were
also obtained during these outdoor exposure tests. These
data were vital to establish that the coatings would not, in
themselves, create a skid hazard.
6.1 Procedure
All coatings were applied by spray techniques to give 0.01 cm
dried films. The site location, test area sizes and section
numbering systems are defined in Appendix C, Figures C-2 and
C-4.
6.2 Numerical Data and Observations
The numerical skid value measurements and degradation observa-
tions are presented in Table 4-9. The comments are self-
explanatory. A quantitative discussion of the skid numbers
is given in 6.4 below. In general, friction coefficient is
proportional to the values and values below 45 are unacceptable
from a safety standpoint. The variation of skid numbers with
time is an indication of change.
Note the coatings that, even in this zero traffic situation,
disappear or degrade with time (Formula 125, Cartaretin F-4,
for example). Note also the materials that have unacceptable
skid values (Arothane, Cartaretin F-4, Arolon) suggesting
water solubility, since the skid tests are run with water on
the surfaces. Note further that some of the unformulated
silicone resins (DC92-009 and DC 732) are unacceptably
slippery. Finally, note the components (Silanox 101, Arolon,
Arothane and Cartaretin F-4) which degrade asphalt, indicating
oleophilic solution of the asphaltic binder.
6.3 Photos
Photos indicating the test layout and some of the points made
above are presented below.
Figure 4-9 (first asphalt tests) showing:
A-9a: Lot #1
A-9b: Lot #3 showing degradation already in progress
A-9c: Lot #5
A-9d: Lot #7
61
-------
Table 4-9
FRICTION (ASTM ESOS) AND DEGRADATION TESTS
MATERIAL (SECTION)
ALL MATERIALS APPLIED
AT A RATE EQUAL TO
A 0.010 on. THICK FILM
SUBSTRATE/
DATE Mil.. APP.
UNCOATED
SUBSTRATE
SKID VALUES
ASPHALT
DRI-SIL 73 (HI)
AROLON 376/F-12S (13)
DRI-SIL 73/SILANOX 101 (US')
AROTHANE 190HSO/FREKOTE (ป7A)
AROIHANE 190M50/DRI-Sil (ซ9)
CARTARETIN F-4 (ป11A)
DRI-SIL 73/FREKOTE (*13)
DRI-SIL 73/SILANOX 101 (J11B)
PETROSET AT (I7B)
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT/ 6/21/74
ASPHALT / 6/24/74
ASPHALT/ 7/3/74
72/75/76/75
73/74/75/77
68/72/72/70
76/75/75/73
75/76/75/76
77/76/77/77
73/75/75/77
77/76/77/77
76/75/75/73
TEST ONE
DATE
TEMP
(ฐC)
VALUES
SKID TEST DATA
TEST TWO
DATE
TEMP
rc)
VALUES
TEST THREE
DATE
TB1P
(ฐC)
VALUES
NOTES
CONTACT
ANGLES
MEASURED
7/2/74
ESTIMATED
CONTACT
ANGLES'
"2ฐ
9/3/74
FIRST ASPHALT TESTS
6/24
38
78/76/76/75
37/36/37/36
87/86/86/84
49/52/51/49
59/60/60/59
NOT hEASURED
STILL TACKY
73/73/70/70
7/15
40
68/68/70/69
42/40/42/40
ASPHALT
DEGRADED
43/43/40/40
36/33/33/33
COATING
DEGRADED
73/77/75/76
ASPHALT
TffifiRAT)ETl
65/65/67/67
9/3
15
74/77/76/77
62/62/60/58
83/84/82/84
57/58/56/56
65/66/65/63
ASPHALT
RUINED
70/70/70/69
83/83/83/82
77/77/78/78
(86ฐ)
ASPHALT BADLY DEGRADED
YELLOW COLOR SHOWS (104ฐ)
DEGRADATION
ASPHALT RUINED (55ฐ)
ASPHALT RUINED (63ฐ)
ASPHALT AND
COATING RUINED
LOOKS O.K. (90ฐ)
SAME AS 15
LOOKS O.K.
60ฐ
30ฐ
70ฐ
30ฐ
30ฐ
30ฐ
90ฐ
60ฐ
CONCRETE TESTS
PETROSET AT (11)
DRI-SIL 73 (ซ2)
DRI-SIL 73/ DC 732 (13)
FORMULA 125 (ป4)
TT-P-11SD/DC 732 (15)
TT-P-H5D/4044 (ป6)
190M50/FREKOTE 33 fป7)
190MSO/4044 CS)
CARTARETIN F-4 (ป9)
CONCRETE/ 7/11/74
CONCRETE/ 7/11/74
CONCRETE/ 7/11/74 '
CONCRETE/ 7/11/74
CONCRETE/ 7/11/74
CONCRETE/ 7/11/74
CONCRETE/ 7/12/74
CONCRETE/ 7/12/74
CONCRETE/ 7/12/74
72/72/72
78/78/78/77
73/75/74/73
7/15
32
57/53/53/50
67/65/65/64
67/67/68/68
76/79/75/76
79/78/82/78
93/93/90/91
67/66/67/65
35/35/34/34
19/17/20/20
7/30
30
63/63/63/63
62/60/60/60
58/56/57/56
68/69/69/69
76/77/76/77
96/94/96/96
43/43/43/43
43/40/40/41
9/3
15
71/70/70/70
76/74/73/75
64/63/65/65
74/73/73/73
83/83/83/85
100/100/98/95
70/68/68/68
41/40/38/40
60/61/63/62
F-125 GONE BY
9/3/74
F-4 GONE BY
9/3/74
30ฐ
60ฐ
90ฐ
30ฐ
90ฐ
fin0
30ฐ
30ฐ
30ฐ
to
"DEGRADATION OF ASPHALT CHARACTERIZED BY LIFTING AND PEELING OF SURFACE
-------
Table 4-9 FRICTION (ASTM E303) AND DEGRADATION TESTS (Continued)
MATERIAL (SECTION)
ALL MATERIALS APPLIED AT
A RATE EQUAL TO A 0.010 Cm
THICK FILM
SUBSTRATE/
DATE MIL. APP.
UNCOATED
SUBSTRATE
SKID VALUES
SKID TEST DATA
TEST ONE
DATE
TEMP
ฐC
VALUfcS
TEST TWO
DATE
TEMP
ฐC
VALUES
TEST THREE
DATE
TEMP
ฐC
VALUES
NOTES
ESTIMATED
CONTACT
ANGLES
H20
9/3/74
SECOND ASPHALT TESTS
DRI-SIL 73/DC 732 (ป2J
TT-P-115D/DC 732 (*4)
TT-P-11SD/4044 (*6)
190M50/FREKOTE 33 C*8)
HDD. TT-P/ 4044 (ป10)
DC 92-009 (ป12)
MDD. TT-P/DC 92-009 (NE)
HDD. TT-P/DC 732 .[SE)
MOD. TT-P/FC 321 (2-4)
G31, 2x (ป14)
G31 THIN (*14)
XYLAN 2052 (S14)
FC-321 C*l)
FREKOTE 33 (ป2)
DC 732 (ป3)
ASPHALT / 7/16/74
ASPHALT / 7/16/74
ASPHALT/ 7/16/74
ASPHALT / 7/16/74
ASPHALT/ 7/16/74
ASPHALT/ 7/16/74
ASPHALT/ 7/29/74
ASPHALT/ 7/29/74
ASPHALT/ 7/30/74
ASPHALT/ 9/19/74
ASPHALT/ 9/19/74
ASPHALT/ 9/19/74
ASPHALT / 10/9/74
ASPHALT / 10/9/74
ASPHALT / 10/9/74
73/74/74/74
76/78/78/78
73/74/76/75
65/63/63/62
67/71/68/73
73/73/75/76
78/80/80/80
78/80/80/80
78/80/80/80
72/75/76/75
73/75/74/77
68/72/72/70
7/17
9/20
10/9
39
26
25
73/77/78/79
68/67/67/66
88/88/88/88
43/44/43/43
84/86/84/84
45/46/45/46
67/69/68/68
79/78/79/80
59/56/56/56
63/63/60/63
73/72/73/73
46/44/44/44
7/30
30
66/68/68/69
68/68/69/70
85/85/86/85
34/33/33/34
83/85/87/87
34/35/34/35
59/61/62/62
54/54/54/53
87/89/89/88
9/3
9/18
IS
27
66/65/67/66
70/70/70/70
85/84/84/85
40/38/38/39
96/98/98/96
39/36/36/35
58/58/55/60
60/61/60/61
81/84/88/88
30ฐ
90ฐ
60ฐ
60ฐ
30ฐ
90ฐ
90ฐ
90ฐ
60"
Oi
CO
-------
Oi
(a)
(c)
(d)
Figure 4-9 Tests of Various Materials on BBRC Asphalt Parking Lot
-------
Figure 4-10 (first asphalt tests) showing:
A-lOa: Lot #9
A-lOb: Lot #11A -- Note poor wetting by the coating
A-lOc: Lot #11B with degradation starting
A-lOd: Lot #13
Figure A-ll showing:
A-lla: An overall view of the asphalt area of Phase II
A-llb: Severely degraded Cartaretin F-4 (the narrow
strip) and more advanced degradation in adjacent
11B due to Silanox 101
The relative appearance of STD TT-P-115D and
modified TT-P-115D with the smooth coatings
obtained
Figure 4-12 showing:
A-12a: Severely degraded asphalt due to Arolon 376
A-12b: Severely degraded asphalt due to Arothane 190M50
A-12c: Severely degraded asphalt again due to an
Arothane formulation
Figure 4-13 showing various views of the concrete sidewalk
coatings immediately after spraying.
6.4 Skid Value Interpretation
Figure 4-14 shows a photo of the ASTM E303 portable skid
tester used in making the skid value measurements. The unit
is basically a pendulum with a rubber foot that slides a
given distance across the (wet) test surface and swings up
an amount inversely proportional to the frictional energy
dissipated.
Figure 4-15 shows two correlations for friction coefficient
as a function of skid value scale reading. The BBRC deriva-
tion was from a simple balance of potential energy loss
(during the tester swing) against frictional energy gain.
The Colorado Department of Highways' correlation is from their
65
-------
05
O5
(c)
(d)
Figure 4-10 Tests of Various Materials on BBRC Asphalt Parking Lot
-------
Oi
^=^
&&&&+.?; .,
i "i_ *">- " e
f&
*^
** -ป.; *
.. ' -*Hf- ' - I
>*. ซasS-- -.-,.'
(c)
(d)
Figure 4-11 Tests of Various Materials on BBRC Asphalt Parking Lot
-------
(a)
(b)
(c)
Figure 4-12 Severely Degra'ded Test Sections on BBRC
Asphalt Parking Lot
68
-------
(a)
(b)
(c)
Figure 4-13 Tests of Various Materials on BBRC Concrete
Sidewalk
69
-------
Figure 4-14' ASTM E303-69 Portable Skid Tester
Figure 4-15
Correlation of
Value (R) from
Friction Coefficient
Portable Skid Tester
(ฃ) with Skid
70
-------
data files. The cited speed is that at which the tester foot
first contacts the surface. Due to the uncertainty of the
correct correlation, tabular data has been left as "skid
values". If it is desired to convert the data to friction
coefficients, it is suggested that the BBRC correlation be
used. The Colorado Highways' correlation is based on a com-
parison with grooved tire data whereas the skid tester foot
is not grooved.
The other reason for leaving the skid values as such is shown
in Table 4-10. The skid values are, through use of the table,
directly related to highway safety --a matter of vital in-
terest 'to any state Highway Department.
Finally, it should be noted that even the poorest coatings
have a friction coefficient of about 0.25 compared to 0.06
to 0.12 for ice (Figure 1 of Reference 54 in Appendix A).
6.5 Conclusion
The results of the friction and degradation tests showed
that, in general
Water soluble materials are unacceptably slippery.
Very highly hydrophobic materials, in their pure
form, also provide too little traction.
Highly oleophilic materials and surface-active
agents badly degrade asphalt.
The skid-number tests and associated degradation observations
proved to be one of the most effective screening techniques
employed in this program.
7.0 ULTRAVIOLET STABILITY TESTS
The ultraviolet stability test, which was conducted primarily
because of indications that hydrophobic silicones are
especially sensitive to this degradation mechanism (Reference
7), is described below.
7.1 Theory
Per Reference 7, the Si-0 bond is especially vulnerable to
rupture from ultraviolet radiation. Since silicones have
this bond and are frequently useful hydrophobes, this type
of evaluation was felt to be necessary. Furthermore, although
it is not pointed out specifically in Reference 7, C-0 bonds
71
-------
Table 4-10
SUGGESTED VALUES OF 'SKID RESISTANCE1
WITH THE PORTABLE TESTER
FOR USE
CATEGORY
A
B*
C*
D
TYPE OF SITE
MOST DIFFICULT SITES SUCH AS:
(i) ROUNDABOUTS
(ii) BENDS WITH RADIUS LESS THAN
500 ft. ON DERESTRICTED ROADS
(ill) GRADIENTS, 1 in 20 OR STEEPER,
OF LENGTH GREATER THAN 100 yd
(iv) APPROACH TO TRAFFIC LIGHTS ON
DERESTRICTED ROADS
GENERAL REQUIREMENTS, i.e. ROADS
AND CONDITIONS NOT COVERED BY
CATEGORIES A AND C
EASY SITES, e.g. STRAIGHT ROADS,
WITH EASY GRADIENTS AND CURVES,
AND WITHOUT JUNCTIONS, AND FREE
FROM ANY FEATURES, SUCH AS MIXED
TRAFFIC, ESPECIALLY LIABLE TO
CREATE CONDITIONS OF 'EMERGENCY
ALL SITES
'SKID- RESISTANCE1
ON WET SURFACE
ABOVE 65
ABOVE 55
ABOVE 45
BELOW 45
STANDARD OF SKIDDING RESISTANCE
REPRESENTED
GOOD' : FULFILLING THE REQUIREMENTS
EVEN OF FAST TRAFFIC, AND MAKING IT
!>OST UNLIKELY THAT THE ROAD WILL BE
THE SCENE OF REPEATED SKIDDING
ACCIDENTS
GENERALLY SATISFACTORY : MEETING ALL
BUT THE MOST DIFFICULT CONDITONS
ENCOUNTERED ON THE ROA0S
SATISFACTORY ONLY IN FAVORABLE
CIRCUMSTANCES'
POTENTIALLY SLIPPERY'
* ON SMOOTH-LOOKING OR FINE-TEXTURED ROADS IN THESE CATEGORIES, VEHICLES HAVING SMOOTH TYRES MAY NOT FIND
THE 'SKID-RESISTANCE1 ADEQUATE. FOR SUCH ROADS ACCIDENT STUDIES SHOULD ALSO BE MADE TO ENSURE THAT THERE
ARE NO INDICATIONS OF DIFFICULTIES DUE TO SKIDDING UNDER WET CONDITIONS.
CHART FROM 'ROAD NOTE NO. 27 OF THE (BRITISH) ROAD RESEARCH LABORATORY
72
-------
(as in ethers and alcohols), with a bond energy of 75 Kcal/
mole, should be even more vulnerable to rupture than the Si-0
bond.* For a 75 Kcal/mole bond, energy radiation at -3800 A
should be most disruptive and this is near the intensity peak
of solar ultraviolet radiation (see Table 4-11).
Assuming a solar constant of 140 milliwatts/cm2, that an
average of 13 percent of this reaches ground level and'that
5 percent of this is in the ultraviolet wavelength region
(2900 A - 4000 A); normal exposure in real time would be 0.91
milliwatts/cm2. To test for an equivalent of 150 days ex-
posure, an energy input of about 9.1 milliwatts/cm2 for 15
days is required. This translates to 1.2 by 101* J/cm2 total
dosage. It must be emphasized that this is for 150 24-hour
days and for a normal winter season represents an overtest
by a factor of about four.**
7 .2 Procedure
Films of the sample coatings were applied (by pouring for
this test) to about one-half of one side of glass microscope
slides. A preliminary 39-hour water soak was performed and
contact angles were obtained to aid in the test decision con-
cerning the materials to be irradiated.
The samples were mounted on a temperature-controlled platen
and irradiated for 16 days to a total dose of 1.3 by 101*
joules/cm2. Due to sample placement, the variation over the
sample area was less than ฑ10 percent. Periodic measurements
of water contact angle and irradiation intensity were made
during the exposure period.
At the end of the test, additional water soaking, qualitative
ice release on some samples and sample coating conditions
were used to evaluate ultraviolet degradation on a go, no-go
basis.
*Note that it is not the magnitude of the bond strength that
is important in this case. It is the resonant frequency
which controls ultraviolet degradation sensitivity, as is
completely discussed in Reference 7.
**With respect to dose rate this is an even greater overtest
when compared to ASTM D795/1148 which is discussed in
5.4 of Chapter 6.
73
-------
Table 4-11
ULTRAVIOLET DEGRADATION SCREENING
MATERIAL CONSIDERED
DRI-SIL 73
EC 92-009
SS-4044
FREKOTE 33
RTV 11 (CATALYZED)
FORMULA 125
DRI-SIL 73/SILANOX 101
TT-P-115D, TV II
AROTHANE 190MSO
FC-321
FC-210
DC 732
BEFORE TEST
WATER CONTACT ANGLES
(DEGREES)
7/1/74
7/3/74
AFTER 39 HRS.
AT 1001 R.H.
TEST DECISION
WATER CONTACT ANGLES
AFTER EXPOSURE
(DEGREES)
2 DAYS
EXPOSURE
4 DAYS
EXPOSURE
16 DAYS
EXPOSURE
SAMPLE CONDITION
AFTER 16 HOUR
WATER SOAK
QUALITATIVE
ICE ADHESION
STRENGTH
CONCLUSION
START IRRADIATION - 7/11/74
90/96,89
92,92,96
88,9189
100,101,105
90,88,93
13
112,115, US
83,85,87
*93,93,91
115,109,106
*41, 37,26
93,86,92
*91,91,90
94,92,97
91,90,92
99,93,99
97,102,101
*116,112,105
69,63,75
*86,89,89
101,104,102
89,83,83
NO
YES
YES
YES
NO(POT LIFE
TOO SHORT)
NO
YES
YES
YES
YES
NO
YES
92,94,94.
88,88,88
92,89,87
106,110,110
66,70,70
91,90,90
103,103,103
96,96,96
100,99,102
90,96,94
92,91,92
104,110,110
68,68,60
81,87,89
105,108,108
90,89,89
95,98,94
89,86,88
102,98,100
111,115,114
61,65,60
84,82,82
114,112,111
102,102,100
NON-WETTED, TOUGH
NON-WETTED, TOUGH
NON-WETTED, TOUGH
WETTED, TOUGH
WETTED, VERY TOUGH
NON-WET, VERY TOUGH
WETTED, VERY SOFT
NON-WETTED, TOUGH
COATING
REMOVED
HARD RELEASE
EASY RELEASE
COATING
REMOVED
EASY RELEASE
NO DEGRADATION
NO DEGRADATION
NO DEGRADATION
NOT USEFUL OR
DEGRADED
NOT USEFUL, BUT
NO DEGRADATION
NO DEGRADATION
DEGRADED
NO DEGRADATION
(WATER WETTED SAMPLE = *)
SAMPLE TEMPERATURE: :29C i 1C
IRRADIATION INTENSITY: 7/11/74: 9.3 mW/on2
7/15/74: 9.4 nW/cm2
RELATIVE INTENSITY
WAVE LENGTH- A
3100
7/27/74: 9.4 mW/cm2 3300
TOTAL DOSE: 1.3 x 104 J/on2 3500
3700
3900
4100
INTENSITY
0.08
0'.32
0.66
1.00
0.72
.0.30
-------
7.3 Numerical Data
All data and test conditions are summarized in Table 4-11.
The judgment factors are self-explanatory. The Dri-Sil 73
is presumed to be satisfactory based on vendor exposure data
and the toughness of the Dri-Sil 73/Silanox 101 combination
film despite the presence of the Silanox 101, which is known
to be sensitive to outdoor exposure from the data in Section 6
above.
The virtual destruction of the FC-321 was somewhat surprising
but may be the reason for 3M's opinion of non-suitability for
this material in the subject application (see Chapter 3}.
7.4 Photos
Figure 4-16 shows:
4-16a: The samples applied to the glass plates
4-16b: The general test setup showing the enclosed
irradiation cabinet with blower tubes to remove
ozone, the temperature controller for the sample
platen and the ultraviolet source power supply
4-16c: The irradiation cabinet open and the platen in
a horizontal position during contact angle
measurement
7.5 Conclusion
Materials, such as DC92-009 and DC 732, which were suspected
of being sensitive to ultraviolet-radiation degradation, were
in fact found to be stable while one material (FC-321) from
a class usually considered quite stable (i.e., fluorinated
compounds) was in fact found to be extremely sensitive. This
tends to confirm the frequency, rather than absolute energy,
dependency mentioned in Reference 7. Note that additional
ultraviolet exposure data for the three road-tested coatings
are presented in Chapter 6.
8.0 SOLUBILITY DATA
Basic solubility data are presented in Sections 1 and 2 above
A further discussion of coating solubility and solvents re-
quired for application is given in the Environmental Impact
section of Chapter 5.
75
-------
(a)
(b)
(c)
Figure 4-16 Ultraviolet Stability Test Samples and
Apparatus
76
-------
In any event the basic criteria in this area are:
Negligible or very low water solubility for the
applied coatings as demonstrated by the contact angle
test series (Section 2 above), weather endurance
(Section 6 above and Chapter 6) and quantitative
solubility from environmental-hazard-related tests
(Section 9 below and Chapter 6).
Negligible solubility of oil in the coating to avoid
degradation of asphalt surfaces as detected during
the tests described above in Section 6.
9.0 ENVIRONMENTAL IMPACT TESTS
Environmental impact tests on components showing the most
promise from the above tests are reported below. As discussed
in the Recommendations and Summary, Chapter 1, hydrophobic
coatings -- no matter how efficient -- cannot be justified
unless their environmental impact compared to conventional
deicing chemicals is substantially less.
9.1 Procedure
The test coatings were sprayed on one side of 7.6 cm by 15.2
cm stainless steel plates. The plates were cured overnight
at ambient temperature and water contact angles were measured.
The plates were soaked for 48 hours in one liter of distilled
water per plate. Note that this is equivalent to the con-
centration of the coatings' water-soluble material in only
an 8.6 cm (3.4-inch) deep rain, which is much less precipi-
tation than would be expected over a- winter season. The
water samples were then analyzed per USEPA methods. The
coatings were re-examined for contact angle and physical
characteristics.
9.2 Numerical Data and Observations
The data are summarized in Table 4-12. Most of the items are
self-explanatory and indicate quite low pollution potential
for most of the coatings. Again, the FC-321, which looked
rather promising in the ice adhesion tests, softened (de-
graded) during the extended water-soaking period. The Frekote
33 was the biggest surprise since other tests had indicated
good water repellency.
77
-------
Table 4-12
ENVIRONMENTAL SCREENING TEST RESULTS
-q
oo
MATERIAL
'SAMPLE!
.NUMBER]
BLANK
190M50
FREKOTE 33
(El)
(E2)
TT-P-llSD.TY. II (E3)
MODIFIED TT-P-115D
TV, II (E4)
FC -321
4044
DC 732
92-009
(ES)
(E6)
(E8)
(E7)
TT-P-115D/DC 732 (E9)
190M50 / FREKOTE (E10)
PETROSET AT
(Ell)
*7Sth STREET
SEWAGE TREATOEN
PLANT, 1/2/74
(INFLUENT]
(EFFLUENT)
* WATER
TREATMENT
PLANT, 1/2/74
f INFLUENT)
(EFFLUENT}
FILM
AREA (cm2) /WEIGHT (gin)
116
116
116
116
116
116
116
116
116
116
116
116
...
0.76
0.07
1.67
1.73
1.01
0.30
O.OS
0.41
2.06
0.52
1.42
WATER CONTACT
ANGLE-DEGREE
(7/29/74)
86,89,86
98,99,101
98,95,75
94,96,98
107,107,112
92,90,91
107,108,109
96,95,96
102,106,109
100,98,98
flER
DEGREE
FILM
AFTER 48 HOUR SOAK
(8/23/74)
82,82,84
99,103,102
89,89,89
96,99,96
101,105,105
87,83,83
106,103,103
99,103,102
101,106,114
96,85,95
VERY TOUGH
EXC. ADHESION
TOUGH
GOOD ADHESION
VERY HARD
GOOD ADHESION
HARD FAIR
ADHESION
SOFT.GOOD
ADHESION
TOUGH, GOOD
ADHESION
STILL TACKY
TOUGH.PCOR
COHESION
TOUGH, GOOD
ADHESION
TOUGH, HARD
EXC. ADHESION
STILL TACKY
EXC, ADHESION
PH
SOLIDS
(gms)
BOD
mg/LITER
COD
mg/LITER
ENVIRONMENTAL DATA
(HAUSER REPORT 74-314) (REF. 60)
6.37
6.10
5.95
6.60
6.40
6.73
6.10
5.90
5.90
6.98
6.90
6.10
-0.0006
+0.0063
+0.0040
+0.0137
+0.0103
+0.0023
+0.0020
+0.0023
+0.0007
+0.0140
+0.0013
+0.0183
3
11
4
8
9
4
3
2
5
14
22
170
10
0.5
0.4
11
42
15
32
34
16
16
5
15
55
84
378
49
1.0
0.9
WEIGHT %
OF FILM
DISSOLVED
0.8
5.7
0.8
0.6
0.2
0.7
4.6
0.2
' 0.7
0.3
1.3
*REFERENCE 60 SUPPLEMENT
-------
9.3 Conclusion
Most of the coatings exhibit quite low environmental contami-
nation potential. This is borne out by the numerical data,
the comparative numbers cited at the bottom of the table and
the discussion of the test data (Reference 60) included in
Appendix A.
As regards total runoff water solids content, consider a
one-meter highway lane (3.66 m wide) coated with DC 732. Per
meter of length, there is 366 cm3 of material (for the 0.01
cm thickness used). For the total life of the coating, if
it were all DC 732, the runoff water could contain no more
than about 18 grams of dissolved material per meter of length.
The application rate for salt cited in the problem statement
of the Recommendations and Summary, Chapter 1, gives 560 grams
of salt per meter of length, or more than 25 times the amount
of material possible from a DC 732 coating.* Noting that
most of the coating materials give 20 percent or less solids
dissolved than DC 732 (per the last column of Table 4-12) ,
it is concluded that most of the coatings have truly negligi-
ble contamination potential once applied to the roadway.
*Note that weights are being compared, not necessarily en-
vironmental impact.
79
-------
Chapter 5
PHASE III APPLICATION STUDY
1.0 INTRODUCTION
In this chapter are presented the various considerations em-
ployed in the selection, application and environmental evalua-
tion of the coatings to be used in the Phase IV highway tests .
Specific topics are material rating factors, the exact composi-
tion of the solutions as applied, a summary of material data
required to compute application rates, a complete cost summary
comparison including updated factors for salt, the formulae
used to determine spray rates and application vehicle speed
and data on spray techniques and calibration methods. Finally,
a complete environmental impact discussion including wear
debris, coating solubility considerations and hazards during
application is presented.
2.0 RATING FACTORS AND FORMULATION SELECTION
Not all materials investigated were explicitly rated. Certain
materials and/or combinations were deleted for the following
(typical) reasons:
Cationic Surfa.ce Active Agents. These materials
showed no tendency to be hydrophobic. Although they
are attractive from a cost standpoint and may exhibit
a "residual" release effect, extensive tests with one
such material (Cartaretin F-4) indicated very rapid
degradation of asphalt and very high BOD/COD demand
due to high water solubility and its chemical nature
(i.e., amines and amides create high demand levels).
Cost. While cost alone was not used as a factor in
arbitrary deletion, high cost combined with less than
outstanding wear resistance (Nyebar F) or likely high
material and application costs combined with very
limited availability (the NRL sample) caused elimina-
tion.
Toxicity. Toxicity "as received" was not heavily
weighted since limited use and/or solvent replacement
80
-------
could reduce the hazard. However, one binder
(TT-P-85D) contains sufficient lead in the dried
film (per shipping label) to present a health-hazard
increase over the existing high levels found in road
dust (Reference 69) if used as a road coating rather
than the current 7 cm (3-inch) wide stripes.
2.1 The Ratings
As noted in Table 5-1, the ratings are divided into four
groups. These groups are so diverse that it was felt a
single composite rating factor would be more confusing than
useful. The ratings are so devised that higher numbers or
"+" signs are favorable. The detailed rating system is de-
fined below.
Ice Adhesion
> 9 kg/cm2 = 0
6-9 kg/cm2 = 1
3-6 kg/cm2 = 2
< 3 kg/cm2 = 3
Removal of the coating or an upward trend per succes-
sive release is indicated by "-".
RoadFriction
< 45 skid value = 0
45-55 skid value = 1
55-65 skid value = 2
> 65 skid value = 3
Water Contact Angle
< 65ฐ = 0
65ฐ- 80ฐ = 1
,80ฐ-100ฐ = 2
>100ฐ = 3
81
-------
Table 5-1
MATERIAL/FORMULATION RATINGU) SHEET
oo
bo
MATERIAL
AID/OR
FORWJIATION
FC-321
FREKOTE 33
G31, 2X
G31, THIN
DC S2-009
TT-P-115D
TT-P-11SD/DC 732
TT-P-115 D/SS-4044
TT-P-11SD/ DC 92-009
TT-P-11S D/ FC-321
TT-P-11S D/FREKOTE 33
MOD TT-P-115 D/ FC-321
HOB 1T-P-115 D
(5 MOD. IT -P-115 D/DC 732
MOD TT-P-115 D/DC 92-009
Vim TT-P-11SD/SS-4044
DC 732
ABOTHANE 190MSO
AROIHANE 190MSO/FREKOTE
AROIHAJE 190M50/SS-4044
AROIHANE 190M50/DRI-SIL 73
DRI-SIL 73
DRI-SIL/SILANOX 101
DSI-SIL73/FREKOTE 33
ฉDRI-SIL 73/DC 732
DRI-SIL 73/DC 92-009
ฉPETROSETAT
WLAN 2052
FUNCTIONAL FACTORS
ICE
AIIIESION
2
2
3
2
3
1
ซ->
1
2
2<-)
1
O(-)
3
3(i>
OC-)
3
2C-)
2<-)
2
1(1)
K-)
O(-)
1(1)
2
1 -
0
2(1)
ROAD
FRICTION
2
3
3
3
0
2
3
2-3
2
2(1)
3
2-3
2
2-3
0
0-3
0
0-2
3
3
3
2-3
2-3
2
JUDGMENT
FACTORS
CONTACT
ANGLE
3
J
2
2
3
2
3
3
'3
3
3
2(1)
1
3
3
3
3
2
1
2
2
2
3
3(1)
3
3
0
0-1
BOD/COD
LEVEL
1
1
2
1 (1)
2
2
2
2
2
1
1
1
1
1
1
1
2
2
0
2
1(1)
1
1
1
1
1
0
0(1)
USEFUL LIFE FACTORS
MATERIAL
OR
SUBSTRATE
D3GRADATION
f
*
* (SHORT)
(TERM)
<
*
*
*
*
*
+
*
*
+
+
*
*
-A
-A
-A
A
+
-A,H
*
*
*
ป(SIORT TERM)
UV
STABILITY
ป
*
+
+
+
*
*
*
+
*
*
*
*
*
7
1
?
1
1
1
ซ(D
WEAR<2>
AND / OR
HARD-ESS
1(11)
2(H)
1(H)
1(H)
1(H)
3(10
2(H)
2(11)
200
3(H)
2(H)
2(K)
3(H)
300
2(W)
300
1(H)
2(H)
2(K)
200
100
3(H)
2(11)
200
100
100
300
1(11)
APPLICATIOJ COST FACTORS
EASE OF
APPLICATION
3
3
0
0
2
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
3
1
2
2
2
3
1
CURRENT
AVAILABILITY
2
1
1
1
2
2
2
2
2
2
1
1
1
1
1
1
2
2
1
2
2
2
2
1
2
2
2
2
MATERIAL
COST
0
0
0
2
0
3
2
1
2
1
0
1
2
2
2
1
1
3
3
2
2
2
2
2
2
2
3
0
ROAD TEST CONCLUSION
OUT. COST, M=AR,
STABILITY
CUT. COST, AVAIL.
PRICE IN
DETAIL
OUT. FRICnOtl,
HEAR
PRICE IN
DETAIL
an. Ann-sice.
COST
OUT. AD3ESKN,
COST
PRIGS IN
DETAIL
CUT. ADHESION,
STABILITY
CUT. ACHESION,
COST
CUT. STABILITY,
COST, INFERRED AD.
OUT. ADHESION
PRICE IN
DETAIL
PRICE IN
DETAIL
OUT. ADHESION
OUT. htAR, COST
OUT. DEGRADATION,
ADHESION
OUT. FRICTION
DEGRADATION
OUT. FRICTION
DEGRADATION
OUT. FRICTION,
DEGRADATION
OUT. ACHESION
OUT. AIHESION,
DEGRADATION
PRICE IN
DETAIL
PRICE IN
DETAIL
OUT. ADHESION,
h-RAR
PRICE IN
DETAIL. TEST
OUT. hIAR, COST
EXACT
FORMULA COST
./ป2
590
336
96
20
66
37
SS
87
68
7
1. (1) INFERRED FROM OTHER DATA
2. W - ESTIMATE BASED ON HEAP. DATA, II ESTIMATE BASED ON QUALITATIVE SCRATCH TEST
3. ICE ADHESION AND ROAD FRICTION HERE CONSIDERED FIRST IN THE
SELECTION OF MATERIALS A, B AND C BUT SEE ALSO SECTION 2.2 OF
THIS CHAPTER.
-------
In general, the angles given are those that were
measured following the ice adhesion tests or other
screening tests.
BOD/COD Level
Rated on the basis of reported COD levels for the
materials or major components as follows:
> 50 mg/liter = 0
20-50 mg/liter = 1
< 20 mg/liter = 2
Material or Substrate Degradation
"+" = No degradation
"-" = Degradation
M = Material
A = Asphalt substrate
UV Stability
"+" = Stable
"-" = Degraded
Wear and/or Hardness
Quantitative rating based on the road tests and on
scratch resistance (usually after exposure to 100
percent relative humidity for 24 hours).
1 = Very soft or high wear
2 = Moderate
3 = Low wear or very hard (not the same as tough)
Ease of Application
Based on a scale of 0 (most difficult) to 3 (easy)
by positive considerations of (a) standard spray
83
-------
truck application, (b) low settle-out rate, (c) long
pot life and (d) ease of equipment clean-up.
Availability
A rating of the availability and delivery time
currently estimated with:
0 = Not currently available
1 = Available but not a stock item
2 = Delivery available from stock
o Material Cost
A rating of the cost of the material (ฃ) to cover a
one square-meter area with solids equivalent to a
thickness of 0.010 cm.
> 300 ฃ/m2 = 0
100-300 */m2 = 1
30-100 ฃ/m2 = 2
< 30 ฃ/m2 = 3
2 . 2 Discussion
With one exception (Scotchgard FC-321) , ten coatings appeared
promising enough to price in detail (pricing factors are given
in Sections 3 and 4 below) . These costs are given at the
right edge of Table 5-1. At the left edge are given the letter
designations for the three formulations selected for highway
evaluation tests. Formulation B appears to violate most of
the basic ground rules. However, per the contact report in-
cluded in Appendix B, it is one of only two materials studied
which was reported to be directly applicable for this study.
It should also be mentioned that, had the program ground rules
permitted consideration of (and funds for) incorporation of
materials into resurfacing mixtures, other materials such as
Viscpspin B would certainly have been rated.
3.0 COMPOSITION SUMMARY
The exact compositions of the coatings rated in Table 5-1 are
given in Table 5-2. These compositions were determined on a
84
-------
Table 5-2
COMPOSITIONS OF RATED COATINGS
ฉ
DESIGNATION
FC-321
FREKOTE 33
G 31, 2X
G 31, WIN
DC 92-009
TT-P;115D
TT-P-11SD/DC 732
TT-P-11SD/SS-4044
TT-P-115D/DC 92-009
TT-P-11SD/FC-321
TT-P- HSD/FRETOIE 33
MOD. TT-P-115D/FC-321
HDD. TT-P-115D
MOD. TT-P-115D/DC 732
MOD. 1T-P-11S D/92-009
MOD. TT-P-115 D/ SS-4044
DC 732
AROTHAN6 190M50
ATOIHANB 190MSO/FREKOTE 33
AROTHANE 190M50/ SS-4044
AROTHANB 190MSO/DRI-SIL 73
DRI-SIL 73
DRI-SIL 73/SILANOX 101
DRI-SIL 73/FRHCOTE 33
DRI-SIL 73/DC 732
DRI-SIL 73/DC 92-009
PETROSETAT
XYLAN 2052
MAJOR MTL./AMOUNT
FC-321/SO cm3
FREKOIE 33 / lOOt
SS-4044 / 33 go
DRI-SIL 73/49 gm
DC 92-009 / SO cm3
TT-P-115D / 100 cm3
TT-P-115D / 80 on5
TT-P-11SD / 80 cm3
TT-P-11SD / 80 cm3
TT-P-115D / 80 cm3
TT-P-11SD / 80 era3
MTT-P-115D/ 80 era3
MTT-P-115D / 80 cm3
MIT-P-llSD / 80 cm3
MTT-P-11SD / 80 cm3
MTT-P-11SD / 80 cm3
DC 732 / 14 gm
190MSO / 85 cm3
190M50 / 85 cm3
190MSO / 85 cm3
190M50 / 85 cm3
DRI-SIL 73 / 92 era3
DRI-SIL 73 / 100 cm3
DRI-SIL 73 / 100 cm3
DRI-SIL 73 / 100 era3
DRI-SIL 73 / 100 of
PETROSET / 100 on3
XYLAN 2052 / 100S
2ND. MTL/AMT.
VMP/2Scm3
DRI-SIL 73 / 8 gm
RTV-11/7 gra
VMP / 50 on3
VMP / 50 cm3
VMP / 40 cm3
VMP / 40 cm3
92-009 / 20 era3
FC-321 / 20 cm3
FREKOTE / 15 on3
FC-321 / 20 on3
VMP / 40 era3
DC 732 / 14 gn
92-009 / 15 cm3
VMP / 40 era3
VMP / 31 cm3
VMP / 51 era3
FREKOTE / 22 era5
4044 / 14 era3
DRI-SIL / 57 era3
VMP / 46 cm3
S-101 / 6 gn
FREKOTE / 57 cm3
DC 732 / 13 gm
92-009 / 100 cm3
WATER / 200 cm3
OTHER ODMPONENIS/AtOUNTS
RTV 11/3 gm
CAT./.l gra
DC 732/13.7 gn
4044/11 cm3
VMP/55cm3
VMP/40 era3
VMP/40 on3
VMP/40 cm3
VMP/71 era3
VMP/ SO cm5
4044/10 cm3
ISOPROP/3 cm3
VMP/49 era3
VMP/49 on3
VMP/114 era3
VMP/50 cm3
VMP/80 cm3
VMP/100 cm3
CATALYST/. 04 gra
VMP/31 cm3
ISOPROP/3 cm3
ISOPROP/3 on3
ISOPROP/3cm3
FORMULATION OF TTP-11SD
COMPONENT
SHELL TOLU-SOL 19EC
METHANOL/KA1ER (95/5)
CLORAFIN40
VELSICOL XL-37
BEfnONE-38
SOYA LECITHIN
PLIOLITli VTL
TITANOX 2061
DUSAMITE
ASBESTINE X
CELITE 110
HINERALITB 3X
AMOUNT
POUNDS/100 GALS.
340
2
35
35
5
8
107
150
210
53
83
59
85
-------
somewhat trial-and-error basis according to what was required
for efficient spraying. The composition of Fed. Spec, paint
TT-P-115D, Type II, is given at the right-hand side. The
modified version (MOD. TT-P-115D) omitted the Titanox. Note
that during this program, it was discovered that isopropanol
is capable of stabilizing DC 732 in solution for extended
periods of time (six months or more). Finally, it must be
emphasized --as pointed out in the Recommendations section --
that the compositions are not necessarily optimized with
regard to either major/minor component ratio or solvent type.
4.0 COST/COVERAGE SUMMARY
The data required to compute the required coverage rates (for
a 0.010 cm film of non-volatiles) and material costs are
presented in Table 5-3 for the more seriously considered
materials. The formulae used in computing coverage rate (A)
and unit material cost (<ฃ/m2) are noted on the table. It would
appear that the Arothane (which degrades asphaltic surfaces)
might merit special study as a concrete sealant"in view of
its low cost.
As a sample computation for mixtures, consider formulation A --
the MOD. TT-P-115D/DC 732 mixture. From the formulation table,
Table 5-2, we have:
MOD. TT-P-115D 80 cm3
VMP Naphtha 71 cm3
Isopropanol 3 cm3
Total Volume ^ 150 cm3
DC 732 14 gm
From the cost/coverage table, Table 5-3:
Non-volatile solids content of MOD. TT-P-115D plus
DC 732 = 14 gm + 80 cm3 (0.81 g/cm3) =78.8 gms
Estimated film density p = 1.1 g/cm3 (average from
table)
For a 0.01 cm thick film, coverage rate A = W-^-
86
-------
Table 5-3
BASIC MATERIAL COST/COVERAGE DATA
oo
-q
MATERIAL
TT-P-11SD, TYPE II
HDD. TT-P-115D, TYPE II
PETROSET AT
DRI-SIL 73
DC 92-009
AROTHANE 190M50
FC-321
RTV 11
FREKOTE 33
SS - 4044
DC 732
XYLAN 2052
CARTARETIN F-4
NYEBAR F
FOR 0.010 cm FILM; A -
VHP NAPHTHA
ISOPROPANOL
VENDOR'S QUOTED COST
C
$6.00 / GAL. (158f/l)
$5.00 / GAL. (13U/1)
$2.00 / GAL. (S3*/l)
$12.00 / GAL. (316f/l)
$50.00 / GAL. (1320^/1)
$3.33 / GAL. (88$/l)
$18.00 / LB. SOLIDS (1180^/1)
$8.00 / LB. (2000f/l)
$10.00 / GAL. (264*/l)
$29.00 / GAL. (765*/l)
$3.50 / LB. (756*/l)
$60.00 / GAL. (1585^/1)
(SOf/LB. SOLIDS (4Z{/1)
3750* / 1
O.lp/P AND
-------
Where
A is in &/m2
p is in g/cm3
P is in kg/a
And
Cost/unit area = C A
Where
C is in t/S,
Therefore, for the above example
0.150
Cost/Area = Q'Q [131(0.080) + 53(0.071) +-211(0.003)
+ 756(0.014) ]
= 35
-------
The use of this formula is illustrated in following sections.
6.0 COST SUMMARIES AND COMPARISONS
Material costs have been given in Section 4 above. An estimate
of application costs for these materials and the cost of
salting is presented below in Sections 6.1 and 6.2, respec-
tively.
6.1 Hydrophobic Material Application Cost
From spraying work in Phase II and in Phase III (see Section 7
below) , it is known that all the hydrophobic materials can be
applied by a standard roadway distributor.
According to Reference 65, standard distributors are capable
of a wide range 2of application. For this cost analysis,
assume 0.28 &/m -- the highest rate used for applying the
coatings tested in Phase IV (see Section 7.2). Also assume
a spray rate of 18.9 A/minute (5 gallons/minute) which,
according to Reference 65, is on the low side. Both assump-
tions result in a conservative (high) cost. Using the formula
from Section 5 and a lane width of 3.66 m (12 feet) we have:
V = 0.06 (18.9)/1 (3.66) (0.28)
=1.11 km/hr (0.69 mph)
For the current operating expense of $36/hr (Reference 65),
the cost is :
Cost = 3600/1.24 (1000) (3.66) = 0.9 (fr/m2
or less than one cent per m2 to apply the hydrophobic coatings.
6.2 Salting Cost
To be able to estimate the cost effectiveness of the hydro-
phobic coatings, the data on Reference 4 (page 36) for the
possible cost savings from replacing salt with a non-corrosi-ve ,
environmentally-benign material must be updated to the 1975
level used for hydrophobic materials .
Per Reference 65, the current cost of a commonly-used sand/
salt mixture (4:1 ratio) is $0.0127/kg ($11 . 50/ton) . From
Reference 70, 8.2 billion kg (9 million tons) of .salt are
used per year. This gives a sand and salt material cost of
M.C. = 0.0127 (5) (8.2 x 109) = $0.5 billion/year
89
-------
From the data of Reference 4, the application cost is estimated
to be equal to the material cost or
A.C. = $0.5 billion/year
The vehicle corrosion damage due to salt (and other chemical
deicers) is cited as 2 billion dollars per year under very
conservative assumptions (Reference 70). Therefore
V.C.D. = $2 billion/year
Also from Reference 70, bridge deck damages in the United
States related to salt were estimated to exceed $0.5 billion/
year.
B.D. = $0.5 billion/year
Maintenance cost for cities, counties and townships for spring
clean-up of sand (per Reference 71) (including catch basin
and sewer cleaning) has been cited as $.Oil/kg ($10/ton) of
sand. Based on the commonly-used sand/salt mixture (4:1 ratio)
(Reference 65), cleaning cost on an annual basis is estimated
1971-1975 from Reference 68):
C.C. = 0.011(1.42)(4)(8.2 x 109) = $0.5 billion/year
The above totals give a yearly cost of about $4 billion per
year with no consideration of pollution damage or road repair
costs. Using the mileage analysis of Reference 4, page 36,
(i.e., assume approximately 1 million miles of 30 foot wide
roadway to be treated) the allowable applied cost of a
hydrophobic coating becomes 28<ฃ/m^ which is in the range of
some of the coatings investigated here (see Table 5-3).
ALLOWABLE APPLIED COST = 4 x 109/1 x 106(30)(5280)( .09) = 28<ฃ/m2
7.0 SPRAY TECHNIQUES AND CALIBRATION
During the evaluation and screening tests conducted during Phase
II (Chapter- 4), various application methods for the coating
solutions were studied. These are discussed in 7.1 below.
application methods selected for the Phase IV road tests and
equipment calibration techniques are reported in Section 7.2
The
i
2.
7.1 Spray Application Techniques
During the Phase II screening tests reported in Chapter 4, many
different methods were employed to apply the materials to the
test substrates. These included dipping, pouring, painting
90
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and spraying. Since spraying is the only economical applica-
tion method usable on real-life highway surfaces, the various
spray methods evaluated are reported below.
Conventional air spraying. This method uses air
(or a propellant) to draw the fluid from a reservoir
and propel the partially vaporized mixture. Various
types employed included artist's air brushes, SPRAY-
ON brand "Jet-Pack" units and a conventional Binks
Model 630 spray gun. In addition to low volumetric
capacity, the primary deficiency noted was a tendency
for these types of units to vaporize solvent at an
excessive rate. The mixtures reached the surface to
be treated too dry for even spreading and good pene-
tration into roadway-type substrates.
Airless (Electric) Spray Units. Although not used
at BBRC, the Project Leader (George Ahlborn) studied
the use of one such unit (Burgess Model VS-860) in
applying the coatings to small (4 m by 4 m or so)
surfaces. Although too slow for roadway use, good
wetting and penetration on concrete was achieved.
Compressor-Powered Airless Spraying. This method
was selected for application of the coatings in
the Phase IV highway tests. Adequate flow rates
were possible with very little solvent vaporization
before reaching the roadway surface.
7.2
Application and Equipment Calibration
Application of the coatings was performed using two Model
ST 7000 Wagner "Spraytech" airless spray units with four
#2680 spray tips. The tips were mounted vertically 46 cm
above the roadway surface to give a 1.83 m-wide spray pattern
(1/2 lane width). Photos are given in Chapter 6.
The spray tips were calibrated using the actual formulations
to be supplied. The results were, for four tips operating
together:
Formulation A: 9.46 liters/minute
Formulation B: 8.78 liters/minute
Formulation C: 9.46 liters/minute
91
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Including about 10 percent extra for spray losses, the actual
application rates were (see Section 4.0 above for sample
computation):
Formulation A: 0.226 liters/m2
Formulation B: 0.282 liters/m2
Formulation C: 0.282 liters/m2
Using the formula given in Section 5.0 above, the required
vehicle speeds were:
Formulation A = 0.06 (9.46)/ 1/2 (3.66) (0.226)
=1.37 km/hr (75 ft/min)
Formulation B = 0.06 (8.78)/ 1/2 (3.66) (0.282)
=1.02 km/hr (56 ft/min)
Formulation C = 0.06 (9.46)/ 1/2 (3.66) (0.282)
= 1.10 km/hr (60 ft/min)
The available truck at BBRC used to carry the compressors,
barrels of treatment formulations, the spray tips and operators
was not capable of the required low speeds. Accordingly, an
International Harvester Tractor Model 340 was rented to pull
the truck. The tractor tachometer was calibrated against
speed to achieve the required road speed for each formulation.
8.0 ENVIRONMENTAL IMPACT SUMMARY
The expected environmental impact data for the hydrophobic
coatings are presented in various sections of this report.
The summary, in three categories, is presented below.
8.1 Solid Wear Debris
In Section 5.4 of Chapter 4, the wear rate of the screen-
tested hydrophobic coatings was shown to be about equal to
the combined tire/asphalt wear rate under the same traffic
loads.
Using the same road area as assumed for cost comparison pur-
poses in Reference 4, page 36, we now consider that this area
(1.43 x 1010 m2) is coated with a hydrophobic material 0.01 cm
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thick. If all this material were worn off, we would have 1.5
billion kg of chemically inert debris. The inert character
of this debris is verified by Reference 60 data and the known
inert character of silicones and of the traffic paint com-
ponents. Comparing this with the nine billion kg of salt
cited in Reference 4, we must conclude that, even if hydro-
phobic coatings were applied at the same rate traffic paints
are applied (about four times the application rate considered
here), the hydrophobic coatings would present much less of
a quantitative threat than does the salt currently employed.
By the same reasoning, coating debris during the winter is
only one-half the tire-rubber/asphalt debris generated in the
United States during one year (again assuming four times the
coating application rate used above and assuming per Reference
4 that only 27 percent of the total highways require deicing).
8.2 Water Soluble Matter
In Section 9 of Chapter 3, data were presented showing that
a maximum of about 5 percent (and, more typically, less than
1 percent) of the coatings were water soluble after applica-
tion. These data were confirmed by hot water extraction tests
in Phase IV (see Chapter 6). As was also pointed out in
Chapter 4, this water soluble matter (in a more concentrated
form than would be expected in real life) had low oxygen
demand levels and a pH (acidity) within + 0.5 units of neu-
trality compared to the control sample.
On the same basis as that used in 8.1 above, the total water
soluble matter that can be obtained from these coatings can
at most be 0.05 (1.5 by 109) or 75 million kg for the entire
United States. This is literally negligible compared to the
more than nine billion kg of salt used per year.
8.3 Air-Borne Contamination
For the two formulations showing promise, this is a real prob-
lem during the application of the coatings to the road.
Consider the application of Formulation A to one lane-
kilometer of highway. This involves covering 1000 (3.66) or
3660 m2 of surface. From 7.2 above, 3660 (0.226) or about
830 liters of solution is required. During application and
shortly thereafter the following are evaporated into the
atmosphere:
VMP Naphtha: 393 liters
93
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Isopropanol: 17 liters
Shell Tolu-Sol 19EC: 242 liters
A copy of EPA Regulation Number 7 (as adopted by the State of
Colorado) is included in Appendix B. Per the requirements of
Section G, Paragraphs 2, 3 and 10, the solvents cited above
(equivalent to about 900 pounds) would have to be vaporized
over at least a two-hour period. However, this only holds if
the concentration of aromatics in the Tolu-Sol (which can
vary significantly from batch to batch) is such that the.con-
centration of aromatics in the total solvent mixture is less
than 20 percent. If the concentration of aromatics in the
mixture exceeds 20 percent, the entire mixture must be classi-
fied as being photochemically reactive and the rate at which
the mixture may be vaporized becomes impracticably low.
Time did not permit BBRC to experiment with paint formula-
tions (one ground rule was the use of commercial materials).
It is certain that photochemically reactive volatiles could
be eliminated. However, for the classes of materials showing
promise for application to existing roadways, some organic
solvent appears to be a necessity. This remains a problem
area for this concept. Certainly, a flammability problem also
exists. However, in the application of Formulations A and C
to highways in Phase IV, reasonable precautions and the very
rapid dissipation of the solvents (requiring only a few
minutes in a two km/hr wind) created no problems.
94
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Chapter 6
PHASE IV HIGHWAY APPLICATION AND TESTING
1.0 INTRODUCTION
In this chapter are presented the program efforts during the
application of three coatings to selected sites, visual ob-
servations of these sites during the winter of 1974-1975 and
post-winter field and laboratory evaluations. The three coat-
ings applied have been completely defined in Chapter 5.
2.0 SITE SELECTION AND DESCRIPTION
The decisions involved in test site selection, the geographical
location of the sites and a precise definition of the coatings'
application configuration are given in this section.
2.1 Site Selection Decisions
Site selection factors and related decisions are given below.
Snow Fall. Per Reference 22, the entire State of
Colorado historically experiences snow falls in
excess of 50 cm (20 inches) per winter season and
the area near Boulder, Colorado, typically has snow
ground cover over 60 days per winter season. More
precise data could not be obtained due to the recent
discontinuance of season weather records by local
agencies (see "Other Contacts" in Chapter 3).
Personal observations by the Project Leader indicated
severe icing conditions in prior winter seasons
periodically in the Boulder area.
Nearness to BBRC. It was originally proposed that
at least some of the test sections be located in the
high mountain country near Boulder, Colorado. Three
practical factors eliminated this concept:
1. Extensive travel and cost would be required to
check such areas. Rapid checking by aerial
flights was ruled out due to dangerous flying
conditions in these areas and further contacts
with aerial photographic experts and airports
indicating a two-day notice before flights could
95
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be made. In this region, the two days are long
enough to completely change the surface condi-
tions .
2. The (justifiable] refusal by the Colorado Depart-
ment of Highways to allow application of the
coatings to areas of extreme hazard (such as
curved mountain roads) until the coatings had
proved not to be skid hazards in themselves in
less hazardous locations.
3. For safety reasons, the Highway Department is
required to salt/sand or plow roadway areas as
soon as hazardous conditions become evident.
Efforts were made to avoid such treatment of the
coated sections but this was not always possible.
Accordingly, areas near BBRC were selected to
permit rapid (prior to sanding or plowing) and
frequent inspection with a minimum of expense.
Road Surfaces. It was considered a necessity that
locations include:
1. Both concrete and asphalt in adjacent sections
at one high traffic location.
2. Worn asphalt in a high traffic location.
3. Asphalt in a low traffic location.
4. Asphalt in a zero traffic location.
5. Concrete in a zero traffic location.
This exceeded the original scope but was felt
necessary to gain the maximum useful data.
Proximity of Sites. Due to the expense of recording
weather data at five sites (some $8000 for two sites),
it was considered a requirement that the sites not
only be near BBRC but also in close proximity to each
other to be able to assume that at least temperatures
would be relatively constant from site to site.
History. To satisfy ourselves and the Colorado
Department of Highways that the coatings were not
safety hazards, it was necessary to have at least
two locations for which the headquarters of the
96
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Colorado Department of Highways could provide accident
records. These accident reports are included in
Appendix D and will be referred to in a later section.
2.2 Geographical Site Location
The geographical locations of the sites are defined in
Appendix C, Figures C-l and C-2.
Figure C-l of Appendix C shows the relationship of the local
area to the Denver Metropolitan area in north-eastern Colorado.
In Figure C-2 of Appendix C are indicated all the test areas
employed in the program. Indicated areas are:
The wear-test location used in Phase II (Chapter 4).
BBRC, where the Phase II friction and degradation
tests were made (Chapter 4) and where the zero-
traffic asphalt and concrete sites used in Phase IV
were located.
The asplalt-only location (medium wear, high traffic)
required in Phase IV (Highway 7).
The high-traffic-load location with adjacent sections
of new asphalt and medium-worn concrete (Highway 36).
The very worn low-traffic-load asphalt section used
in Phase IV (East Pearl Street).
Note that hereafter in this chapter the above locations will
be referred to simply as
BBRC asphalt and concrete
Highway 7
Highway 36 asphalt and Highway 36 concrete
East Pearl Street
Except for the BBRC sites, all test sections were located on
straight and level sites where traffic could move at relatively
constant speeds.
97
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2.3 Site Application Configuration
The exact location, configuration and size of the treated areas
are defined in the figures in Appendix C. None of the figures
are drawn to scale.
Figure C-4 defines the areas used at BBRC.
Figure C-5 shows the Highway 7 coating placement and the
estimated traffic load based on October, 1974 data.
Figure C-6 gives the same information for Highway 36 concrete,
and Figure C-7 gives the data for Highway 36 asphalt.
(Coating A in Figure C-7 was about 100 m west of coating C in
Figure C-6.)
Figure C-8 shows the East Pearl Street location.
3.0 APPLICATION OF COATINGS
The application of the coatings is described in this section.
The application rates for formulations A, B and C, their
exact composition, the equipment employed and its calibration
and application considerations have been defined in Chapter 5.
Presented below are the details of the actual coating operation.
3.1 Coating Application Factors
Various factors and procedural considerations were:
The three formulations were mixed about two weeks
prior to application. Very little separation for
even the paint formulation was observed.
Application dates were controlled by projected
weather forecasts from the U. S. National Weather
Service in Denver. Dates and approximate applica-
tion times are summarized in the tabular observations
summary sheets in Section 4 below.
No surface pre-treatment (washing, sweeping, etc.)
was employed nor was any post-treatment used,
Formulations were applied in the time sequence "C,
B, A" since the drying times decrease in the same
sequence. This minimized tracking of one coating
over following sections.
98
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Adjacent-lane traffic was stopped during the few
minutes of actual spraying for each 1.83 m (1/2 lane)
strip of each section to eliminate any hazard from
the naphtha vapors.
Treated highway sections were opened to traffic
about two hours after the last section was coated.
9 Skid test data were taken shortly after application.
These data and final skid values are given in
Section 5 below.
3.2 Conditions and Observations
Prevailing conditions and observations during the actual
applications are summarized below:
BBRC Phase II and IV Concrete:
Date: 7/11 - 7/12/74
Temperature: Pavement + 37 C
Wind: Nil
Highway 36 Concrete:
Date: 12/12/74
v
Temperature: Air + 10 C; Pavement + 14 C
Wind: 10-20 km/hour
Petroset "fisheyed"
Drying faster on concrete than asphalt
Highway 36 Asphalt:
Date: 12/12/74
Temperature: Air + 10 C; Pavement + 14 C
Wind: 10-20 km/hour
Petroset "fisheyed"
99
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Highway 7 Asphalt:
Date: 12/13/74
Temperature: Air + 4 C; Pavement + 6 C
Wind: 4-6 km/hour
East Pearl Street:
Date: 1/14/75
Temperature: Air + 7 C
Wind: Gusts to 35 km/hour
Coatings somewhat uneven due to wind ,
BBRC Phase IV Asphalt:
Date: 2/13/75
Temperature: Air + 10 C; Pavement + 15 C
Wind: Nil
3.3 Photos
Figure 6-1 shows the application truck with compressors,
spray tips and barrels containing the coating formulations
during application on Highway 36.
Figure 6-2 shows the entire application rig including the
tractor found necessary to achieve the low road speed required
due to our low total spray rate.
Figure 6-3 shows the control possible at the highway edge
(thus little overspray and vegetation damage on roads with
narrow shoulders).
Figure 6-4 shows the first one-half lane strip of formulation B
immediately after its application to Highway 36. The section
of Formula C that had been applied earlier in the day can
be seen in the background.
Figure 6-5 shows a closeup of the second one-half lane strip
of Formulation A being applied to Highway 36 concrete. Note
the small amount of drifting vapors with this technique and
100
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the even spray pattern ("fisheyes1
due to lack of pre-cleaning).
in completed strip were
Figure 6-1
Application Truck on Highway 36 Showing Barrels
of Coating Formulations and Spray Apparatus
Figure 6-6 shows a complete lane with Highway Department
traffic control in background.
By early February, 1975, it became apparent that definitive
results might not be obtained from the Highway and street
sites. Accordingly, the three formulations were applied to
asphalt at BBRC, using air rather than airless spraying.
Figure 6-7 shows:
a and b: Formulation A on BBRC Phase IV asphalt. Note
poor condition of asphalt. Note also uneven
spray pattern due to use of air type spray
gun in this case (see discussion of spray
methods in Chapter 5).
101
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Figure 6-2 Entire Application Rig During Coating of
Highway 36
Figure 6-3 Application of Coating on Highway 36 Concrete
Showing Level of Edge Control Obtainable
102
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Figure 6-4 First One-Half Lane Strip of Formulation B
Applied to Highway 36 Concrete
L=r * f"- ^LzL.- ^. .*-.'* ""' / j._ r^^iflL* .'-Tj^L'^vI.'.'r'" - ^' '^''' '
1
Figure 6-5 Application of Formulation A to Highway 36
Concrete Showing Even Spray Pattern and Small
Amount of Vapor Drift
103
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Figure 6-6 Completed Application of Formulation B to
Highway 36 Concrete
c and d: Formulation B on BBRC Phase IV asphalt. Same
comments as above.
e and ฃ: Formulation C on BBRC Phase IV asphalt. Same
comments as above.
3.4 Conclusion
Due to the planning in Phase III, less difficulty than ex-
pected was experienced in applying the coatings. Of general
note are:
Application was quite even except for the Pearl
Street location where winds were quite high.
The superiority of airless versus air gun spraying
was again demonstrated.
Formulation A (Paint/DC 732) sprayed with the least
"fog".
104
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^ivr
' "l^W1". -^'"/' v" :O"W-""**'' v ฐV^*S
-""i'T"'.->ป'**'.- 'W "*;** -v-i*.^" -
*-%-ii-:i^i!si.i* Jv*-'.-ป<*- -.?JH
^^s'.-v^^r- C-*-,;-^'
SiS&v^'^Hf&sS^.s.
__,.v.-._^.,,
- ."i.'j.-Vv:
^W^'^^^J*^
-ฎ^i
>rQi;
Figure 6-7 Formulations A, B and C on BBRC Asphalt
Test Site
105
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The Petroset AT (Formulation B), being a water-
based mixture, went on the most unevenly but evened
out to virtual invisibility on asphalt in a few hours.
Formulation C (Dri-Sil 73/DC 732) had the most "fog"
but this could be corrected by cutting solvent
quantity.
Adverse weather the week before application resulted
in the Highway 36 and 7 surfaces being slightly
damp during application. However, this is probably
a typical real-life condition so the test was con-
sidered valid in this respect.
It must be noted that a standard distributor could not be
used due to the small quantity of material being applied (less
than 100 liters per formulation per day). Use of standard
equipment would permit faster, more uniform application.
4.0 WINTER OF 1974-1975 OBSERVATIONS
Visual observations, temperature and precipitation data and
qualitative ice release data for the six outdoor test sites
during the winter season are presented below.
4 .1 Measurement Methods
Visual observations of release effectiveness were
made by at least two observers. Where there was
disagreement, this is indicated.
Precipitation amounts were based on broadcast data
and at-the-site measurement.
Temperatures were measured at the site during the
visual measurements using an Omega Engineering Model
T-151C41 electronic temperature indicator.
Qualitative estimates of wind velocity were also made.
It was regrettable that so much of the data were qualitative.
However, especially in the case of weather factors, even the
nearest station at Jeffco Airport (about ten miles from the
sites) could not supply the quantitative data desired.
4.2 Observations and Data
Table 6-1 presents the recorded weather data for every date
observations were made at any site. Note that the precipitation
106
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Table 6-1
WEATHER DATA DURING ROAD TEST PERIOD
Date
12-23-74
1-9-75
1-21-75
2-4-75
2-14 to 2-17-75
2-18-75
3-7-75
3-10-75
3-12-75
3-13-75
3-26 to 3-28-75
4-1-75
to
4-3-75
Temperat
Surface
-1C
5C
2C
-2C
-1C
6C
2C
2C
1C
-1C
2C
-2C
ures
Air
- 3C
-IOC
- 2C
- 3C
- 4C
- 4C
- 7C
- 6C
-12C
Precipitation
Amount
5 cm ('2 in)
2.5 cm (1 in)
7.5 cm (3 in)
Trace
25 cm (10 in)
None
None
Trace
None
None
20 cm (8 in)
10 cm (4 in)
20 cm (Ace) (10 in)
Precipitation
Type
Dry, fluffy snow, light wind
Dry, powder snow, light wind
Moderately wet snow, no wind
Freezing rain, some sleet
Wet snow, light wind
Wet snow, no wind
Heavy wet snow, no wind
Heavy wet snow, moderate wind
Heavy wet snow, moderate wind
-------
amounts, up through mid-March, were far below seasonal normals
(see 2.1, above). In addition, surface and air temperatures
were above normal during this period. Note also the large
differences between air and ground temperatures and the rare
periods when surface temperatures would allow ice formation.
By the end of March when weather conditions became more
favorable for test purposes, the coatings on Highways 36 and
7 were over three months old and no longer effective,
especially in the wear tracks. (However, see Section 5.3
data below.)
Table 6-2 presents the observations for Highway 36. The data
for the concrete section were particularly disappointing.
Several causes for this were:
Heavy sanding. Due to the presence of an exit at the
end of the section, the interests of safety overrode
test considerations.
Concrete was rather old and weathered, which probably
accelerated the coating wear.
Concrete, being far more porous than asphalt (see
Reference 54), may well require higher application
rates than used here or a lower solvent ratio to
reduce penetration.
The asphalt section on Highway 36 yielded some data. Up to
about one month of age, all coatings appeared to have a
beneficial effect. After nearly two months, Formulation C
remained effective.
Table 6-3 gives the data for Highway 7 and Pearl Street. On
Highway 7:
Early observations indicated release from Formula-
tions A and B.
At about two months after application Section A was
still showing qualitative ice release.
At three months, Formulation C was demonstrating lower
adhesion than the untreated roadway.
At no time did qualitative car braking tests indi-
cate a skid danger from the coatings applied.
The Pearl Street location yielded little data. The asphalt
here was quite worn. This, combined with the high winds
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Table 6-2
ROAD TEST OBSERVATIONS ON HIGHWAY 36
DATE
12-23-74
1500
1-9-75
1-21-75
2-4-75
2-14 to
2-17-7S
3-10-75
3-26 to
3-28-75
CONCRETE (APPLIED 12-12-74 Vl-1/2 Mrs)
Heavy traffic and light wind did not
allow the snow to accumulate on the
pavement. No meaningful data could be
taken.
Very light, dry snow, light wind. No
meaningful data could be taken.
No difference could be distinguished between
treated and untreated sections of roadway.
No differences could be observed. This
site had been heavily sanded.
This was a heavy wet snow. When the area
was first observed, the snow cover was
too thick to tell if anything was hap-
penning on the pavement . When the area
was next observed, it had been plowed and
all that remained was slush.
No ice had formed. The area was very heavily
sanded. No difference could be seen between
coated and uncoated surfaces. It appeared that
the coatings were very nearly gone.
ASPHALT (APPLIED 12-12-74 vl-1/2 Hrs)
Heavy traffic and light wind did not allow the snow
to accumulate on the pavement. No meaningful data
could be taken.
Very light, dry snow, light wind. No meaningful data
could be taken.
Noticeable difference could be observed between treated
and untreated areas, especially Section C. All
treated sections appeared freer of snow and slush
than untreated sections.
Section C appeared to have less snow and ice accumu-
lated than the other areas, both treated and un-
treated. All sections had been heavily sanded.
This was a heavy wet snow. When the area was first
observed, the snow cover was too thick to tell if
anything was happening on the pavement. When the
area was next observed, it had been plowed and all
that remained was slush.
Not as heavily sanded as the concrete. The traffic
paths were about equally dry on treated and untreated
sections
Highway 36 will no longer be reported. The extreme heavy sanding on this road, the wear of coatings (applied in
the high speed lane) and the high traffic density (resulting in very rapid "wear through" of snow or ice in all
sections) have made further observations non-productive.
o
to
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Table 6-3
ROAD TEST OBSERVATIONS ON HIGHWAY
7 AND PEARL STREET
DATE
12-23-74
0800
1530
12-24-74
0800
1330
1-9-75
1-21-75
2-4-75
2-14-75
3-10-75 '
3-26-75
4-1-75
HIGHWAY 7
ASPHALT CAPPLI'ED 12-13-74 ^2 Hrs)
Light powder snow, M..2S cm (1/2 in.) on curbside
lane. Traffic on inside lane had removed most
of the snow from treated and untreated areas.
Sections of A and B, on the outside, (curbside)
lane showed more snow displacement and more bare
surface, than untreated areas. No difference
could be distinguished between Section C and
untreated sections.
About 2.5 cm (1 in.) of dry snow had accumulated.
The inside lane was still bare due to heavy
traffic. No difference could be distinguished
between treated and untreated areas in outside
alternately applying brakes lightly and accelerating
to regain speed. Could tell no difference bet-
ween treated and untreated sections.
The snow had packed in the outside lane, the inside
lane was clear. No difference in snow pack
could be distinguished.
The packed snow appeared to be releasing from
the surface and breaking up on Sections A and B.
This could not be seen on Section C.
The light wind kept most of the snow off the
pavement, but a slight difference could be seen
between Sections A and B and untreated areas.
No difference could be seen on Section C.
No difference could be seen, in the packed
snow, between the treated and the untreated
sections, however the packed snow on Section C
did seem. darker in color than other sections.
Section A released ice more easily than un-
treated sections. This was determined by
chipping the ice away on both treated and
untreated areas. There was no difference
in "slipperiness11 between treated areas.
"Slipperiness" was determined by driving a
car across the area and lightly applying the
brakes, then accelerating.
No differences in accumulated ice slush.
Chipping at the ice on Section A did indicate
low adhesion. No other observations could
be made due to the heavy sanding.
Some possible differences could be observed.
Test site was very heavily sanded.
Section C appeared definitely clearer of
packed snow than untreated areas.
No observations made.
PEARL STREET
ASPHALT (APPLIED 1-14-75 -H-1/2 Hrs)
More snow on treated sections. This street has light
traffic normally, so the snow had more of a chance
to accumulate. It appeared that the coating was
insulating the snow from the ground warmth.
Hone of the sections, treated or untreated were iced.
No difference in "slipperiness" could be determined.
Slipperiness" was determined by driving a car
across the area and lightly braking and accelerating.
No ice had formed at this site.
This site was not checked.
This site will no longer be checked. Heavy sand-
truck traffic from city of Boulder yard makes effects
difficult to judge.
110
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during application, probably resulted in poor penetration of
the coatings and a short life. However, one dramatic effect
was the ability of the coatings to apparently insulate the
ground from the colder air above.
Although the three formulations applied to asphalt at BBRC
were not as well applied as they were on the highways (since
air, rather than airless spraying, was employed), they did
yield positive results. Table 6-4 gives these observations
for the BBRC, Phase IV, asphalt and concrete sites (see
Appendix C, Figure C-4). For asphalt, note:
The insulating effect again.
On 3/13/75 and 4/2/75, the dramatically easier re-
lease for the coatings.
The concrete site was notable for reconfirmation of the in-
sulation effect and the good conditions of the coatings after
nine months of weathering.
4.3 Photos
Photos could not be obtained at the highway sites. When
differences were visually apparent, light level and direction
were such that sufficient photographic contrast could not be
recorded. It is suspected that aerial photos might have
worked but, as explained in Section 2.1 of this chapter, the
two-day notice required for flights is much too long a delay.
Figure 6-8 shows the BBRC Phase IV asphalt after a brief
snow on 3/10/75. Figure 6-8a is an overall view showing the
frames used to hold water for ice release tests placed on
treated and untreated sections of the site. Figures 6-8b, c
and d are formulations A, B and C, respectively. Note the
beading up of water near the frames in b and c and the
excellent beading over the entire area of d.
Figure 6-9 illustrates the release data of 3/13/75 on the
BBRC Phase IV asphalt. 6-9a and b are formulations A and C
and 6-9c and d are adjacent, untreated areas. Note the re-
lease of large chunks of ice in a and b and the inability to
force release in c and d.
Figure 6-10 illustrates the ice release observed on 4/2/75 on
the BBRC Phase IV asphalt. 6-10a, b and c are formulations A,
B and C, respectively. Note the release of large ice chunks
in all three cases.
Ill
-------
Table 6-4
OBSERVATIONS ON BBRC ASPHALT AND CONCRETE SITES
tss
DATE
2/18/75
0730
2-27-75
3-7-75
3-10-75
3-12-75
3-13-75
4-1-75
BBRC PARKING LOT (APPLIED TO ASPHALT 2-13-75 M Hrs)
Most of the snow had melted off of the parking
area the previous day. Water was poured on treated
and untreated areas. The ice was tapped and chipped
to check release. The treated sections appeared to
release the ice more easily than the untreated sections.
Wooden frames were placed on treated (SI, P3, #5)
and untreated (#2 and S4) areas to contain water. When
ice is formed the areas will be checked for ice/
pavement adhesion.
Frames had film of ice. No data taken.
Ice not formed, but beading evident near frames on
sections A and B.
Ice frozen to pavement only in frame 82 (untreated area).
Ice would not release with screwdriver. The ice was
nearly frozen to pavement in frame S4 (untreated area).
The frames on the treated surfaces all had l-5mm of
water at the bottom. This could indicate the insulating
effect of the coating again.
Ice frozen in all frames except S3. Number 3 frozen
along one edge.
The ice in frame SI released in large chunks only at
ice/pavement interface. Ice in frame S2 (untreated)
could only be chipped away in small shards . It would not
release at ice/pavement interface. The ice in S3
released only at ice/pavement interface. The ice in
frame S4 was frozen to the untreated pavement and could
not be broken away. The ice in frame IS released at
the ice/pavement interface, but not as easily as in
frames 1 and 3.
Sections A and C released excellently at the ice/
pavement interface. Section B also released excel-
lently, but was partly melted at ice/pavement
interface. The untreated sections would not
release from the pavement. The frames could not be
chipped away without damage to the frames.
BBRC
9/3/74
BBRC CONCRETE SIDEWALK (APPLIED 7-11-74 M Hrs)
Lots 1,4,7,8,9 had poor beading.
Lots 3,5 had good beading
Lots 2 and 6 beading was medium
The two sections treated with traffic paint mixtures
were covered with snow, while the remainder of the
sidewalk was wet. This could indicate, once more, the
insulating effect of the coatings containing paint.
-------
(a)
(b)
(c)
(d)
Figure 6-8 BBRC Asphalt Test Site, Showing Overall View and Hydrophobicity
of Tested Formulations A, B and C
-------
(a)
(c)
(b)
(d)
Figure 6-9 BBRC Asphalt Test Site Showing Release of Ice From Sections
Treated with Formulations A and C Compared to Lack of Release
From Untreated Sections
-------
Figure 6-10 BBRC Asphalt Test Site Showing Release of Ice
From Sections Treated with Formulations A, B
and C
115
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Figure 6-11 gives four views of the BBRC concrete sidewalk
during April 1975. Figure 6-lla dramatically shows the in-
sulation effect on sections 5 and 6 coated with paint formu-
lations (see Chapter 4). Figure 6-llb shows the beading of
water on section 3 (Formulation C) . 6-llc and d illustrate
the degradation of two Arothane formulations due to nine
months of weather exposure. The darker areas are the coating
in the process of peeling off.
4.4 Conclusion
A complete discussion of the Phase IV data are given in
Section 6.0 below.
As regards the observations in this section:
Formulation A appears to release ice most easily
but all three demonstrate the ability on unworn
(but weathered) asphalt.
Formulation C appears to have the longest effective
wear life on asphalt.
wear life on asphalt.
Formulation C's effectiveness seems to improve with
(exposure) age. This is reasonable since both com-
ponents cure by exposure to water.
The insulating effect, especially of the paint
formulation (A), is quite pronounced. This might
be a helpful feature on such structures as bridge
decks.
Coatings applied on concrete seem to have shorter
wear life than on asphalt. Higher application rates
may be needed on concrete.
Formulation B was still visible on Highway 36 asphalt
as of July 1975.
5.0 POST-TEST DATA
As a means of clarifying and quantifying some aspect of the
Phase IV highway and lot test work, a number of post-test
examinations and tests were performed. These data, including
(a) wear-life computations, (b) skid-test measurements,
(c) ice adhesion tests on core samples and (d) environmental
contamination tests (including more severe ultraviolet and
water solubility evaluation than performed in Phase II --
Chapter 4), are presented below.
116
-------
(a)
(c)
(b)
(d)
Figure 6-11 BBRC Concrete Test Site Showing Insulating Effect,
Hydrophobicity and Degradation of Various Coating
Materials
-------
5 .1 Wear-Life Estimates
In Section 5 of Chapter 4, visual observations indicated 20
to 30 percent wear after about 200,000 vehicle passes for
coatings similar to the three tested here. The observations
were based on estimates of the amount of the wear stripes
gone (across the lane width) and the wetting/non-wetting of
these stripes during skid tests. The following are based on
high traffic load areas. See Appendix C for the traffic loads
per lane day.
Because of heavy sanding on Highway 36 concrete (see Section
4.2), little can be said about the efficacy of the ice-release
coatings. We can only say that all three coatings were gone
after 500,000 vehicle passes.
On Highway 36 (asphalt):
All three formulations appeared effective after
192,000 vehicle passes.
Formulation C appeared effective after 270,000
vehicle passes.
On Highway 7 (asphalt):
All three formulations were effective after 75,000
vehicle passes.
Formulation A exhibited qualitative ice release
after 151,000 vehicle passes.
Formulation C appeared effective after 228,000
vehicle passes.
As indicated in connection with the tests discussed in 5.3
below, dirt and sand ground into the coatings had a more
detrimental effect than was originally expected.
5.2 Skid Test Measurements
As shown in Chapter 4, Section 6, friction tests with the
portable skid tester are a good indication of the presence of
the coatings. Skid test measurements were made at the six
locations discussed in this chapter, both a few days after
application and on April 14, 1975, when further sub-zero
weather appe'ared unlikely. These data are presented below.
118
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5.2.1 Numerical Data
The numerical data are presented in Table 6-5. Values for
the uncoated surface are given in the "control" column. Note
the following from the values:
On Highway 36 concrete, only formulation C is still
present along the edge.
On Highway 36 asphalt, all formulations are apparently
still present along the edge judging by beading.
Skid values for formulation C also indicated
the presence of the coating.
On Highway 7, beading again indicates the presence
of all three at the edge with the presence of
formulation A also being evidenced by its skid values.
On East Pearl Street, the coatings were no longer
visible and"only one check was made, which showed
that formulation A was in fact gone.
On BBRC parking lot 2, the coatings were, of course,
still present with the formulations again showing
their trends with age (i.e., formulation A, remaining
relatively constant, formulation B becoming less
slippery -- the Petroset being a water-based slow-
cure material -- and formulation C becoming somewhat
more slippery).
The concrete sidewalk also used in Phase II (Chapter
4) shows the same trends as the BBRC asphalt, although
the baseline value has shifted. The formulations
are indicated with A and C still showing excellent
hydrophobicity after nine months of weathering.
In the high traffic areas, all coatings are gone. As is
shown here and well recognized by highway experts (Reference
50, for example), worn highways are more slippery than new
surfaces. Also, worn surfaces seem to retain the coatings
less well than newer ones. It is hypothesized that concrete
becomes more porous and has less strength while asphalt be-
comes compacted so the coatings cannot penetrate sufficiently
to strongly adhere.
119
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Table 6-5
PHASE IV HIGHWAY SKID TEST VALUES
TEST SECTION
AREA
HIGHWAY 36
HIGHWAY 36
HIGHWAY 7
EAST PEARL ST.
BBRC PARKING
LOT 2
CONCRETE WALK
AT BBRC
SUBSTRATE
AND
CONDITION
CONCRETE/WORN
ASPHALT/NEW
ASPHALT/VARIABLE
ASPHALT/VERY WORN
ASPHALT/WORN
CONCRETE/ GOOD
DATE
COATING
APPLIED
12/12/74
12/12/74
12/13/74
1/14/75
2/13/75
7/11/74
TEST CONDITIONS
DATE
TESTED
12/18/74
4/14/75
12/18/74
4/14/75
12/18/74
4/14/75
1/17/75
4/14/7S
2/21/75
4/14/75
7/15/74
4/14/75
TEMP.(C)
AIR
4
6
4
6
6
10
6
11
0
8
26
8
KOAO
7
10
7
10
10
14
10
15
12
22
32
20
SKID TEST VALUES '
CONTROL
62/62/62/62
65/65/63
66/65/66/66
75/75/77 -EDGE
71/70/70-CENTER
70/70/70/73
54/58/60/60
74/74/75
73/75/74/73
66/66/65
FORMULATION A
50/50/50/50(8)
71/72/70-EDGE
77/77/76-CENTER
53/52/52/51(8)
73/73/73-EDGE(B)
7 0/69/70 -CENTER
50/49/49/52(B)
60/61/60-EDGE(B)
73/72/72-CENTER
44/45/48/47(B)
53/59/60-CENTER
63/63/63/63(6)
63/62/63(8)
79/78/82
57/60/61
(HIGH J)
FORMULATION B
63/62/63/62 (B)
64/64/62-EDGE
53/52/52/52(8)
73/73/74-EDGE(B)
73/70/71 -CENTER
60/60/60/60(8)
75/73/73-EDGE(B)
71/71/71-CENTER
52/54/55/SS(B)
71/71/71/70(8)
75/75/74(8)
53/53/50
77/77/76
FORMULATION C
50/49/50/50(6)
54/54/55-EDGECB)
60/58/56/59(8)
69/69/70-EDGE(B)
71/71/71-CENTER
56/65/59/56(8)
70/70/70-EDCE(B)
73/74/74-CENTER
43/49/50/48(6)
76/77/77/78(8)
72/73/74(8)
67/67/68
54/54/54
(HIGH J)
COATINGS
APPARENTLY GONE
bo
o
NOTES: B-BEADING OF WATER NOTED DURING TEST
CENTER = CENTER OF TESTED LANE IN WEAR TRACKS
-------
5.2.2
Conclusion
Perhaps most important to note is the visible presence of
these thin coatings in some areas over four months of traffic
This certainly implies low wear over a normal winter period.
5.3
Ice Adhesion Tests
On 24 March 1975, 10 cm diameter core samples were taken from
selected locations on Highway 7 and from the BBRC asphalt
lot and subjected to laboratory ice adhesion testing.
A photograph of the cores is shown in Figure 6-12. Note that
even after washing the surfaces (Reference 59) considerable
ground-in road dirt is still visible on the formulation A
samples (second from left). Dirt is composed mainly of clays
and silicates -- both of which are hydrophilic. This illus-
trates another practical problem in the evaluation of hydro-
phobic coatings for real-life use on highways.
Figure 6-12
Ice Adhesion Test Core Samples
from Highway 7 and BBRC Asphalt
5.3.1
Numerical Data
The data are summarized in Table 6-6. These tests, as well
as the core tests in Phase II (References 57, 58 and 59 in
Appendix A), were conducted by soaking the cores in water at
ambient temperature for two hours before testing. The porosity
of a particular core sample may account for the variability
in results.
121
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Table 6-6
PHASE IV HIGHWAY CORE ICE ADHESION TEST RESULTS
SITE / LOCATION
HIGHWAY 7: CONTROL
MIDDLE
EDGE
MIDDLE
EDGE
MIDDLE
EDGE
PBA^ING :CONTROL :
LOT 2
ADHESION 9
VALUES - kg/cnT
10.8/11.6/13.5/11.6/14.8/11.6
14.0/10.3/13.2/10.9/16.7/10.7
6.42/3.92/7.07/5.77/13.2
13.4/8.82/13.3/9.38/15.6/10.2 >
14.1/11.3/11.7/13.5/11.8/9.38
8.68/9.17/11.1/10.6/14.2/15.2
7.14/8.26/8.68/9.10/12.1/11.6
15.3/9.87/12.6/12.2/12.7/14.1
8.54/7.21/7.03/8.19/11.6/11.3
11.2/9.52/14.1/13.7/11,8/10.3
11.8/9.94/13.6/10.8/11.9/15.0
DATE
CORES
TAKEN
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
3/24/75
FORMULATION
A
A
B
B
C
C
A
B
C
X
kg /cm
12.35
12.69
7.30
11.83
12.00
11.54
9.53
12.88
9.00
11.80
12.20
R
kg/cm
4.01
6.47
9.28
6.82
4.71
6.54
4.99
5.48
4.57
4.57
5.06
SIGNIFICANCE
OF DIFF.
FROM CONTROL
99%
98%
99%
to
NOTES: DATA FROM HAUSER RPT. 75-168 (REF. 59)
TESTS RUN AT -5C
SIGNIFICANCE VALUES FROM LORD'S TEST IN DESIGNING ENGINEERING EXPERIMENTS: Lipsom et al.; Ann Arbor
1968 (REF. 66)
-------
For the Highway 7 data., note that both formulations A and C
still show a significant (from Lord's test in Reference 66)
reduction in ice adhesion compared to the control at the edge
of the highway. This in spite of the large amount of ground-
in dirt and sand on these cores.
For BBRC lot 2, formulation A shows a significant reduction.
Formulation C gave values over twice (12.20 kg/cm2 versus
5.2 kg/cm2) those obtained in Phase II (Chapter 4). This may
be due to the combined factors of a less-than-ideal applica-
tion technique for this site (see photos in 3.3 above and
discussion of 7.1 of Chapter 5) and/or the demonstrated .
ability of formulation C to improve with time. The fact
remains that all three indicated easy release in the real-life
tests described in Section 4 above.
5.4 Additional Environmental Data
On 21 February 1975, soil samples were taken on the north
side of the East Pearl Street location adjacent to the treated
sections. This site was chosen since the coatings had been
applied only one month previously and visual observation indi-
cated rather rapid removal of the coatings. Thus, this was
felt to be a worst-case situation as regards runoff soil con-
tamination.
The environmental impact of the coatings has been summarized
in 8.2 of Chapter 5. Solubility data were presented in
Section 9 and ultraviolet degradation data were presented in
Section 7 of Chapter 4. The data presented below are an
extension and confirmation of the above.
5.4.1 Test Methods
The test methods and procedures are completely described in
Reference 61 included in its entirety in Appendix A.
5.4.2 Data
A total of twelve samples was taken, four adjacent to each of
the three formulation sections.
In all cases, analysis of the soil samples using Pyrolysis
Gas Chromatographic Techniques failed to detect any of the
formulations in the soil. As a means of using larger soil
samples, Pyrolysis Infrared Spectroscopy was performed. Again,
no detectable amounts of the formulations' components were
found in any of the soil samples. As discussed in Section 9
123
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of Chapter 4, these results are not surprising. The solubility
of the coatings after application to" the roads is so low that
a full-lane width of material would yield -- at most -- 18
grams of material per meter of length if concentrated along
the roadside at one time.
In a final attempt to further define the maximum solubility/
pollution potential of the three formulations, films of the
three formulations 0.05 cm thick were cured (37.8 C for 7 days)
on Teflon sheets. One sheet of each formulation was exposed
to ultraviolet radiation per ASTM D 795/1148. The exposed and
unexposed films were then.extracted for 24 hours at 70 C to
80 C (a very severe condition which would certainly remove
all water-soluble material). The weights lost by the samples
were determined and the non-volatile residues, obtained by
evaporating the extracting solutions, were weighed. From
Reference 61, these data are as follows in Table 6-7.
Table 6-7
HIGH TEMPERATURE WATER EXTRACTION DATA
Sampl
Formulation A,
Formulation A,
Formulation B,
Formulation B,
Formulation C,
Formulation C,
e
Unexposed
Exposed
Unexposed
Exposed
Unexposed
Exposed
Weight Lost
Percent Of
Film Weight
1.3
9.0
4.6
16.7
3.8*
5.4
Residue Weight -
Percent Of
Film Weight
0.6
6.6
0.5
7.8
6.0*
1.7
^Anomalous Results - Residue Weight Cannot Exceed Weight Loss
5.4.3 Discussion of Water Extraction Data
Comparing the data in Table 6-7 with that presented in
Section 9, Chapter 4, we find that the unexposed weight losses
are comparable. This is true especially in view of the much
124
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thicker (5X) films used here, which are thus harder to cure.
Furthermore, except for the anomalous results of unexposed
formulation C, the weight losses and residue weight differences
between the formulations seem consistent with the facts that
formulations A and B contain volatile water-soluble materials
while formulation C cures with water.
The data for the exposed films would seem to indicate severe
ultraviolet degradation. This is in conflict with the data
reported in Section 7 of Chapter 4 and with the stability of
the formulations exposed for 9 months on the BBRC sidewalk
which are discussed in this chapter. The degradation in
the present tests is difficult to understand since the dose
(per Hauser Laboratories) was. 2.28 by 103 joules/cm2 in this
exposure while the dose in Phase II testing was 1.3 by 10*
joules/cm2 --a factor of nearly 6 higher.
It appears that the discrepancies in the data can be explained
by the differences between the two test techniques. In the
Phase II tests, great care was taken to eliminate ultraviolet
generated ozone from the vicinity of the films being irradi-
ated, whereas in the ASTM test, ozone attack of the films is
possible because the ASTM cabinet is not vented.
Of more importance, the temperatures of the tested films were
significantly different in the two different tests. In our
Phase II work, the temperature was held to 29 ฑ 1 C while
during the exposure detailed here the films went to a tempera-
ture of 51 C.
From the Arrhenius equation (see any physical chemistry text),
it can easily be shown that for two different temperatures:
-f)
'i/ CD
Where
R = Reaction rate ratio at T,, and T2, absolute
temperatures in K. (K = C + 273.2)
AH = Reaction enthalpy change, cal/mole
R = Universal gas constant, 1.987 cal/ฐK-mole
Thus equation (1) becomes
1.13 x 10-* AH
~~" C
125
-------
If we consider that, for example, the Si-0 bond is being
broken, AH - 80,000 and R = 8435. For a more normal reaction
mechanism, assume AH ^ 20,000 and JR = 9.6. In any event,
the sample temperature difference in the two exposures has a
very pronounced effect and probably explains the degradation
in these coating film exposures.
5.4.4 Conclusion
On the basis of soil sample testing and high-temperature water
extraction, the environmental pollution effect of the three
road-tested formulations appears negligible.
Even as partially degraded by high-temperature ultraviolet
exposure, the total non-volatile water-soluble matter is still
about the same as the maximum assumed in the Environmental
Impact Summary given in Section 8 of Chapter 5.
6.0 PHASE IV CONCLUSIONS
The results of the Phase IV highway evaluation tests of three
formulations have been presented above. Two of these show
considerable promise with the primary problem areas being
wear life and pollution of the atmosphere during application.
None of the three present a severe safety (skid) hazard in
themselves (see also the accident reports in Appendix D).
While the Petroset AT did not demonstrate notable ice adhesion
mitigation on the highways, it did show such properties in the
asphalt parking lot tests.
Both the Petroset AT and formulation C indicated durability
on the asphalt road surfaces and suggested protection of the
asphalt as well.
All formulations tested show low environmental pollution
potentials.
Applied cost of the tested (as well as those untested, see
Chapter 5) formulations are near the cost of salt/sand mix-
tures when automotive corrosion and bridge damage factors are
included.
126
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REFERENCES
Due to the continuing nature of research in the field and the
delay in obtaining copies of cited material, the following
list of references is not in the same order as given in the
text. In general, books and abstracts from books are listed
first.
1. HYDROPHOBIC SURFACES, Ed. by F. M. Fowkes, Academic
Press, New York, 1969.
2. SNOW REMOVAL AND ICE CONTROL RESEARCH, Symposium held
April 1970, Washington, D. C., (Std Book #309-01828-5).
3. CONTACT ANGLE, WETTABILITY AND ADHESION: Advances in
Chemistry Series #43, American Chemical Society, 1964.
4. A SEARCH: NEW TECHNOLOGY FOR PAVEMENT SNOW AND ICE
CONTROL, Murray, D. M. and Eigerman, M. R., December 1972
(EPA-R2-72-125).
5. TRANSPARENT RAIN-REPELLENT POLYMER COATINGS, Maltenieks,
0. J., October 1971 (SAMPE Quarterly, Vol. 3, No. 1).
6. HOW TIRES WEAR (Based on "New Concept of Tire Wear
Measurement and Analysis" SAE) by Bergman, W. and Crum,
W. B., May 1973 (Automotive Engr., Vol. 81, No. 5).
7. AN APPROACH TO STABILIZING DEICING COATINGS TOWARD SOLAR
RADIATION, Landy, M., 1968 (New Horizons Institute of
Environmental Sciences).
8. ASTM Part 10 (1973): Concrete Testing.
9. ASTM Part 11 (1973): Asphalt Testing and Skid Resistance
Tests.
10. THIN FILM PROTECTIVE POLYMERS FROM AMINES, January 1973,
Naval Civil Engineering Laboratory (AD 757 706).
127
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11. RECENT INVESTIGATIONS ON THE USE OF A FATTY QUATERNARY
AMMONIUM CHLORIDE AS A SOIL STABILIZING AGENT, Dunlap,
W. A., Galloway, B. M., Grubbs, E. C. and House, J. E.,
January 1962.
12. A QUALITATIVE FLIGHT ICING EVALUATION OF POLYETHYLENE
ICEPHOBIC TAPE INSTALLED ON THE ROTOR BLADES OF A CH-3C
HELICOPTER, Roberts, L. A., October 1969 (A70-10695).
13. ADHESIVE SHEAR STRENGTH OF ICE TO BONDED SOLID LUBRICANTS,
Jones, J. R. and Gardos, M. N., December 1972 (ASLE,
Vol. 28, 12).
14. ICING TUNNEL TESTS OF ICEPHOBIC COATINGS, Merkle, E. L.
(A69-11047).
15. ON THE ADHESION OF ICE TO VARIOUS MATERIALS, Stallabrass,
J. R. and Price, R. D., July 1962 (NRG/Canada LR-350).
16. COATING MATERIAL FOR PREVENTION OF ICE AND SNOW ACCUMU-
LATIONS: A LITERATURE SURVEY, Porte, H. A. and Nappier,
T. E., November 1963 (TN-541).
17. COATING MATERIAL FOR PREVENTION OF ICE AND SNOW ACCUMU-
LATIONS: FURTHER INVESTIGATIONS, Hearst, P. J.
(Addendum to TN-541) (AD 600 425).
18. A KIT FOR SERVICE TESTS OF COMPOUND XZ-8-3057 DEICING
COATING SYSTEM (AD 602-030).
19. NATIONAL RESEARCH COUNCIL OF CANADA OTTAWA (ONTARIO), ETC.
METHODS FOR THE ALLEVIATION OF SHIP ICING, Stallabrass,
J. R., August 1970 (AD 721 960).
20. COLD REGIONS RESEARCH AND ENGINEERING LABORATORY, HANOVER,
NEW HAMPSHIRE: Icing Occurrence, Control and Prevention,
Carey, K. L., July (AD 711534).
21. PREVENTION OF ACCUMULATION OF SNOW AND ICE ON OPEN MESH
METAL PANELS, L. D. Minsk; COLD REGIONS RESEARCH AND
ENGINEERING LABORATORY, Hanover, New Hampshire, November
1966 (AD 650 089).
22. CHEMICAL MEANS FOR PREVENTION OF ACCUMULATION OF ICE,
SNOW AND SLUSH ON RUNWAYS, Harris, J. C., March 1965
(AD 615 420) .
128
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23. BONDING OF FLAT ICE SURFACES. SOME PRELIMINARY RESULTS,
Jellinek, H. H. G., July 1960 (AD 696 400).
24. EFFECT OF WEATHERING ON A DEICING COATING (COMPOUND
XZ-8-3057), January 1964, Naval Applied Science Labora-
tory, Brooklyn, New York (AD 427-350L).
25. EFFECTS OF ETHYLENE GLYCOL-TYPE DEICING FLUIDS ON EPOXY
AND POLYURETHANE PAINT FILMS, May 1964, Naval Air
Engineering Center, Philadelphia, Pennsylvania
(AD 440 066).
26. ICE ADHESION TO HYDROPHILIC AND HYDROPHOBIC SURFACES,
Bascom, W. D., Cottington, R. L. and Singleterry, C. R.,
October 1969, (J. Adhesion).
27. INVESTIGATION OF ICE ACCRETION CHARACTERISTICS OF HYDRO-
PHOBIC MATERIALS, D. M. Miller, National Aviation Facili-
ties Experimental Center, New Jersey, May 1970. Note:
Same material as in G. C. Hay's paper on EXPERIMENTS WITH
ICEPHOBIC SURFACES (FAA No. FAA-DS-70-11).
28. Application of MIL-C-6799, Type II, Sprayable, Strippable,
Protective Coating to Pneumatic Deicer Boots (AD 872 440).
29. SCREENING OF 3M ADHESIVE TAPES FOR ICE RELEASIBILITY,
Plumb, R. E., U. S. Army Cold Regions Research and
Engineering Laboratory, Hanover, New Hampshire, July
1970.
30. COMPARATIVE EVALUATION OF THREE NEW SILICONS VARNISHES
FOR ICE RELEASE, Plump, R. E., U. S. Army Cold Regions
Research and Engineering Laboratory, Hanover, New
Hampshire, February 1971.
31. ICE ADHESION AND RELEASE, Plump, R. E., U. S. Army Cold
Regions Research and Engineering Laboratory, Hanover, New
Hampshire, May 1971.
32. DEICER COMPOSITION, Panusch, E., January 1972 (U. S.
Patent 0-3756956).
33. SYNERGISTIC ANTI-ICING COMPOSITION, Rosenwald, R. H.,
February 1971 (U. S. Patent 0-3756795).
34. ANTI-ICING AND LUBRICATING COATING COMPOSITIONS,
Holley, D. and Nika, J. W., November 1971 (U. S. Patent
0-3770633).
129
-------
35. ANTI-ICING GASOLINE COMPOSITION, Larson, A. L., November
1973 (U. S. Patent 0-3771980).
36. CRITICAL SURFACE TENSION OF POLYMERS, E. G. Shafrin, NRL,
Washington (Literature from Dow-Corning, 1974).
37. FOG AND ICE PREVENTATIVE COMPOUNDS, June 1972 (MIL-STD-
1210B) .
38. THE INTERNATIONAL SYSTEM OF UNITS, E. A. Mechtly, NASA
SP-7012, 1969.
39. SURFACE IMPREGNATION OF CONCRETE BRIDGE DECKS WITH POLY-
MERS; PAUL, D. R. and Fowler, D. W.; JOURNAL OF APPLIED
POLYMER SCIENCE; Vol. 19, pp. 281-301 (1975).
40. ICE FORMATION AND REMOVAL ABOARD THE ARCTIC SURFACE
EFFECTS VEHICLE, R. F. Supcoe, Naval Ship Research and
Development Center, August 1972.
41. BOUNDARY LUBRICATION: AN APPRAISAL OF WORLD LITERATURE,
Ed. by F. F. Ling, E. E. Klaus and R. S. Fein, ASME,
New York, 1969.
42. DEVELOPMENT, TESTING AND APPLICATION OF ROADWAY-MARKING
PAINT, Kirchner, S,, STID Trans, from German, October
1965.
43. MEASUREMENT OF CONTACT ANGLES AND EVALUATION OF SURFACE
COATINGS, Fromnsdorff, G. and Tejada, S. B., Gillette Co.
Research Institute, NASA Contract NAS3-13725, August 1971.
44. CLEANING AND CHEMICAL TREATMENT OF AIRCRAFT SURFACES TO
PROVIDE CLEANING PROPERTIES, Miller, R. N., et al.,
October 1971.
45. ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Ed. by Kirk, R. E.
and Othmer, D. F., Vol. 13, pp. 545-546.
46. HYDROPHOBIC SURFACES, Ed. by F. M. Fowker, Academic Press,
New York, 1969 (Hydrophobicity Control of Surfaces by
Hydrolytic Adsorption, M. A. Cook, pp. 205-213).
47. ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Ed. by Kirk, R. E.
and Othmer, D. F., Vol. 13, pp. 962-980 (Waterproofing
and Water Repellency).
130
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48. SOME SNOW AND ICE PROPERTIES AFFECTING VTOL OPERATION,
Minsk, L. D., USA CRREL, Texas Symposium, November 1970,
Preprint SW-70-37.
49. HIGHWAY MARKING PAINTS, Olexander, H., North Dakota
Highway Department for DOT, March 1971.
50. PAVEMENT SLIPPERINESS, Bransford, T. L., Alabama State
Highway Department, August 1973.
51. Federal Standard TT-P-115D.
52. Federal Standard TT-P-85D.
53. FURTHER EVALUATION OF DEICING CHEMICALS, State of Cali-
fornia, Division of Highways, Transportation Laboratory
Research Report CA-DOT-TL-5197-2-74-01, Paper at 53rd
Highway Research Board Meeting, January 1974.
54. CHARACTERISTICS OF HIGHWAY PAVEMENTS AND COATINGS
(PHASE I), Hauser Laboratories Report 5506-74-6.
55. ICE ADHESION TEST REPORT (PHASE II, SERIES 1), Hauser
Laboratory Report 74-225.
56. ICE ADHESION TEST REPORT (PHASE II, SERIES 2), Hauser
Laboratory Report 74-319.
57. SUBSTRATE ICE ADHESION TEST REPORT (PHASE II, SERIES 3),
Hauser Laboratory Report 74-343.
58. ICE ADHESION TEST REPORT (PHASE II, SERIES 4), Hauser
Laboratory Report 74-381.
59. HIGHWAY CORE ICE ADHESION TEST REPORT (PHASE IV), Hauser
Laboratory Report 75-168.
60. ENVIRONMENTAL CONTAMINATION POTENTIAL OF HYDROPHOBIC
COATING MATERIALS (PHASE II, DATA AND DISCUSSION),
Hauser Laboratory Report 74-314 (Data) and Addendum to
Report 74-314 (Discussion).
61. SOIL SAMPLE ANALYSIS FOR ROAD COATING POLLUTION AND UV
ACCELERATED SOLUBILITY TESTS OF ROAD COATING FILMS
(PHASE IV DATA), Hauser Laboratory Report 75-332.
131
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62. Contact Report dated 21 February 1974, BBRC with Colorado
Department of Highways.
63. Traffic Accident Report, dated 4 October 1974, Colorado
Department of Highways.
64. Traffic Accident Report, dated 6 June 1975, Colorado
Department of Highways to BBRC.
65. Verbal Contact Data with Flatiron Paving Company,
Boulder, Colorado on 6/20/75.
66. DESIGNING ENGINEERING EXPERIMENTS, Lipsom, et al., Ann
Arbor, 1968.
67. PREVENTION OF LIQUID SPREADING AND CREEPING, Bernett,
M. K. and Zisman, W. A., NRL Report 5959, Washington,
D. C., 1963.
68. Verbal Contact Data, Ahlborn with University of Colorado
Libraries Technical Reference Service, 6/20/75
69. CONTRIBUTIONS OF URBAN ROADWAY USAGE TO WATER POLLUTION,
Environmental Protection Agency, Environmental Protection
Technology Series #EPA-600/2-75-004; March, 1975 (Table
B-2, Part 4).
70. AN ECONOMIC ANALYSIS OF THE ENVIRONMENTAL IMPACT OF HIGH-
WAY DEICING, Murray, D.M. and Ernst, U.F.W., Environmental
Protection Agency, Environmental Protection Technology
Series, EPA-600/2-76-105; May 1976.
71. ENVIRONMENTAL IMPACT OF HIGHWAY DEICING; Environmental
Protection Agency Edison Water Quality Laboratory,
Edison, New Jersey, June 1971 (Report 11040 GKK 06/71) .
132
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APPENDIX A
HOUSER LABORATORIES REPORTS
(Reference 54)
CHARACTERISTICS OF HIGHWAY PAVEMENTS & COATINGS
A Materials Study For
Ball Brothers Research Corporation
Boulder, Colorado
Report No. 5506-74-6
March 18, 1974
133
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TABLE OF CONTENTS
Page
1. Introduction 1
2. Properties of Concrete Paving 1
3. Properties of Bituminous Paving 7
4. Pavement Paints and Coatings 11
REFERENCES 13
List of Tables
Table 1. Chemical Requirements of Portland Cement,
Specification M85 2
Table 2. Physical Requirements and Strength Properties of Portland
Cement, Specification M85 3
Table 3. Physical Requirements and Strength Properties of Portland
Cement, Specification Ml34 4
Table 4. Typical Portland Cement Paving Mix and
Aggregate Grading 5
TableS. Asphalt Requirements for AASHO Specification M20 8
List of Figures
Figure 1. Coefficients of friction for rib tread and smooth tread
tires on various surfaces in wet and dry conditions, ref. Moyer,
"A Review of the Variables Affecting Pavement Slipperiness" 6
Figure 2. Effects of traffic wear and residues on the friction
coefficients of bituminous and portland cement paving 7
Figure 3. Friction coefficients for skidding tires on bituminous
pavings with different aggregates 10
134
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CHARACTERISTICS OF HIGHWAY PAVEMENTS AND COATINGS
1. Introduction
The objective of this study was to provide a background of information relating
to prospects for using ajbhesive materials to prevent ice adhesion to highways. This study
was performed on BBRC subcontract ^01460 dated February 5, 1974, directed by Mr. George
H. Ahlborn.
2 . Properties of Concrete Paving
Practically all concrete paving consists of Portland cement plus aggregate. The
American Association of State Highway Officials Specification M85 is concerned with
Portland cement, and Specification M134 is concerned with air-entrained Portland cement.
Type I General purpose
Type II For use in areas of moderate sulfate concen-
tration in the soil or ground waters
Type III For use where high early strength is
required
Type IV For use when a low heat of hydrate ion is
required (very large bulk of concrete,
seldom used for paving)
Type V For use where high sulfate concentration
may exist in the soil or ground waters.
The chemical specifications for the five types of Portland cement are noted in
Table 1.
During the setting reaction, Portland cement is very alkaline, a pH about 13 is
common, and some alkalinity remains after cure. For this reason, organic esters may be
135
-------
Page 2
Table 1. Chemical Requirements of Portland Cement,
Specification M85.
ปSulfur trioxuio (SOi), max, percent:
godium and polasaium oxide (Na:0 + 0.658' KiO), max,
Tctra calcium aluminofcrrit c plus iปvicp Lhซ tricalcium alumi-
niate' MCaO'Al2pj*Fp:0: -ฃ- 2f3CaOAhOj), or Bolid
solution MCaO'AljOi'FeiOi -f- 2CaO'FeiOi), as ap-
Type 1
5.0
2.5
3 0
3.0
0."75
0.6
Type TI
21.0
fi.O
(1 0
It I)
2.r>
.i.o'
0.76
0.6
CO
R
Typn III
5.0
3.0
4 0
3.0
0.7B
O.fi
ir/'
Typo IV-
6 B
n.ll
2.3
2.5
.075
0.6
35
40
'1'ypp. V"
4.0
2.3
3.n
0.7D
d.r>
5
20.0
Seci Note 1.
s This requirement applies only when the engineer specifies "low-alki cement." Such cement should be npcrificd
only when alkali-reactive aggregates are to be used in the concrete. The maximum value of 0.6% may be reduced
when thp'cxpericncc of the engineer indicates that such action is desirable.
ซ The expressing of chemical limitations by means of calculated assumed compounds does not necessarily mean
that the oxides are actually or entirely present as such compounds.
When the ratio of percentages of aluminum oxide to ferric oxide is 0.64 or more, the percentages of tricalcium
silicate, djcalcium silicate, tricalcium aluminate and tetracalciura aluminoferritc shall be calculated from the
chemical analysis as follows:
Tricalcium silicate = (4.071 X per cent CaO) (7.600 X per cent SiOO (6.718 X per cent AI.Oi)
(1.430 X per cent FesOi) (2.852 X per cent SOi)
Dicalcium silicate = (2.S67 X per cent SiOO (0.7544 X per cent CiS)
Tricalcium aluminate - (2.650 X per cent AUG.) - (1.692 X per cent Fe.Oi)
Tetracalcium aluminoferrite = 3.043 X per cent FeiOi
When the alumina-ferric oxide ratio is less than 0.64, a calcium aluminoferrite solid solution (expressed as
ss (CiAF -j- C:F) is formed. Contents of this solid solution and of tricalcium silicate- shall be calculated by the
following formulas:
ss (C.AF + C,F) = (2.100 X per cent AUCM + (1.702 X per cent Fc.Oi)
Tricaicium silicate ซ (4.071 X per cent CaO) (7.600 X per cent SiO>) - (4.470 X per cent AliOi) -
(2.6T)'.) X per cent Fe:0.) - (2.852 X per cent SOi).
No tricalcium aluminate will be present in cements of this composition. Dlcnlcium siiirafco shall be calculated
as prcvisouly shown.
In the calculation of CiA, the values of AUOi and Fc,O> determined'to the nptmsfc 0.01 per rent shall bo lisrd.
Values for CsA and for the sum of CiAF + 20iA shall be reported to the nearest 0.1 PIT rrnl. Values fปr othur
compounds shall he reported to the nearest 1 per cent.
d When moderate sulfatc resistance is required for type IIT cement, tricnlcium nhirninalo may on limited to
8 per cent. When high sulfatc resistanrn is required, the tricalcium aluminato may be limited lo 6 per cent.
subject to saponification in presence of concrete. For example, oil-base paints have always
had decomposition problems on concrete surfaces.
Portland cement is easily attacked by weak or strong acids. Hydrochloric acid is
often a recommended treatment to prepare Portland cement concrete surfaces for bonding to
other materials. The acid treatment removes any loosely bonded lime materials at the sur-
face of the concrete. Sometimes any excess acid is neutralized with a tflsodium phosphate
wash, but often the great reservoir of alkalinity in the concrete is used for self-neutralization,
136
-------
Page 3
The physical requirements of cement per M85 Specifications are noted in Table 2
Table 2. Physical Requirements and Strength Properties
of Portland Cement, Specification M85.
Kinr-nesS. specific Biirfnco, HI), cm. per f,. (alternate. mul.lio
-------
Page 4
Type MIA For use where high early strength is
required.
The chemical requirements for air-entraining cements are almost identical to
those of Types I, II and III of Table I. The physical requirements are noted below in
Table 3.
Table 3. Physical Requirements and Strength Properties
of Portland Cement, Specification Ml34
Fineness, specific surface, sq. cm. per e. (alternate methods}
Turbidimeter test:
Air permeability test:
Soundness:
Time ft selling (nltcrnntc methods) (2):
Gillrnorc test:
Vicat test (T 131):
Air content oฃ mortar, prepared nnd tested' in accordance with
Tensile strength, psi. (3):
The average tensile strength of not less than three standard
mortar briquettes, prepared in accordance with Method
T 132. shall be equal or higher than the values specified
for the ages indicated below:
Comprossivc strength, p.ti. (3) :
Tho compressive strength of mortar cubes, composed of 1
part cement nnd 2.75 parts graded standard sand, by
weight, prepared and tested in accordance with Method T
10G, shall be equal to or higher than t'le values specified
for the ages indicated below:
False set, final penetration, min., per cent (4)
Type IA
1,600
1 600
2,800
2,000
O.EO
60
10
46
19 ฑ8
160
27B
350
900
1,600
2,800
50
Type IIA
1 00
1 500
2 600
0 50
CO
10
45
19 ?fc3
12G
260
325
760
1,400
2.800
60
Type IIIA
t
.
0.60
60
10
45
19 ฑ3
27u
376
(3)
1,200
2,600
50
(1) Either of the two alternate fineness methods may be used at the option of the testing laboratory.
However, in cose of dispute, or when the sample fails to meet the requirements of the Blame
meter, the Wagner turbidimcter shall be used, und the requirements in Table II for this method
shall govern.
(2) The purchaser should specify the type of setting time test required. In case he does not BO specify.
or in the case of dispute, the requirements of the Vicat test only shall govern.
(3) The purchaser shall specify the type of strength test desired. In case he does not so specify the
requirements of the comprcssive strength test only shall govern. Unless otherwise upccificd the
strength tests for Types IA and IIA cement wilt be made only at 3 -and 7 days. The strength at
any age shall be higher than the strength of the next preceding age.
(4) This requirement applies only when specifically requested.
A typical mix of Portland cement with aggregate for highway paving is noted in
Table 4.
138
-------
PageS
1.
Table 4. Typical Portland Cement Paving Mix
and Aggregate Grading
Approximate Mix Proportions by Volume (Dry loose rnoasuro):
1 part cement (type IA)
2 parts sand (2 NS grading)
3-3/4 parts gravel, stone, or slab (4A &. IOA or 6A)
Estimated cement content: 5,5 saeks/cu.yd.
Fine and Coarse Aggregates:
2 NS Gradation
Coarse Aggregate Gradation
Sieve
Size No.
3/8 in.
4
3
16
30
50
100
Percent
Passing
100
95-100
65-95
35-75
20-55
10-30
0-10
Sieve Size,
inch
2-1/2
2
1-1/2
1
1/2
3/8
No. 4
4A*
100
95-100
65-90
10-40
0-20
0-5
--
Percent Passing
6A
--
100
55-100
60-90
25-55
--
0-8
IOA*
--
--
100
95-100
35-6S
--
0-8
*4A and IOA, when used in a concrete mix, are combined 50-50
The void content of an air-entraining concrete as in Table 4 is approximately
19 percent (Table 3) of the 14 percent cement volume in the cured concrete, or about 2 .7
percent of the paving. If a Type 1 cement is used (maximum 12 percent air) the void con-
tent of the paving should not exceed 1J percent.
Voids in the concrete are intended to improve freeze-thaw resistance, but they
also make the paving slightly permeable to water and they provide a grip for mechanical
adhesion of ice on the surface *
Water has a high affinity for untreated concrete, virtually a zero contact angle .
The highly polar characteristics of the concrete and the aggregate minerals are responsi-
bility for this hydrophilic characteristic.
The friction coefficient of Portland cement paving is dependent upon vehicle speed,
tire tread, and surface wetness. Figure I presents one of several friction coefficient studies
reported in the "Proceedings of the First International Skid Prevention Conference".
139
-------
Page 6
I.O
O.9
O.8
. O.7
^
.o
"ง 0.6
ฃ
^ 0.5
K.
15
.
-------
Page 7
for traffic lanes (well worn) and passing lanes (less traveled) for both concrete Portland
cement and bituminous paving.
2
O
I-
O
a
u.
IL.
O
O
lu
w
O
O
GRAVEL LIMESTONE
BITUMINOUS CONCRETE
PORTLAND CEMENT
CONCRETE
Figure 2. Effects of traffic wear and residues on the friction coefficients
of bituminous and portland cement paving.
3. Properties of Bituminous Paving
Like concrete highways, bituminous paving consists of a binder phase and a par-
ticulate phase. Bituminous highways use asphaltic materials as binder (about 6 weight
percent) and natural aggregates as economical and efficient filler. Many of the highway
specifications and publications refer to asphalt/aggregate pavement as bituminous concrete.
Asphalts for highway paving are specified by AASHO designation M20-63 in five
different grades. These petroleum derivatives are largely polycyclic compounds of variable
molecular weight, hence the five different grades of hardness and ductility of the "asphalt
141
-------
Page 8
cement". The five grades refer to the hardness as measured by a special needle penetra-
tion test, and specifications are noted in Table 5.
Table 5. Asphalt Requirements for AASHO Specification M20.
I'ciMilrtiUuM Knultt
Penetration at 77 F., 100 gt 5 ace., .
Flash point, Cleveland open cup,
Ductility nt 77 K., 0 cm. per min.ป
Solubilly in cnrhnn tctrachloridc
Thin-film oven lcnl, y, in., 32 C> K.
T> hour
IViielmtion, til ri'Hlduii, pprrpnl
l)llfllllly <>r n'Hiclui- lit. 77 K,
S|ml teal (wlu'ii nnil UK H[icclll-
Min.
85
450
100
99
fin
75
inn-
Max.
100
i.6
1,0
120
Min.
120
425
100
99
4G
100
ir.o
Max.
160
i!6
1.3
200
Min.
200
350
99
40
100
300
Max.
SOU
i'.o
1.5
Negative for all grades
Negative tor all grades
Negative tor all grades
NOTK l.iTho use of the' Hpol tint iซ optional. When it is specified, thn engineer ahall indicule whether tho standard
naphtha solvent, the nuphlha-jtylcne solvent, or ihc heptanc-xylcne solvent will bo used in determining
compliance with tho requirement, and also, in tho case of the xylcnc solvents, the porccntugu of xylcno
to be used.
Aggregates may be either natural gravel or crushed rock. Fractional characteristics
of the highway may be highly dependent upon both the type and the amount of aggregates
used.
The asphaltic cements are generally resistant to chemical reaction at normal highway
temperatures, but they are highly susceptible to softening or dissolution by solvents. Lubri-
cating oils, automotive fuels, paint thinners and chlorinated solvents can rapidly damage
the surface of the asphaltic cement if present in large quantities.
The amount of solvent used in a highway striping paint is generally insufficient to
cause any degradation of the asphalt, and the solvent rapidly evaporates to leave the high-
way surface in its original condition. On the other hand, oil spills on the highway can
cause slackness for a fairly long period of time.
142
-------
Page 9
Anti-ice adhesion treatments in relatively volatile solvents should cause no
chemical deterioration of bituminous highway paving.
Compared to Portland cement paving, bituminous highways are rather soft. The
asphaltic portion of the paving surface wears away with traffic or it may become displaced
by forces from vehicle tires. New surfaces are continually exposed, and as one aggregate
particle may become polished by traffic, another rough aggregate particle may become ex-
posed to the surface.
The friction coefficient of bituminous paving is of the same magnitude as friction
between Portland cement paving and automobile tires. Again, the friction is dependent
upon the vehicular speed, road conditions and surface wear or glazing. Figure 1 shows
that the asphaltic paving may have a friction coefficient comparable to Portland cement
concrete if aggregate is properly exposed, but the friction may be less if there is excess
asphalt on the surface (bleeding).
Additional friction coefficient data showing the effects of three different aggregates
in bituminous paving are shown in Figure 3. The effects of aggregate polishing by traffic
are demonstrated in Figure 2, where the traffic lane has about 70 percent the friction coef-
ficient of the passing lane for both bituminous and Portland cement paving.
The surface tension of water on bituminous paving is normally high and the contact
angle is near zero. The pavement surface is about 85 percent aggregate with high wetta-
bility. Slight oxidation of the organic asphalt, probably accelerated by sunlight, causes
high water affinity on the remainder of the surface.
Bituminous paving is normally considered to be non-porous and relatively imper-
meable to water. Some publicity has been given to recent development of a permeable
143
-------
Page 10
.7
.6
ง .5
.4
.J
Qj
O
.o
Angular aggregate
Rounded aggregate
Bleeding surface
SMOOTH THEAD TIRE-LOCKED-WHEEL TESTS.
j [ \
to 2O 3O 4O
Speed in MPH
A. Asphalt Seal Coat
SO
on
Fr
s^
D
en
.<0
Coe
ซ
Opengr
Open gr
Densegn
*=^
^^^
^^
aded, an.
tded,roui
ided,sano
j
I.-,-
-.
~
^ular cru
idedgravt
'-crushed
""^
.
slicd ' stor
'laggrego
jrave/ ag._
i
~I
^*-iป^
"-" ^'^/^*1'
e aggro.-*
J~JTJ"^"*
fe
"rsSPJ-L
\Dry
I"
O IO 2O JO 4O SO
Speed in MPH
B. Asphalt Plant Mix
Figure 3. Friction coefficients for skidding tires on bituminous
pavings with different aggregates.
asphaltic paving material. In our opinion, a permeable asphalt is of real value in
parking lots where water retention and absorption into the water table may help to miti-
gate flooding. However, a permeable asphalt could cause major subgrade problems in a
highway.
An anti-ice adhesion treatment will have to stick to bituminous paving by means
other than mechanical penetration and interlock.
144
-------
Page 11
4. Pavement- Paints and Coatings
Several Federal Specifications describe the traffic paints appropriate for marking
highways, but state highway departments frequently have their own specifications. Three
of the Federal Specification paints are as follows:
TT-P-85 Paint, Traffic, Reflectorized for Airfield Runway Marking
TT-P-110 Paint, Traffic, Black
Type I Vinyl tolunene-butadiene
Type II Chlorinated rubber-alkyd
TT-P-115 Paint, Traffic, Highway
Type I Alkyd
Type II Vinyl toluene-butadiene
Type III Chlorinated rubber-alkyd
The first of these coatings may be white or yellow. The specification does not describe
the chemical nature of the coating, but emphasizes performance properties. The coating is
used at a "rate of 105 sq. ft ./gallon and the glass spheres are used at the rate of 10 pounds per
gallon of paint.
Specification TT-P-llOb is for marking on concrete pavement and for obliteration of
white and yellow striping on bituminous pavements. It is normally used in a wet film thick-
ness of 16 mils. Type I uses a polyvinyl toluene-butadiene copoiymer, chlorinated paraffin
and petroleum hydrocarbon resins in a thinner of VM & P Naphtha (boiling range 200-230ฐF).
It dries more slpwly than Type II which uses both alkyd resin and chlorinated rubber in
toluene/xylene solvents. This specification describes both formulation and performance re-
quirements of the paints.
The third traffic paint specification, TT-P-115D describes the resin type and content
and the pigment content for each of the three types, in addition to performance requirements.
145
-------
Page 12
All three types of coating are intended for application in 15 mil wet film thickness.
Glass spheres may be added for reflection at the rate of six pounds per gallon of paint.
Traffic paints normally penetrate into the pores of concrete paving, or the sol-
vent softens and impregnates molecularly a bituminous paving. When traffic paints spall
off concrete paving, they often have a portion of the Portland cement concrete on the
paint chip.
Olexander Hnojewyj in "Highway Marking Paints" describes a method for measuring
the depth of penetration of a traffic paint or primer y and the same test may be appropriate
foranti-ice-adhesion materials.
In recent years, linseed oil has been touted as an impregnant for concrete to
minimize water absorption and to improve freeze-thaw resistance. A linseed oil pretreat-
ment might prevent "sponge" absorption of an expensive anti-ice compound. On the
other hand, prior linseed oil treatment on the pavement might prevent the concrete from
acting as a sponge and wicking medium for an inexpensive 'anti-ice-adheslon treatment.
Dr. Ray L./Hauser, Research Director
146
-------
Page 13
REFERENCES
Standard Specifications for Highway Material Part 1, Ninth Edition (1966),
American Association of State Highway Officials, AASHO, 341 National
Press Building, Washington, D. C. 20004.
Proceedings, First International Skid Prevention Conference, Part I (August,
1959), Virginia Council of Highway Investigation and Research, Charlottes-
ville, Virginia.
Olexander Hnojewyj, etal, Highway Marking Paints (March, 1971), North
Dakota State University, Fargo, North Dakota, PB 204 271.
147
-------
(Reference 55)
CLIENT:
MATERIALS:
June 30, 1974
Test Report No. 74-225
Ball Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado
Attn: Mr. George Ahlborn
P.O. #40770
Supplied by client, 15 steel plates, 1/4" thick, with coatings,
identified below.
Control
Al
A2
A3
A5
A6
A7
A8
A9
A10
All
A12
A13
A14
A15
No Coating
Cortoretin F4
Plate A2
FC 321 (11)
Drisil + 101
Nyebar F
NRL Sample
Frekote 33
FC210
6-31-2X
92-009
Drisil 73
FC210W/A43
Drisil +92-009
6-31 Thin
TESTS:
Ice adhesion in shear. Two teflon rings 0.50" |.D. x 0.25" high
were located on each plate, filled with water, then frozen. These
specimens were allowed three to 12 hours temperature soak at approxi-
mately 10ฐF. Specimens were tested by attaching a 0.025" diameter,
nylon jacketed, steel cable to the upper or fixed crosshead member of
a tensile test machine. The cable was looped around the teflon ring
where upon the specimen plate, attached to the movable crosshead
member was pulled away at crosshead rate 0.50 cm/sec. (11.8 inch/
minute). Load was measured by a 500 Ib. Bytrex Load Cell with elec-
tronic readout to an X-Y Recorder. Tests were conducted at precisely
-12ฐ + 1ฐC. This procedure was repeated three times.
148
-------
Force Shear Strength
RESULTS: Coating No. Sequence (Ibs.) (psi) Remarks
Control
Coating Al
A2
A3
A5
la
Ib
2a
2b
3a
3b
Disintegrated
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
20.2
15.7
19.7
22.9
20.9
22.9
103
79.7
100
116
106
116
Upon Exposure to Water at Room Temperature.
18.7
19.5
24.9
19.6
20.4
13.3
12.6
11.1
6.65
8.05
7.95
7.40
50 +
35.7
41.3
68.7
19.9
21.2
95.2
99.1
127
99.8
104
67.7
63.9
56.5
33.9
41.0
40.5
37.7
255 + Part of the coating
182 was removed from the
210 plate during each test
350 with nearly 100% bare
101 metal for #3 tests.
108
149
-------
Force Shear Strength
Coating No. Sequence (Ibs.) (psi) Remarks
A6
A7
A8
A9
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
11.5
18.9
10.8
12.8
11.7
10.9
20.5
15.7
6.6
12.8
14.5
17.6
18.6
14.1
9.75
12.5
15.0
10.9
14.0
20.4
14.3
17.4
11.9
10.3
58.6
96.0
55.0
65.2
59.3
55.5
104
80.0
33.4
64.9
73.6
89.4
94.7
71.8
49.7
63.4
76.1
55.5
71.3
104
72.8
88.6
60.6
52.5
150
-------
Force Shear Strength
Remarks
Coating No.
A10
All
A 12
A13
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
(Ibs.)
9.75
6.90
8.10
7.95
5.70
3.60
4.35
4.30
2.90
3.50
2.60
2.80
25.9
20.2
26.2
24.0
14.8
14.5
17.3
11.4
12.4
7.9
13.0
17.5
(psi)
49.7
35.1
41.3
40.5
29.0
18.3
22.2
21.9
14.8
17.8
13.2
14.3
132
103
133
122
75.1
73.8
88.1
57.8
63.2
40.2
66.2
88.9
151
-------
Force Shear Strength
Coating No.
A14
A15
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
(Ibs.)
36.4
32.0
21.6
16.3
21.0
22.1
15.5
12.1
9.80
9.35
10.5
8.40
(psi) Remarks
185
163
110
83.0
107
112
78.9
61.6
49.9
47.6
53.2
42.8
Tests Supervised & Certified By:
Dr. Ray L. Mauser, Research Director
152
-------
(Reference 56) September 10, 1974
Test Report No. 74-319
CLIENT: Ball Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado 80302
Attention: Mr. George Ah I born
P.O. 41280
MATERIALS: Seventeen coated steel plates supplied by client.
TESTS: Ice adhesion in shear. Two teflon rings 0.50 inch I.D. x 0.25
inch high were located on each plate, filled with water, then
frozen. These specimens were allowed 16 hours temperature
soak at approximately 10ฐF. Specimens were tested by attaching
a 0.025 inch diameter, nylon jacketed, steel cable to the upper
or fixed crosshead member of a tensile test machine. The cable
was looped around the teflon ring then the specimen plate attached
to the movable crosshead member was pulled away at crosshead
rate 0.50 cm/seconds (11.8 inch/minute). Load was measured by
a 500 pound bytrex load cell with electronic readout to an X-Y
recorder. Tests were conducted at precisely -12ฐ + 1ฐC. This
procedure was repeated until three tests had been completed at each
location.
RESULTS: Shear Strength
Coating No.
A2
A3
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
Force (Ibs.)
2.85
2.43
6.85
11.70
3.10
8.10
17.4
19.3
23.1
20.5
19.9
21.1
(psi) Remarks
14.5
12.4
34.9
59.6
15.8
41.3
88.4
98.0
117
104
101
107
153
-------
RESULTS: Shear Strength
Remarks
Coating No.
A5
A6
A8
A 10
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
Force (Ibs.)
12.9
12.7
21.9
16.3
17.2
13.8
13.5
10.2
12.6
22.4
11.6
23.1
12.4
16.0
11.2
18.4
12.7
13.3
11.5
9.55
20.9
11.6
20.5
19.4
(psO
65.7
64.4
112
83.0
87.6
70.3
68.8
51.9
64.2
114
59.1
117
63.2
81.2
56.8
93.5
59.1
67.7
58.6
48.6
106
58.8
104
98.5
154
-------
RESULTS: Shear Strength
Coating No.
A 11
A 13
A 14
A 18
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
Force (Ibs.)
20.1
22.2
15.4
11.7
22.8
23.1
9.84
10.5
19.2
25.3
29.4
27.4
13.1
23.8
18.0
22.8
25.9
23.5
9.46
15.0
16.9
16.9
21.4
18.5
(psi) Remarks
102
113
78.4
59.6
116
118
50.1
53.5
97.8
129
150
139
66.7
121
91.7
116
132
120
48.2
76.4
85.8
86.1
109
94.2
155
-------
Shear Strength
Coating No.
A21
A 23
A 24
A 25
Sequence
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
,3b
la
Ib
2a
2b
3a
3b
Force (ibs.)
. 11.6
11.1
20.3
13.6
22.4
20.2
22.9
24.2
41.9
36.9
9.2
10.6
16.6
12.8
26.8
28.2
25.2
16.6
26.0
17.3
22.6
21.9
32.5
33.6
(psf)
59.1
56.5
103
69.3
114
103
117
123
213
188
46.9
54.0
84.3
65.2
136
144
128
84.5
132
88.. 1
115
112
166
171
Remarks
shear line through
ica, not at inter-
face
coating removed
from plate with ice
coating removed
from plate with ice
primarily bare
steel tested
156
-------
Shear Strength
Coating No.
A 26
A 28
A 29
Sequence Force (Ibs.)
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
Tests
/
2.40
0.50
2.30
2.55
2.50
2.05
19.1
25 +
31.2
28. '3
30.5
36.4
20.1
16.2
27.4
21.6
26.0
25.4
Supervised and Certified
'"7
^ ^ /I^^&L^
(psi)
12.2
2.55
11.7
13.0
12.7
10.4
97.0 .
127 +
159
144
155
185
102
82.5
139
110
132
129
By:
Dr. Ray L. Hauser, Research Director
157
-------
(Reference 57)
September 27, 1974
Test Report No. 74-343
CLIENT: Ball Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado
Attention: Mr. George Ahlborn
P.O. 48046
MATERIALS: Two concrete and two asphalt pavement cores cut from U.S. 36
supplied by client.
TESTS:
RESULTS:
Ice Adhesion. Shear tests were devised to duplicate as nearly as
possible the test conditions in previous tests of adhesion to coatings
on steel plates (Test Reports No. 74-225 and 74-319).
The cores were soaked in water for two hous then cooled to approxi-
mately 10ฐF. Two teflon rings 0.50 inch I.D. x 0.25 inch high were
located on each core, filled with water, then frozen. The cores were
allowed approximately 16 hours temperature soak at 10ฐF. Specimens
were tested by attaching a 1/16 inch diameter steel cable to the upper
or fixed crosshead member of a tensile test machine. The cable was
looped around the teflon ring whereupon the core, attached to the
movable crosshead member, was -pulled away at crosshead rate 0.50
cm/sec. (11.8 inches/minute). Load was measured by a 500 Ib.
Bytrex load cell with electronic readout to an X-Y Recorder. Tests
were conducted at -12ฐ + 1ฐC with triplicate tests at each location.
Core
#1 concrete with
greater amount of
asphalt on surface
Test
#
la
Ib
2a
2b
3a
3b
Max Load
(Ibs.)
34.5
32.0
40.7
33.4
41.6
34.4
Shear Strength
(PS?)
176
163
207
170
212
175
158
-------
Test
Core #
^2 concrete with la
lesser asphalt .,
2a
2b
3a
3b
#3 pavement la
Ib
2a
2b
3a
3b
^4 pavement la
Ib
2a
2b
3a
3b
Max Load
(Ibs.)
38.2
37.5
30.9
40.7
35.7
35.4
33.7
35.6
38.9
41.4
32.6
34.7
34.2
45.2
49.9
30.3
36.5
38.4
Shear Strength
(psi)
195
191
157
207
182
180
172
181
198
211
166
177
174
230
254
154
186
196
Tests Supervised & Certified By:
Dr. RaylL. Hauser, Research Director
159
-------
(Reference 58)
October 15, 1974
Test Report No. 74-381
CLIENT: Ba" Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado 80302
Attention: Mr. George Ahlborn
P.O. N6229
MATERIAL: Concrete and asphalt cores supplied by client (reference Test
Report No. 74-343, September 27, 1974). The asphalt cores
were cut in half, then each of the six specimens were coated
by Bill Deshler of Bali Brothers.
TESTS:
RESULTS:
Ice Adhesion. The same test procedure was used as was detailed
in Test Report No. 74-343.
Core Type Coating
Concrete Mod
Concrete Pet
Test
No.
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
Max Load
(Ibs.)
22.5
17.5
14.7
16.4
36.3
20.8
26.8
28.3
25.4
20.6
41.9
27.9
Shear Strength
(psi)
partial coating
114 removal
89.1
74.6 ป
83.5
185
106
136
144
129
105
213
142
160
-------
RESULTS:
Core Type Coating
Asphalt Mod
Asphalt Pet
Asphalt DR1
Asphalt G31
Test Max Load Shear Strength
No. (Ibs.) (psi)
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3q
3b
20.4
26.1
26.6
29.9
30.6
26.7
37.3
24.8
25.3
31.4
29.0
29.9
13.6
12.7
13.2
9.4
17.5
20.7
28.8
23.9
15.7
28.7
24.0
26.4
partial coating
104 removal
133
135
152
156
136 "
190
126
129
160
148
152
69.0
64.4
67.2
47.9
89.1
105
146
122
79.7
146
122
134
Tests Supervised and Certified By:
Dr. Ray L. Hauser, Research Director
161
-------
(Reference 59)
April 8, 1975
Test Report No. 75-168
CLIENT: Ball Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado 80302
Attention: Mr. George Ahlborn
P.O. No. 20282
MATERIALS: Eleven pavement cores supplied and identified by client.
TESTS: Ice Adhesion. The test procedure was identical to that described in
Test Report No. 74-343, dated September 27, 1974, except that:
1. The test temperature was -5ฐC.
2. The cores, as received, had varying amounts of road dirt and
dust on them. To equalize the tests as much as possible, the
cores were given a warm water rinse of approximately two minutes
per core with a kitchen sink type spray attachment.
RESULTS:
Core Designation
H 7 Control
H 7 A (Inside)
H 7 B (inside)
Max Load
(Ibs.)
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
la
Ib
2a
2b
3a
3b
30.3
32.6
37.8
32.4
41.4
32.4
39.2
28.8
37.2
30.4
47.0
30.1
37.5
24.8
37.3
26.3
43.8
28.6
Shear Strength
154
166
193
165
211
165
200
147
189
155
239
153
191
126
190
134
223
146
162
-------
Test Max Load Shear Strength
Core Designation No. (Ibs.) (psi)
H7C (inside) la 24.3 124
Ib 25.8 131
2a 31.2 159
2b 29.6 151
3a 39.9 203
3b 42.7 217
H7A (outside) la 18.0 91.7
Ib 11.0 56.0
2a 19.8 101
2b 16.2 82.5
3a 37.0 188
3b
Partial coating removal occurred during each test. When 3b test
was run, we didn't get a proper force/distance recording. A repeat
test was thought to be more misleading than useful.
H 7 B (outside) la 39.4 201
Ib 31.6 161
2a 32.8 167
2b 37.9 193
3a 32.9 168
3b 26.4 134
H7C (outside) la 20.0 102
Ib 23.1 118
2a 24.4 124
2b 25.5 130
3a 34.0 173
3b 32.5 166
BB Control la 43.0 219
Ib 27.6 141
2a 35.3 180
2b 34.4 175
3a 35.7 182
3b 39.7 202
163
-------
Test Max Load Shear Strength
Core Designation No. (Ibs.) (psi)
BB A la 23.9 122
Ib 20.2 103
2a 19.7 100
2b 22.9 117
3a 32.4 165
3b 31.7 161
BB B la 31.5 160
Ib 26.8 136
2a 39.5 201
2b 38.2 195
3a 32.9 168
3b 28.9 147
BB C la 33.2 169
Ib .27.8 142
2a 38.1 194
2b 30.2 154
3a 33.4 170
3b 42.1 214
Tests Supervised & Certified By:
Dr. Ray L/. Hauser, Research Director
164
-------
(Reference 60)
Septembers, 1974
Test Report No. 74-314
CLIENT:
Ball Brothers Research Corporation
Aerospace Division
P.O. Box 1062
Boulder Industrial Park
Boulder, Colorado 80302
Attention: Mr. George Ah I born P.O.#41142
MATERIAL:
TESTS:
METHOD:
RESULTS:
Sample
Blank
E 1
E2
E3
E4
E5
E6
E 7
E8
E9
Eleven 3 inch x 6 inch coated coupons, E prefix #1 - #
pH, solids, BOD and
Per US EPA.
COD.
11.
Samples were soaked 48 hours in one liter distilled water per sample.
Tests were performed on portions of the water solutions. Blanks were
treated in a manner identical to the samples.
LJ
6.37
6.10
5.95
6.60
6.40
6.73
6.10
5.90
5.90
6.98
Total Solids
(grams/sample)
-0.0006
40.0063
-K).0040
40.0137
0.0103
0.0023
0.0020
0.0007
0.0023
0.0140
Residue Color
None
White
White
White
White
White
White
White
White
Yellow
BOD
5 day @
3
11
4
8
9
4
2
3
5
mg / liter
COD
20ฐ
11
42
15
32
34
16
5
16
15
165
-------
E 10 6.90 0.0013 White 14 55
Ell 6.10 0.0183 Orange 22 84
Tests Supervised By:
Dr. Timothy D. Ziebarth, Chief Chemist
166
-------
September 25, 1974
Addendum to Test Report No. 74-314 (9/5/74)
CLIENT: Ball Brothers Research Corporation
Aerospace Division
P.O. Box 1062
Boulder, Colorado 80302 P.O. #48046
DISCUSSION OF BOD/COD VALUES
In raw sewage wastes and polluted natural waters, Biochemical Oxygen Demand
(BOD) indicates the concentration of oxygen-demand ing organic materials. A high BOD
discharge into a natural watercourse can seriously result in oxygen depletion within the
water course or streama serious threat to aquatic, vegetation and fish life. Contamina-
tion of down stream water supply sources is also possible.
BOD test results are affected by a number of factorsair temperature, biological popu-
lation, water movement, sun light, oxygen concentration, etc. Because of these factors,
acceptable fluctuations of BOD test results may vary -t- 20 percent for samples taken at the
same time and same location. The BOD test is most effective when used as a long term mea-
sure of the efficiency of a sewage treatment plant by giving a daily measure of the removal
of waste loading of the plant by tests on both influent and effluent. As an example, the tables
on the following page lists BOD values for two sewage treatment stations and the water treat-
ment plant within the city of Boulder for random days during January, 1974.
Simply described, the BOD test involves incubating a sealed waste water sample (or
a prepared dilution) fora period of five days, and then determining the change in dissolved
oxygen content. The BOD value is calculated from the results of the dissolved oxygen tests
before and after the incubation period. The loss of dissolved oxygen is due to the ingestion of
the oxygen by the microbic life in the sample.
167
-------
TABLE 1. TYPICAL BOD VALUES, 5 day, 20ฐ mg/liter
Day/ 1974
75th Street Sewage
Treatment Plant
Pear! Street Sewage
Treatment Plant
Water Treatment
Plant
Influent
Effluent
Influent
Effluent
Influent
Effluent
Jan. 2
170
10
246
113
0.5
0.4
Jan. 8
195
35
168
79
0.3
0.4
Jan. 13
132
9
345
120
0.5
0.4
Jan. 19
339
22
210
112
0.4
0.3
Jan. 25
390
124
176
110
0.4
0.3
TABLE 2.TYPICAL COD VALUES mg/liter
75th Street Sewage
Treatment Plant
Pearl Street Sewage
Treatment Plant
Water Treatment
Plant
Influent
Effluent
Influent
Effluent
Influent
Effluent
378
49
451
175
1 .0
0.9
367
118
362
241
0.6
0.6
321
480
185
1 .0
0.8
414
84
335
120
0.7
0.5
566
215
467
219
0.6
0.4
168
-------
In like manner, the chemical oxygen demand (COD) test is another indicator of
the oxygen demanding characteristics of waste water. This test measures the oxygen
equivalent of materials present in waste water that are subject to oxidation by dichromate.
Acceptable variation in laboratory results may run + 10 percent. Typical COD values
for the city of Boulder are shown in the previous table.
Both BOD and COD tests together are used as industry standards (and waste water
treatment can certainly now be respectably described as an "industry") for evaluating the
efficiency of treatment methods. While the BOD is a bacterial measure of oxygen demand and
the COD is a chemical measure, no valid correlation or definitive relationship exists between
them and EPA warns against making such an erroneous assumption.
Staff of the Region VIII Environmental Protection Agency in Denver were contacted
to learn BOD/COD information in regard to possible contaminants in rain and melted snow
run off from highway surfaces. Discussion with Mr. Dale J. Vodehnal and Mr. Robert J.
Burrndefined such a possibility of pollution as a non-point source of contamination (as con-
trasted with a point source of contamination such as an industrial discharge of wastes into
a natural water course). No BOD/COD criteria exist at present for non-point sources. For
point sources, the maximum BOD loading permissible is 30 milligrams per liter and no value
given for COD. Since newEPA standards and criteria are being finalized on a day-to-day
basis in the Federal Register, this information is valid only for the date on this report.
In light of the above discussion and a review of the BOD/COD test values in
Mauser Laboratories Report No. 74-314, the following comments can be made:
(1) Under current EPA regulations the BOD/COD values as reported are
allowable in snow-melt/rainwater run off discharges into natural
water courses.
169
-------
(2) The BOD/COD values as reported Indicate very little contamination
compared to average sewage effluent flows (Table 1 and 2). These
BOO/COD values are not exactly in line with water for domestic use
processed by the Boulder water treatment plant/ but they certainly are
tolerable.
Mrs. Cdnsuelo M. Hauser/.'Rrojfect Engineer
7
170
-------
(Reference 61) May 14, 1975
Test Report No. 75-332
CLIENT
Ball Brothers Research Corporation
Aerospace Division
P.O. Box 1062
Boulder Industrial Park
Boulder, Colorado 80302
Attention: Mr. George Ahlbom P.O. No. 20180
DESCRIPTION OF WORK
Hauser Laboratories was retained to collect and analyze soil samples for content of anti-
ice surface treatment chemicals. The soil samples were collected at a BBRC test location
on East Pearl in Boulder, Colorado. Analysis was a prior? to be performed by pyrolysis gas
chromatography, but as this method proved unsatisfactory for quantifying amount of surface
treatment material present in the soil, other experiments were subsequently conducted.
Samples of three surface treatment formulations were supplied and labeled as follows:
Sample A - Traffic Paint/Silicone Rubber
Sample B -Phillips "PetrosetAT"
Sample C - Siliconate/Silicone Rubber
FIELD SAMPLING
Four samples of soil were taken from each of three test areas, identified as areas A, B, and
C to correspond to the type of surface treatment given the particular stretch of road. Two
samples, labeled one and four, were taken at a distance of about six inches from the asphalt
surface, and at a depth not exceeding one inch. Two samples, labeled two and three, were
taken at distances of from 18 to 24 inches from the asphalt surface, and at a depth of up to
three inches. Samples one and four in each set were very dry, while samples two and three
were quite wet as this area was below road level. The ground was frozen at the time of
sampling at about the three inch level.
SAMPLE TREATMENT
Formulation samples A through C were dried at 105 C for twenty four hours before use as gas
chromatographic reference materials. Samples A and C were converted to solids but Sample
B remained a sticky oil as a result of this treatment.
The soil samples were dried twenty four hours at 105ฐC, then sieved to give 80 plus and 80 minus
mesh fractions. The 80 plus powders were used fpr the pyrolysis gas chromatographic experiments.
171
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Doped soil samples were prepared of each of the twelve field samples by adding known
amounts of the appropriate coating formulation (diluted) to tared soil samples. The doped
samples were then hand mixed, and subsequently tumbled for twenty four hours to provide
homogeneity.
PYROLYSiS GAS CHROMA TO GRAPH 1C ANALYSIS
The gas chromatograph used was a Varian 920 equipped with thermal conductivity detector.
Samples were pyrolyzed in the GC injection port using a CDS Pyroprobe TOO and a coil
probe. Samples were generally pyrolyzed at 1000ฐC for five seconds in quartz tubes.
The pyrograms of the three dried formulation samples were recorded on a number of columns,
including the following:
3 ' x 1/8" 10% SE30 on 60/80 Chromasorb W
10' x 1/8" 10% SE30 on 60/80 Chromasorb W
5' x 1/4" 1.5% OV101 on 100/120 Chromasorb G H/P
5' x 1/8" 10% Carbowax 20M on 60/80 Chromasorb W
5' x 1/4" Porapak Q
This assortment of conditions allowed perusal of components ranging in volatility from gases
(CO2 / CH4 , etc.) to those of low volatility (estimated molecular weights up to 400).
There were significant differences observed in the pyrograms. The characteristic peaks were
ostensibly of use in assessing levels of contamination in the soil samples.
Pyrolysis of the soil samples, including the doped references, failed to reveal any contamination
by the surface treatment formulations in all samples. The pyrograms were generally not quanti-
tatively reproducible, apparently due to the large amount of sample required and the resulting
non-uniform heating in the pyroprobe itself. The large amount of pyrolyzable organic matter
in the soil, as well as the variation in its composition, added to the problem.
The lower limit of detection is estimated to be a minimum of 500 ppm. Inability to consistently
observe pyrolysis peaks characteristic of the polymer formulations in both soil and doped soil
samples did not allow a firm lower contamination level to be set.
Experiments were also performed where the pyrolysis product compositions were recorded as a
function of pyrolysis temperature. These efforts were generally unsuccessful in demonstrating
a viable analytical technique for the soil.
172
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PYROLYSIS INFRARED SPECTROSCOPY
An attempt was made to use infrared spectroscopy as a fool to evaluate contamination levels
in soil samples. This method seemed a viable alternative to gas chroma tog raphy because
much larger samples could be pyrolyzed. Raw formulation samples and doped soil samples
were pyrolyzed in an evacuated system connected to an infrared gas cell. However, no
absorptions were obtained which were characteristic of the formulation type, and which
could be observed in the pyrolysis gases from the soil samples.
WATER SOLUBILITY-EXPOSURE TESTS
An alternative to the analysis of soil for contamination was the determination of the suscep-
tibility of the coating formulations to water dissolution. The following experiments were
therefore constructed.
Approximately 20 mil films (wet) of each formulation were made on teflon sheets. These films
were dried at 10.0ฐF for one week. One film of each formulation was then subjected to UV
irradiation fora one year outdoor exposure equivalent, and a remaining film of each was
healed an additional week at 100ฐF . UV exposure was for one week in an ASTM D795/1148
test unit.
The exposed and unexposed films were then removed and subjected to soxhlet extraction for
twenty four hours with distilled water. The water which was in contact with the films was
70 to 80ฐC. These conditions are probably more severe than those encountered by the road
films in a natural environment, but should give good upper limit solubility characteristics.
Data were collected by quantifying the weight loss from each film sample, and the weight
extracted by evaporating the water extracts and quantifying the residue. Results were as
follows:
As Percent of Dry Film Weight
Sample Weight Lost Residue Weight
A Unexposed 1.3 0.6
A Exposed 9.0 6.6
B Unexposed 4.6 0.5
B Exposed 16.7 7.8
C Unexposed 3.8 6.0
C Exposed 5.4 1.7
173
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The results show that there is some water solubility to all three polymer films. Second,
the solubility increases markedly with UV exposure for formulations A and B, but may in
fact decrease for formula C.
If further investigation of the environmental contaminating potential of these three road
treatments is required, we can suggest the following program. First, water soluble compo-
nents of the three films can be isolated and identified. Second, water solubility as a func-
tion of film age can be studied. Third, other conditions of exposure more closely approxi-
mating those actually encountered by the road surface can be used, such as setting up
exposure-wash basins and asphalt coated samples on the roof at Mauser Laboratories where
we have other equipment designed for outdoor exposure testing. With the water solubility
and extracted moieties identified, a program of water (soxhlet) extractions on large soil
samples could be made to assess soil contamination levels.
Dr. Timothy D. Ziebarth, Chief Chemist
174
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DEPT. B5501
APPENDIX B
CONTACT REPORT
(Reference 62)
MSP
ORGANIZATION CONTACTED: Colorado Department of Highways fC. D.H.I
ADDRESS: 4201 East Arkansas Avenue
BY:.
G. H. Ahlborn
Denver. Colorado
ZIP CODE 80202
REF. NO.:.
680-3-03SQ
TIME OF DATE OF 0/01/_, DATE OF _._,,_.
TYPE OF CONTACT El FIELD DAT BBRC D PHONE CONTACT A.M. CONTACT 2/21/74 REPORT 2/21/74
PH<~>NP M",; 759-9266
CONFEREES
B. B. Gerhardt
Bud A. Brakey
Betty Davey
TITLE
Research Engineer
Head Materials' Engineer
Clerk C?) -Accident Report Summaries
PHONE
EXT
757-9267
757-qmi
757-9345
MAILING LIST
YES
NO
ADD
SUMMARY OF DISCUSSION:
Bob Jackman and writer visited the Colorado Department of Highways for
preliminary information on road testing and material application to roads for
the EPA Contract.
A. SPECIFIC DATA/SPECIFICATIONS
Copy of State of Colorado version of EPA Regulation No. 7. This governs
allowable quantities of solvents discharged into atmosphere. Needed
in planning application techniques.
Copy of letter to C.D.H. on powdered glass source and photomicrographs
of same on road surface. May be needed to reduce slackness of other-
wise good coatings.
Copy of latest traffic density map for Denver Metro area. Covers i
sufficient area to be used for primary site selection (for road tests).
ASTM E303-69 governs portable road-skid tester; ASTME274-70 governs
trailer skid road tester; C.D.H. has both items and we may be able to
borrow the portable unit.
C.D.H. maintains accident records and road/weather conditions for most
areas in the state. Betty Davey can supply such information for selec-
ted sites as background data and during road test phase.
We must contact the local C.D.H. maintenance foreman for special road
treatment at selected site(s) during the application phase.
175
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CONTACT REPORT (Continued)
ACTION REQUIRED:
Check weather instrument at Boulder airport and NCAR.
Check composition of Highways 119, 7 and 93 near Boulder.
Library - Get (borrow) copy of ASTM 1973 Parts 10 and 11.
Bob, please write letter of thanks to C.D.H.
DISTRIBUTION:
OEPT. MGR. X
FILE
DIRECTOR
ADDITIONAL
.Tackman
Noble
C.D.H. regards 0.02-0.0'4 gallons per (yd) as "normal" for coat-
ing application. (0.00009 meters to 0.00018 meters in SI units.)
Our original estimates of 250-500 ft2/gallon look close to actual
practice.
"Average" road macrostructure is about 0.04 to 0.06 inches
(AMS) and controls high speed skid resistance. Studs as used
in Colorado tend to reduce this value.
Microstructure controls low speed skid resistance. Studs
increase this roughness value (no numbers cited) and would also
remove coatings. Note, coatings would thus also reduce this and
may create low speed skid problems (see also reference on "How
Tires Wear" in writer's EPA file).
Buck Scott (825-2307) can make cast replicas of highways. We'll
need this during application study.
B. GENERAL COMMENTS
C.D.H. very cooperative and helpful. Feeling seemed to be "select a
site and we'll help as much as possible". Bridge icing seems to be their
biggest worry. This is rather out of the spirit of our contract (opinion
by writer based on EPA report R2-72-125) and I emphasized long stretches
of road. General agreement that Boulder vicinity would be a good test
region if sufficient past history and types of roads can be found in close
proximity.
176
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Adopted: September 13, 1973
Effective Date: November 28, 1973
REGULATION NO;. 7
Regulation to Control the Emissions of
Hydrocarbon Vapors
A.
1. Sections F and G shall apply Statewide.
2. Sections B, E, H, I, and J, shall apply only to designated
air pollution control areas.
3. sections C and D shall apply only to the designated Denver-
Metro air pollution control area.
4. All references to designated air pollution control areas,
throughout this regulation, shall be as shown on page 1.13
of the Commission Regulation No. 1.
B. PETROLEUM PRODUCT STORAGE:
1. The storage of any type of petroleum distillate in any stationary
tank, reservoir, or other container of more than 40,000 gallons
(152,000 liters) shall be in a pressure tank capable of maintaining
working pressures sufficient at all times to prevent vapor loss to
the atmosphere. Said tank, reservoir, or other container shall be
equipped with one or more of the following, properly installed, in
good working order, and properly maintained:
(a) A pontoon-type or double deck-type floating roof, or
internal floating cover, which shall rest on the
surface of the liquid contents and shall be equipped
with a closure seal or seals to close the space
between the roof edge and tank wall. This control
equipment shall be acceptable for said tanks, reservoirs,
or other containers only if any type of petroleum
distillate has a vapor pressure not exceeding 11 pounds
per square inch absolute (568mm.Hg) under actual storage
conditions. All gauging or sampling devices shall be
vapor-tight, except when tank gauging or sampling is
taking place; or
(b) A vapor recovery system, consisting of a vapor gathering
system capable of collecting the hydrocarbon vapors
discharged, together with a vapor disposal system capable
of processing such vapors so as to prevent their emission
to the atmosphere. All gauging and sampling devices shall
be vapor-tight except when gauging or sampling is taking
place.
177
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(c) Other equipment of equal control efficiency, provided the
design and effectiveness of such equipment as documented
is submitted to and approved by the Division.
2. This Section B.I shall also apply to the storage of crude oil
within the designated Denver-Metro air pollution control area.
3. Propane or butane and similar products shall be stored in pressure
tanks maintaining working pressures sufficient at all times to
prevent hydrocarbon vapor loss to the atmosphere, or at refrigerated
low temperature, or in low pressure storage equipped with vapor
collection and compression equipment designed to prevent the loss
of hydrocarbon vapor to the atmosphere.
4. The storage of any petroleum distillate in any stationary storage
vessel of more than 3,500 gallons (13,300 liters) capacity shall
be in a vessel equipped with a permanent submerged fill pipe or
with a vapor recovery system.
C. PETROLEUM DISTILLATE LOADING INTO TANK TRUCKS, TRAILERS, AND OTHER
TRANSPORT VEHICLES:
1. The loading of any type of petroleum distillate into any tank truck,
trailer, or other transport vehicle shall be from a loading facility
equipped with a vapor collection and disposal system or its equivalent,
properly installed, in good working order, and properly maintained.
Also, the loading facility shall be equipped with a loading arm with
a vapor collection adaptor. Said system must also have pneumatic,
hydraulic, or other equivalent mechanical neans to force a vapor-tight
seal between the adaptor and the hatch. A means shall be provided to
prevent drainage of petroleum distillate from the loading device when
it is removed from the hatch of any tank truck, trailer, or other
transport vehicle, or to accomplish complete draining before the
removal. When loading is effected through means other than hatches,
all loading and vapor lines shall be equipped with fittings which
make vapor-tight connections and which close automatically when
disconnected.
2. Vapor recovery may be accomplished by one or more of the following:
(a) A vapor-liquid absorber system where vapor emissions do not
exceed 1.5 pounds (1,000 gallons loaded at 70ฐF, 1 Atmosphere)
(b) Bottom loading (closed hatches) at terminal racks where vapor
emissions do not exceed 1.5 pounds (1,000 gallons loaded at
70ฐF, 1 Atmosphere).
(c) Other equipment where vapor emissions do not exceed 1.5
pounds (1,000 gallons loaded at 70ฐF, 1 Atmosphere) and as
approved by the Division.
178
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3. This section C shall apply only to petroleum distillate loading
facilities where 40,000 gallons or more, averaged over the work
days of any month, are loaded in any one day. Facilities loading
under 40,000 gallons per day, such as bulk plants, shall install
telescoping top-loading equipment, or a demonstrated equivalent,
to provide 97% submerged fill.
4. For the purpose of this regulation, "loading facility" means any
aggregation or combination of petroleum distillate loading equipment
which is (1) owned or operated by one person, and (2) located so
that all the petroleum distillate loading outlets for such aggregation
or combination of loading equipment as encompassed within a circle of
300 feet in diameter.
D. WATER SEPARATION FROM PETROLEUM PRODUCTS:
1. Single or multiple compartment oil and effluent water separation
equipment which receives effluent water containing 200 gallons
(760 liters') or more a day or more of any petroleum product or
mixture of petroleum products from any equipment used for processing,
refining, treating, storing, or handling of petroleum products having
a Reid vapor pressure of 0.5 pound or greater, shall be equipped with
one or more of the following vapor loss control devices, properly
installed, in good working order, and properly maintained:
(a) A solid cover with all openings sealed and the liquid
contents totally enclosed. All gauging and sampling
devices shall be vapor-tight except when gauging or
sampling is taking place.
(b) A pontoon-type or double deck-type floating roof, or
internal floating cover, resting on the surface of the
contents and equipped with a closure seal or seals to
close the space between the roof edge and container
wall. All gauging and sampling devices shall be vapor-
tight except when gauging or sampling is taking place.
(c) A vapor recovery system consisting of a vapor gathering
system capable of collecting the hydrocarbon vapors
discharged and a vapor disposal system capable of
processing such hydrocarbon vapors so as to prevent
their emission to the atmosphere. All container gauging
and sampling devices shall be vapor-tight, except when
gauging or sampling is taking place.
(d) Other equipment of equal or greater efficiency, provided
the design and effectiveness of such equipment as documented
is submitted to and approved by the Division.
2. This section D shall also apply to oil and effluent water separators
used in conjunction with the production of crude oil.
179
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E. PUMPS AND COMPRESSORS:
1. No person may build, install, or permit the building or installation
of any rota'ting pump or compressor handling any type of petroleum
distillate unless said pump or compressor is equipped with mechanical
seals or other equipment of equal efficiency. If reciprocating-type
pumps and compressors are used, they shall be equipped with packing
glands properly installed, in good working order, and properly main-
tained so no emissions occur from the drain recovery systems.
2. This section E shall also apply to pumps and compressors handling
crude oil within the designated Denver-Metro air pollution control
area.
F. WASTE GAS DISPOSAL;
Any waste gas stream containing hydrocarbon compounds from any polymer
process emission source shall be burned at 1,300ฐF (704ฐc.) for 0.3
second or longer, in a direct-flame afterburner or an equally effective
device. The emissions of hydrocarbon vapors from a vapor blowdown
system or emergency relief shall be burned in smokeless flares, or
equipment of equal efficiency, provided the design and effectiveness of
equipment, as documented, is submitted to and approved by the Division.
G. ORGANIC SOLVENTS:
1. No person may discharge into the atmosphere more than 15 pounds of
organic materials in any one day, nor more than 3 pounds thereof in
any one hour, from any article, machine, equipment or other contri-
vances in which any organic solvent or any material containing
organic solvent comes in contact with flame or is baked, heat-cured,
or heat-polymerized, in the presence of oxygen, unless said discharge
has been reduced by at least 85 percent. Those portions of any
series of articles, machines, equipment, or other contrivances designed
for processing a continuous web, strip, or wire which emit organic
materials and use operations described in this subsection 1 shall be
collectively subject to compliance with this subsection.
2. No person may discharge into the atmosphere more than 40 pounds of
organic materials in any one day, nor more than 8 pounds in any one
hour, from any article, machine, equipment, or other contrivance used
under conditions other than described in section 1, for employing,
or applying, any photochemically reactive solvent, as defined in
subsection 10 of this section, or material containing such photo-
chemically reactive solvent, unless said discharge has been reduced
by at least 85 percent. Emissions of organic materials into the
atmosphere resulting from air or heated drying of products for the
first 12 hours after their removal from any article, machine,
equipment, or other contrivance described in this section G shall be
included in determining compliance with this section. Emissions
resulting from baking, heat-curing, or heat-polymerizing as described
in subsection 1 of this section shall be excluded from determination
of compliance with this section. Those portions of any series of
articles, machines, equipment, or other contrivances designed for
processing a continuous web, strip, or wire which emit organic
materials and use operations described in this subsection 2 shall be
collectively subject to compliance with this subsection 2.
180
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3. Ho person may, after December 31, 1974, discharge into the atmosphere
more than 3,000 pounds of organic materials in any one day, nor more
than 450 pounds in any one hour, from any article, machine, equipment,
or other contrivance in which any non-photochemically reactive organic
solvent or any material containing such solvent is employed or applied,
unless said discharge has been reduced by at least 85 percent. Emissions
of organic materials into the atmosphere resulting from air or heated
drying of products for the first 12 hours after their removal from any
article, machine, equipment, or other contrivance described in this
section G shall be included in determining compliance with this
subsection 3. Emissions resulting from-baking, heat-curing, or heat-
polymerizing as described in subsection 1 of this section shall be
excluded from determination of compliance with this subsection. Those
portions of any series of articles, machines, equipment, or other
contrivances designed for processing a continuous web, strip, or wire
which emit organic materials and use operations described in this
subsection 3 shall be collectively subject to compliance with this
section.
4. Emissions of organic materials to the atmosphere from the clean-up,
with photochemically reactive solvent as defined in subsection 10 of
this section, of any article, machine, equipment, or other contrivance
described in subsections 1, 2, or 3, of this section G shall be included
with the other emissions of organic materials from that article,
machine, equipment, or other contrivance for determining compliance with
this section G.
5. Emissions of organic materials into the atmosphere required to be
controlled by subsections 1, 2, and 3 of this section G shall be reduced
by:
(a) Incineration, provided that 90 percent or more of the carbon
in the organic material being incinerated is oxidized to
carbon dioxide,
(b) Adsorption, or
(c) Processing in a manner to be not less efficient than (a) or
(b) above, provided said processing and equipment, as documented,
is submitted to and approved by the Division.
6. A person processing organic materials pursuant to this section G shall
provide, properly installed, in good working order, and properly main-
tained devices as specified in the authority to construct and the permit
to operate, or as otherwise specified by the Division, for indicating
temperatures, pressures, rates of flow, or other operating conditions
necessary to determine the degree and effectiveness of air pollution
control.
7. Any person using organic solvents or any materials containing organic
solvents shall supply the Division, upon request and in the manner
and form prescribed by it, written evidence of the chemical composition,
physical properties, and amount consumed for each organic solvent used.
181
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8. The provisions of this section G shall not apply to:
(a) The manufacture of organic solvents, or the transport
or storage of organic solvents or materials containing
organic solvents.
(b) The use of equipment for which other requirements are
specified by subsections 1, 2, and 3,-of this section G
this regulation, or which are exempt from air pollution
control requirements.
(c) The spraying or other employment of insecticides,
pesticides, or herbicides.
(d) The employment, application, evaporation, or drying of
saturated halogenated hydrocarbons, perchloroethylene, or
trichloroethylene, provided the emission of organic
materials is controlled to less than 40 pounds per day
or 8 pounds per hour.
-------
10. For the purposes of this Regulation No. 7, a photochemically reactive
solvent is any solvent with an aggregate of more than 20 percent of
its total weight composed of the chemical compounds classified below
or which exceeds any of the following individual percentage composition
limitations, referred to the total weight of solvent.
(a) A combination of hydrocarbons, alcohols, aldehydes, esters,
ethers, or ketdnes having an olefinic or cyclo-olefinic type
of unsaturation: 5 percent;
(b) A combination of aromatic compounds with eight or more carbon
atoms to the molecule, except ethylbenzene: 8 percent:
(c) A combination of ethylbenzene, ketones having branched
hydrocarbon structures, trichloroethylene or toluene:
20 percent.
Whenever any organic solvent or any constituent of an organic solvent
may be classified from its chemical structure into more than one of
the above groups of organic compounds, it shall be considered as a
member of the most reactive chemical group, that is, that group having
the least allowable percent of the total volume of solvents.
11. For the purposes of this section Gf organic materials are defined as
chemical compounds of carbon excluding carbon monoxide, carbon dioxide,
carbolic acid, metallic carbides, metallic carbonates, and ammonium
carbonate.
For the purpose of this section G the terms "baked, heat cured, or
heat polymerized" refer to coatings and other organic, solvent
containing materials which;
(a) have been heated in devices in which the air temperature
exceeds 175ฐF (80ฐC), and
(b) which have become insoluble in solvents in which they were
soluble before being subjected to heat.
H. ARCHITECTURAL COATINGS:
1. No person may sell or offer for sale for use in containers of
one quart capacity or larger, any architectural coating containing
photochemically reactive solvent, as defined in subsection 10 of
section G of this regulation.
2. No person may employ, apply, evaporate or dry any architectural
coating, purchased in containers of one quart capacity or larger,
containing photochemically reactive solvent, as defined in
subsection 10 or section G of this regulation.
183
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3. No person may thin or dilute any architectural coating with a
photochemically reactive solvent, as defined in subsection 10
of section G of this regulation.
4. For the purposes of this section H, an architectural coating is
defined as coating used for residential or commercial buildings
and their appurtenances, or industrial buildings.
I. DISPOSAL AND EVAPORATION OF SOLVENTS:
No person may, during any one day, dispose of a total of 1 quart capacity
or larger, any photochemically reactive solvent as defined in subsection
10 of section G of this regulation, or of any material containing 1 quart
or more of any such photochemically reactive solvent by any means which
will permit the evaporation of such solvent into the atmosphere.
J. DRY CLEANING SOLVENTS:
1. No person may operate a drycleaning operation unless the uncontrolled
organic vapor emissions from such operation have been reduced by at
least 85 percent. Drycleaning operations emitting less than 3 pounds
per hour and less than 15 pounds per day of uncontrolled organic
vapors are exempt from this section j.
2. Any owner or operator of a source subject to this section j shall
achieve compliance with the requirements of subsection 1 of this
section j by discontinuing the use of photochemically reactive
solvents as defined in subsection 10 of section G of this regulation,
3. If incineration is used as a control technique, 90 percent or more
of the carbon in the organic compounds being incinerated must be
oxidized to carbon dioxide.
K. DECREASING OPERATIONS:
No person may use for a degreesing operation any photochemically reactive
solvent as defined in subsection 10 of section G of this regulation unless
the emission of organic materials is controlled to less than 40 pounds per
day or 8 pounds per hour.
L. EFFECTIVE DATE:
Except as otherwise stated in this regulation, said regulation shall become
effective November 28, 1973, as to new sources of hydrocarbon vapor emissions
and effective December 31, 1974 as to existing sources, except that acceptable
compliance schedules and permit applications for all existing sources affected
by this regulation must be received by the- Division by no later than March 1,
1974.
184
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(General References)
February 1, 1974
Mr. Bob Jackman
Ball Brothers Research Corp.
Box 1026
Boulder, Colorado 80302
Dear Mr. Jackman:
Confirming your telephone inquiry yesterday, we are
Pleased to send you, under separate cover, samples of
the following cat ionic materials which may meet your
requirements for application on forming hydrophobic
road surfacing:
Chemical 39 Base
Chemical 39 High Cone
Chemical 39S
Ceranine HCA Granules
Ceranine PNS Granules
Cartaretin F-4
Cartaretin F-8
Cartarex FL
Viscospin B
We have learned that Viscospin B is being used at a
concentration of 30% in kerosene as an additive to
asphalt for the purpose in which you are interested.
Unfortunately we have no data on this application.
If in your evaluations we can be of any technical
assistance, please do not hesitate to contact us.
Thank you for your interest in our products.
Very truly ,/yurs,
Herman Bryvm
HB/db SANDOZ Colors & Chemicals
Enclosures (8)
185
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CONTACT REPORT
DEPT. B5501
MSP
ORGANIZATION CONTACTED: Goodyear Chemical
ADDRESS:
RV- G. H. Ahlborn
ZIP CODE
REF. MO. 680-5-0359
TYPE OF CONTACT Q FIELD D AT BE
PwnK|P Mn- (714) 523-9770
CONFEREES
Jack Ellis
TIME OF ..... DATE OF _.,, DATE OF . .
RC H PHONE CONTACT 1140 CONTACT 5/21/74 RFPflRT 5/21/74
TITLE EXT
Senior Sales Representative
MAILING LIST
YES NO ADD
SUMMARY OF DISCUSSION:
Jack called to check on the potential of the FED. SPEC. TT-D-115D
traffic paint sample I requested. I explained the EPA program and our
thought of using proven traffic paints as binders for hydrophobic materials.
He seems quite interested and offered any help possible.
General Impression from Goodyear and Ashland Contacts: The paint people
seem quite enthusiastic about this.
ACTION REQUIRED:
None - Possible visit in July.
\
DISTRIBUTION:
DEPT. MGR.
FILE
DIRECTOR
186
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CONTACT REPORT
DEPT. B5501 M 5 P
ORGANIZATION CONTACTED: Phillips Petroleum Company. Chemical Division
ADDRESS: 1505 Phillips Building
RV- fi. H. AhlhriT-n
Bart..Oklahoma
ZIP CODE 74004
REF. MO- 680-5-0359
TIME OF DATE OF ,,,_._. DATE OF
TYPE OF CONTACT l~1 FIFI n l~l AT PRRP R1 PHOMF CONTACT 1400 CONTACT 6/17/74 RFPDRT 6/17/74
PMOMP Nn. f918) 661-5538
CONFEREES TITLE P"ฐ|IE
Jim Dykes
SUMMARY OF DISCUSSION:
Called Phillips to check on their bridge surface coating.
The coating used in their TV AD is "Petromat"ฎ and consists of
MAILING LIST
YES NO ADD
a polydro-
pylene film impregnated with binders and laid down when the roadway (bridge)
surface is first applied. Does not appear applicable to our EPA Contract
which stresses the treatment of existing, road surfaces.
However, Mr. Dykes mentioned a rubber emulsion that Phillips has used on
their ewn runway. Said emulsion -- when used with a normal asphalt seal coat --
reportedly shows great differences in ice accumulation when compared to un-
treated runway sections. Material is designated "Petroset AT"ฎ.
Mr. Dykes is sending a one-gallon sample and literature.
ACTION REQUIRED:
Test material - If_ time permits.
DISTRIBUTION:
DEPT. MGR.
FILE
Dl RECTOR
ADDITIONAL
CRN
Poehlmann
Rnl 1 PT
187
-------
CONTACT REPORT
DEPT. R52fU M g P
ORGANIZATION CONTACTED: Phillips Petroleum Co.T Chemical Division
ADDRESS: 1505 Phillips Building
BY:.
G. H. Ahlborn
Bart. Oklahoma
TYPE OF CONTACT Q FIELD Q AT BE
PHoNE Mn- T9181 661-5538
CONFEREES
Lou Grey
SUMMARY OF DISCUSSION:
Mr. Grey called due
Explained application.
Mr. Grey reported t
(406) 442-2092) in wint
adhesion of snow and pr
roads .
Rate of application
or about 3/1 our planne
Mr. Grey also recoir
water. Thi-s, to avoid
Petroset AT after dilut
TIME OF ,,nn DATE OF 1n/7q DATEOF1n/oQ
RC m PHONE rnwTAnT liuu CONTACT LO/W RFPDRT 10/^9
TITLE PHONE
TITLE ฃXT
Tech. Representative
MAILING LIST
YES NO ADD
to our recent purchase of a drum oฃ Petroset AT.
hat a test at Wolfcreek, Montana (Contact: Lehman Fox
er of 1971-72, Petroset AT greatly reduced the
evented the formation of frost on treated asphalt
was 0.3 gal/yd2 for this test. This is 1.35 1/m2
d rate of 0.4 1/m2.
mended application within 8-10 hours of dilution with
the "precipitation" we have observed for stored
ion. Also, keep water slightly acid.
ACTION REQUIRED:
Call Mr. Fox, maybe, for report.
Consider uping Petroset AT application rate.
DISTRIBUTION:
DEPT. MGR.
FILE
DIRECTOR
ADDITIONAL
nUJr
188
-------
00
eo
Figure C-l Location of Boulder Test Area in Relation to Denver Metropolitan
Area
C/3
M
1-3
W
C/3 H
. M
ฃ n
-------
X.
E
ROAD PHASE H
"
ฃ'" HIGHWAY)? FJHASE IE TEST
^4/ HIGHWAY 36
SITE.
Sr-EAST
w
0
p
H
CO
P
(/)
0
H
rt
ซ
in
<
fn
-------
WEST BOUND TRAFFIC
ASPHALT
3.66m
-M2FT1-
CONCRETE
SHOPPING CENTER
ENTRANCE AND EXIT
n
3.05m
(IOFT)
0.61m
(2 FT)
EAST BOUND TRAFFIC _
5,200/UNE/DAY
ARAPAHOE ROAD
Figure C-3 Configuration oฃ Arapahoe Road Test Site
BACK PARKING LOT
(ASPHALT)
PHASE 4
EACH SECTION
3m X J.44m
(IOFTX8FT) *
U;
2
fs.
4
'*"
A
'%.
ฅ
*',
'%:
ฃ
-if'
*:
-*"
ป;
'$
'K.
fe
;S"
EACH SECTION
2.44m XL5m
(8 FT X 5FT)
TECH I
TECH H
'.i:
|[
S
J'
10
PHASE I
AND
PHASE E
||
EACH SECTION
OSI5mX0.9l5m
OFT X3FT)
TECH 11
COMMERCE ST
Figure C-4 Configuration of BBRC Test Site
191
-------
EAST BOUND TRAFFIC
DIVIDER
LANE I
LANE 2
LANE 3
.7.32m.
(24 FT)
|<_45.75m J-
(150 FT)
-61.0m
(200 FT]
_45.75m jf-
(150 FT)
WEST BOUND TRAFFIC
-91.50m
(300FT)
45.75m-
[150 FT)
2510/LANE/DAY
HIGHWAY 7
Figure C-5 Configuration of Highway 7 Test Site
EAST BOUND TRAFFIC
DIVIDER
1 45.75 iii-
USO FT)
LANE 2
WEST BOUND TRAFFIC
5,500/LANE/OAY
HIGHWAr 36 CONCRETE
Figure C-6 Configuration of Highway 36 Concrete Test Site
192
-------
EAST BOUND TRAFFIC
DIVIDER
LANE 2
WEST BOUND TRAFFIC
5,500/LANE/DAY
HIGHWAY 36- ASPHALT
Figure C-7 Configuration of Highway 36 Asphalt Test Site
WEST BOUND TRAFFIC
(100 FT)
(IDOFT1
(100 FT)
PEARL STREET
Figure C-8 Configuration of East Pearl Street Test Site
193
-------
APPENDIX D (Reference 63)
COLORADO HIGHWAY DEPARTMENT ACCIDENT REPORTS
STATE OF COLORADO
DIVISION OF HIGHWAYS
E. N. HAASE
CHIEF ENGINEER
C
COLORADO STATE PATROL
COL. C. WAYNE KEITH,
CHIEF
4201 EAST ARKANSAS AVENUE DENVER, COLORADO 8O222 (3O3) 757-9O1I
File Nos. TRAFFIC
880.007.02 (Accidents)
880.036.02
813.31.1
October 4, 1974
Mr. G. H. Ahlborn
Member Technical Staff
Ball Brothers Research Corporation DOH File 16-01
P. 0. Box 1062
Boulder, Colorado 80302
Dear Mr. Ahlborn:
In response to your letter of September 19, 1974, we have checked accident
experience on SH 36 from 1,3 mile west of Jet. SH 157 to the Cherryvale Road
underpass and on SH 7, from 1.0 mile west to 1,0 mile east of the intersection
of Commerce Street for the periods November 1, 1972 to April 1, 1973 and
November 1, 1973 to April 1, 1974. Enclosed for your information and use are
traffic accident summary sheets for both locations. Also enclosed is a
memorandum that explains the Relative Accident Severity Index.
If we can be of additional assistance, please contact us.
Yours very truly,
E. N. HAASE
Chief Engineer
WET:bn
Encl.
cc: D. M. Bower w/encl.
File
By
- -' "7-
.<- - .-/fi
WM. E. TUCKER
Staff Traffic Engineer
194
-------
TOH Form 'No. 404
Rev. May, 1974
STATE DEPARTMENT OF HIGHWAYS
DIVISION OF HIGHWAYS
STATE OF COLORADO
Staff Traffic and Traffic Safety Division
SUMMARY OF TRAFFIC ACCIDENT EXPERIENCE
File No. 880.007.02
Sheet
of
Date October 4. 1974
LOCATION; SH 7, from 1.0 mi. W. to 1.0 mi. E. of the Int. of Commerce Street (2.0 miles)
PERIOD: From November 1, 1972
I.
II.
November 1, 1973
NUMBER OF ACCIDENTS REPORTED
One-car accidents 6_
Two-car accidents 21
Three or more cars 3
Total
SEVERITY
Persons killed
Persons injured
Fatal accidents
Injury accidents
Property damage only
Total
III. TYPES OF ACCIDENTS
Collision
Pedestrian
Head-on
Rear-end
Broadside
Sideswipe S.D.
Sideswipe O.D.
Approach turn
Overtaking turn
Fixed object (curb)
Parked car
Animal
Train
30
30
10
5
3
ToApril 1, 1973
April 1, 1974
III. (Continued)
Noncollision
Overturned on road
Ran off road
VII.
Total
IV. ESTIMATED ECONOMIC LOSS
Deaths
-------
DOH Form No. 404
Rev. Kay, 1974
STATE DEPARTMENT OF HIGHWAYS
DIVISION OF HIGHWAYS
STATE Or COLORADO
Staff Traffic and Traffic Safety Division
SUMMARY OF TRAFFIC ACCIDENT EXPERIENCE
File No. 880.036.02
Sheet * of
Date October 4,
1974
LOCATION; US 36, from 1.3 mi. W. of Jet. SH 157, to Str. E-16-FE (Cherryvale Rd. Underpass)
(2.7 miles) ' ' ~~
PERIOD: From November 1, 1972
To April 1, 1973
II.
November 1, 1973
NUMBER OF ACCIDENTS REPORTED
One-car accidents 28
Two-car accidents 13
Three or more cars 2
Total 43
SEVERITY
Persons killed
Persons injured
Fatal accidents
Injury accidents
Property damage only
Total
April 1, 1974
III. (Continued)
Noncollision
Overturned on road
Ran off road
Other noncollision
Total
IV. ESTIMATED ECONOMIC LOSS
Deaths
-------
File No. '813.51 TRAFFIC
DIVISION OF HIGHWAYS (Accidents)
STATE OF COLORADO
4201 E. Arkansas Ave.
D ENVER, COLORADO 80222
March 14, 1974
TO: District Engineers
FROM: M. A. Kahra DOH File 14-09
SUBJECT:- Relative Accident Severity Index
Enclosed for your information is a listing by accident type of the estimated economic
loss (EEL) per accident and the Relative Accident Severity Index (RASI), RASI is the
quotient of the EEL for the specific accident type and the largest value for EEL deter-
mined by this study -- for TRAIN accidents, EEL = $8391.98/accident.
RASI provides a measure of the relative severity potential of the various accident
types; for example, TRAIN accidents are approximately six times as severe as collisions
with a MEDIAN BARRIER, and HEAD-ON accidents are 4.5 times as severe as REAR-END
collisions. In the future, RASI will be included in certain accident studies and
Safety Improvement Project justifications to describe the severity potential of the
various accidents which occurred. This information will supplement the usual accident
data and hopefully result in an even more effective distribution of corrective action
efforts.
M. A. KAHM
Planning and Research Engineer
.MAK:bn
Encl.
cc: Shuraate-Haase-Capron-Cox w/encl.
All District Traffic and Safety Engineers w/encl.
M. A. Kaha w/encl.
Angelo J. Siccardi .w/encl. (3)
Cordell Smith w/encl.
R. F.
File
197
-------
File.SftJ. 813.51 .March 12, 1974
STATE DEPARTMENT OF HIGHWAYS
DIVISION OF HIGHWAYS - STATS OF COLORADO
PLANNING AND RESEARCH DIVISION - TRAFFIC ENGINEERING SECTION
Relative Accident Severity Index (RASI)
Accident Type
TRAIN
PEDESTRIAN
HEAD-ON
BRIDGE ABUTMENT
BICYCLE
OVERTURNED ON ROAD
RAN OFF ROAD
BRIDGE RAIL
GUARDRAIL
CURB
OTHER
OTHER NON-COLLISION
APPROACH TURN
UNDERCROSSING COLUMN
LIGHT POLE
BROADSIDE
GUARD POST
MACHINERY
TRAFFIC SIGNAL POLE
MEDIAN BARRIER
(based on 1972 accident
7ป of All Accidents
0.1
1.2
1.8
0.2
1.1
0.9
13.2
0.4
0.6
1.2
0.1
0.5
4.8
0.1
0.1
17.7
0.7
0.1
0.2
0.4
SIDESWIPE -OPPOSITE DIR. 2.8
UTILITY POLE
REAR END
BARRICADE
ROCKS IN ROADWAY
SIGN
OVERTAKING TURN
ANIMAL
OTHER OBJECT
PARKED MOTOR VEHICLE
SIDESWIPE-SAME DIR.
FENCE
0.1
24.0
0.2
0.2
0.2
3.1
1.9
0.6
13.0
8.4
0.1
data)
*EEL/Accident
$8391.98
6763.05
6053.09
4791.87
4120.01
3777.50
3340.65
2990.53
2888.34 ,
2627.17
2445.96
2368.40
2282.49
2118.61
1897.52
1834.64
1779.98
1764.59
1469.09
1410.28
1401.22
1393.68
1381.93
1289.47
1163.37
1160.82
1053.89
1007.59
933.05
873.58
800.92
727.22
RASI
1.00
0.81
0.72
0.57
0.49
0.45
0.40
0.36
0.34
0.31
0.29
0.28
0.27
0.25
0.23
0.22
0.21
0.21
0.18
0.17
0.17
0.17
0.16
0.15
0.14
0.14
0.13
0.12
0.12
0.10
0.10
0.09
TOTAL, STATEWIDE 100.0 1885.96 0.22
* Estimated Economic Loss per Accident
198
-------
(Reference 64)
STATE DEPARTMENT OF HIGHWAYS
CHAS. E. SHUMATE
EXECUTIVE DIRECTOR
STATE OF COLORADO
DIVISION OF HIGHWAYS
E. N. HAASE
CHIEF ENGINEER
COLORADO STATE PATROL
COL- C' WAYNE KEITH.
CHIEF
42O! EAST ARKANSAS AVENUE DENVER, COLORADO 8O222 (3O3) 757-9O11
File Nos. 813.31.1 TRAFFIC
880.007.02 (Accidents)
880.036.02
June 6, 1975
Mr. G. H. Ahlborn
Member, Technical Staff
Ball Brothers Research Corporation
P. 0. Box 1062
Boulder, Colorado 80302
DOH File 16-01
Dear Mr. Ahlborn:
In response to your telephone request June 5, 1975, we have checked
accident experience on SH 36, from 1.3 miles west of Jet. SH 157 to
the Cherryvale Rd. underpass and on SH 7, from 1.0 mile west to 1.0
mile east of the intersection with Commerce St. for the period
November 1, 1974 to April 1, 1975. Enclosed for your information
and use are accident summary sheets. This information is supplemental
to that provided in our letter dated October 4, 1974.
Yours very truly,
E. N. HAASE
Chief Engineer
By
WM. E. TUCKER
Staff Traffic Engineer
WET:jmw
Encls.
cc: D. M. Bower w/encls.
File
199
-------
DOH Form No. 404
Rev. January 1975
STATE DEPARTMENT OF HIGHWAYS
DIVISION OF HIGHWAYS
STATE OF COLORADO
Staff Traffic and Traffic Safety Division
SUMMARY OF TRAFFIC ACCIDENT EXPERIENCE
File No. 880.007.02
Sheet 1
Date June 6,
of 1
1975
LOCATION; SH 7. from 1.0 ml. W. to 1.0 mi. E. of the intersection of Commerce Street
(2.0 miles)
PERIOD: From
November 1. 1974
I.
II.
III.
NUMBER OF ACCIDENTS REPORTED
One-car accidents 1
Two-car accidents
Three or more cars
Total
SEVERITY
Persons killed
Persons injured
Fatal accidents
Injury accidents
Property damage only
Total
TYPES OF ACCIDENTS
Collision
Pedestrian
Head-pn
Rear-end
Broadside
Sideswipe S.D.
Sideswipe O.D.
Approach turn
Overtaking turn
Fixed object
Parked car
Animal
Train
8
10
10
To
April 1. 1975
III. (Continued)
Noncollision
Overturned on road
Ran off road
Total
IV. ESTIMATED ECONOMIC LOSS
Deaths @ $90,000
Injuries @ $ 3,700
Vehicle property damage *
Other property damage
Total
V. LIGHT
Daylight
Dark, highway i^ot lighted
Dark, highway lighted
VI. ADVERSE CONpITIONS
Weather -- raining
-- snowing
Road
VII. DRIVER
wet
-- snowy
- icy
unknown
10
$ 90,000
$ ?_
$ 5,255
$ 9_
$ 95,255
"Apparently Asleep"
"Drinking - Under the Influence"
"Driving over safe speed
for existing road, weather,
and light conditions"
COMMENTS;
During the study period there were 10 reported accidents resulting in one
fatality. The total estimated economic loss was $95,255.
* Estimated at $500 per accident if not stated on the report.
200
-------
DOH Form No. 404
Rev. January 1975
STATE DEPARTMENT OF HIGHWAYS
DIVISION OF HIGHWAYS
STATE OF COLORADO
Staff Traffic and Traffic Safety Division
SUMMARY OF TRAFFIC ACCIDENT EXPERIENCE
File No. 880.036.02
Sheet_
Date
of
June 6, 1975
LOCATION; US 36, from 1.3 mi. W. of Jet. SH 157 to Str. E-16-FE (Cherryvale Rd. Underpass)
(2.7 miles)
PERIOD: From November 1. 1974
I. NUMBER OF ACCIDENTS REPORTED
One-car accidents
Two-car accidents
Three or more cars
Total
II. SEVERITY
Persons killed
Persons injured
Fatal accidents
Injury accidents
Property damage only
Total
III. TYPES OF ACCIDENTS
Collision
Pedestrian
Head-on
Rear-end
Broadside
Sideswipe S.D.
Sideswipe O.D.
Approach turn
Overtaking turji
Fixed object
Parked car
Animal
Train
10
16
To
IV.
V.
VI.
April 1. 1975
III. (Continued)
Noncollision
Overturned on road
Ran off road
Total
ESTIMATED ECONOMIC LOSS
Deaths @ $90,000
Injuries @ $ 3,700
Vehicle property damage *
Other property damage
Total
LIGHT
Daylight
Dark, highway not lighted
Dark, highway lighted
ADVERSE CONDITIONS
Weather raining
-- snowing
Road
-- wet
snowy
icy
VII.
16
0
14,800
11,525
350
26,675
11
DRIVER
"Apparently Asleep"
"Drinking - Under the Influence"
"Driving over safe speed
for existing road, weather,
and light conditions"
COMMENTS!
During the study period there were 16 reported accidents resulting in four injuries.
The total estimated economic loss was $26,675. The fixed objects struck included
eight median barriers and one sign.
* Estimated at $500 per accident if not stated on the report.
201
-------
GLOSSARY
All technical concepts employed in this research report are de-
fined in conceptual or mathematical terms where they are first
used. The intent of this glossary is to introduce necessary
concepts and terms in, sd far as possible, non-technical
language.
Adhesion: The sticking tendency of unlike substances, such as
ice to coatings or coatings to surfaces.
Cohesion: The tendency of a single material to hold together,
such as the cohesive strength of ice or the cohesive-
ness of a coating.
Biological (Biochemical) Oxygen Demand (BOD): The degree to
which organic contaminants, when introduced into
water, deplete the dissolved oxygen thus depriving
living vegetation and animal life of this substance.
Chemical Oxygen Demand (COD): The total tendency of all
materials in a water sample to react with dissolved
oxygen thus reducing its availability.
Contact Angle: A measure of the "steepness" of the edge of a
fluid drop with the surface on which it is resting.
For example, water has a high contact angle on a good
car polish.
Deicing Chemicals: As employed in this report, these are
chemicals which "dissolve" ice by being very highly
soluble in water and thus greatly lowering its freez-
ing point.
Dispersion (London) Dipole Forces: Attractive (adhesive)
forces acting over fairly long distances caused by
molecules having magnetic fields. The effect is
similar to the way a bar magnet and a piece of iron
are attracted to each other.
Hydrophobic: Literally, a surface or material property meaning
"hates water". As here employed, it means the rejec-
tion of water by all means including insolubility,
high contact angles, resistance to water vapor and non-
reactiveness with water.
202
-------
Hydrophilic: A surface or material property meaning "likes
water". _ As here used, it means having the reverse
of any of the hydrophobia characteristics listed
above.
Icephobic: A recently coined word describing the ability of a
surface or material to (mechanically) reject ice as
a solid. Thus deicing chemicals, for example, are not
icephobic.
Oleophilic: Literally, likes (attracts) oil. Practically,
oleophilic materials are mutually soluble in oil-like
(in the present case limited to hydrocarbons) sub-
stances. Oleophilic materials are generally hydro-
phobic except where, as in surface active agents with
both hydrocarbon (oleophilic) and water-soluble
(hydrophilic) "ends", molecular orientation is con-
trolling.
Surface Active Agents: Materials which, due to the structure
of the molecule, have "ends" attracted to chemically
different surfaces. They are defined by the charge
of the hydrophobic (hydrocarbon or other type) portion
of the molecule. Thus, soaps like sodium (+) stearate
(-) are called "anionic" since the stearate is nega-
tively charged and is attracted to a positive anode.
Of specific interest here is the practical ability of
surface-active agents to orient themselves on a sur-
face leaving a single type of end protruding. This
changes the wetting characteristics of the surface.
Surface Energy: As here used, a property of a surface con-
trolled by the molecular types outermost on that sur-
face and affecting the wetting by water and the con-
tact angle of water on said surface. For example,
tetrafluoroethylene (TFE) has CF3-and-CF2-groups outer-
most, has low surface energy and is not wet by water
(which also exhibits a very high contact angle on
TFE) .
Surface Tension: The film "strength" of a fluid causing it to
form small droplets. Water is high while gasoline is
low. Low surface tension materials wet better and
have lower contact angles than do high surface ten-
sion materials. This property is controlled by molecu-
lar type and structure.
Wetting: A complex phenomenon involving energy/tens ion
balances, solubility effects and surface/test condi-
tions. Good wetting is characterized by low contact
angles and (usually) high adhesion.
203
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-242
2.
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
DEVELOPMENT OF A HYDROPHOBIC
PAVEMENT ICE ADHESION
SUBSTANCE TO MITIGATE
5. REPORT DATE
December 1976 (Issuing Date)
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
G.H. Ahlborn
H.C. Poehlmann, Jr.
!. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Ball Brothers Research Corporation
P.O. Box 1062
Boulder, Colorado 80302
10. PROGRAM ELEMENT NO.
1BC611
11. CONTRACT/SWWWr NO.
68-03-0359
12. SPONSORING AGENCY NAME AND ADDRESS
Municipal Environmental Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final 1/74 to 10/75
14. SPONSORING AGENCY CODE
EPA-OKD
15. SUPPLEMENTARY NOTES
PO: Hugh Masters
16. ABSTRACT
This research was undertaken to investigate the feasibility of the use of hydro-
phobic substances on highway and bridge deck surfaces to reduce ice adhesion.
Such a coating could reduce or eliminate the possibility of pollution of ground
water by currently-used deicing chemicals and the multi-billion dollar yearly
cost of automotive frame, bridge deck and highway surface deterioration caused
by such chemicals.
The research program herein described was conducted in four phases and, in addi-
tion to the basic technical evaluation, included consideration of all aspects of
prospective coatings such as cost effectiveness, pollution potential, application
techniques, effective life and detailed characterization of the formulations and
chemicals employed.
The feasibility of this approach is demonstrated with three coatings showing
practical promise. Specific recommendations are presented to optimize the con-
cepts developed in this program.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Deicers
Ice Control
Ice Breakup
Water Pollution
Pavements
Economic Analysis
Environmental Impact
Hydrophobic Materials
Pavement Deicers
Water/Ice Phobicity
13B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
218
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
204
&U.S. GOVERNMENT PRINTING OFFICE: 1977-757-056/51(116 Region No. 5-II
------- |