WATER POLLUTION CONTROL RESEARCH SERIES  11024 EQE 06/71
   Impregnation of Concrete Pipe
ENVIRONMENTAL PROTECTION AGENCY • WATER QUALITY OFFICE

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                   WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Reports describe the results and progress
in the control and abatement of pollution of our Nation's waters.  They provide
a central source of information on the research, development and demonstration
activities of the Water Quality Office of the Environmental Protection Agency,
through in-house research and grants and contracts with the Federal, State
and local agencies, research institutions, and industrial organizations.

Previously issued reports on the Storm and Combined Sewer Pollution Control
Program:
11023 FDB 09/70
11024 FKJ 10/70
11024 EJC 10/70

11023 	 12/70
11023 DZF 06/70
11024 EJC 01/71
11020 FAQ 03/71
11022 EFF 12/70

11022 EFF 01/71
11022 DPP 10/70
11024 EQG 03/71

11020 FAL 03/71
11024 FJE 04/71
11024 DOC 07/71
11024 DOC 08/71

11024 DOC 09/71

11024 DOC 10/71
11040 QCG 06/70
11024 DQU 10/70
Chemical Treatment of Combined Sewer Overflows
In-Sewer Fixed Screening of Combined Sewer Overflows
Selected Urban Storm Water Abstracts, First Quarterly
Issue
Urban Storm Runoff and Combined Sewer Overflow Pollution
Ultrasonic Filtration of Combined Sewer Overflows
Selected Urban Runoff Abstracts, Second Quarterly Issue
Dispatching System for Control of Combined Sewer Losses
Prevention and Correction of Excessive Infiltration and
Inflow into Sewer Systems - A Manual of Practice
Control of Infiltration and Inflow into Sewer Systems
Combined Sewer Temporary Underwater Storage Facility
Storm Water Problems and Control in Sanitary Sewers -
Oakland and Berkeley, California
Evaluation of Storm Standby Tanks - Columbus, Ohio
Selected Urban Storm Water Runoff Abstracts, Third
Storm Water Management Model,  Volume 1 - Final Report
Storm Water Management Model,  Volume II - Verification
and Testing
Storm Water Management Model,  Volume III -
User's Manual
Storm Water Management Model,  Volume IV - Program Listing
Environmental Impact of Highway Deicing
Urban Runoff Characteristics
                                    To be continued on inside back cover...

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            IMPREGNATION OF CONCRETE PIPE
                                for the

                  WATER QUALITY OFFICE
          ENVIRONMENTAL PROTECTION AGENCY
                                 by

                  Southwest Research Institute
                        8500 Culebra Road
                   San Antonio, Texas 78228
                       Program  11024 EQE
                       Contract #14-12-835
                            June   1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price 75 cents
                           Stock Number 5501-0601

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           EPA Review Notice
This report has been reviewed by the Water
Quality Office, EPA, and approved for pub-
lication.  Approval does not signify that the
contents necessarily reflect the views and
policies  of the Environmental Protection
Agency,  nor does mention of trade names or
commercial products constitute endorsement
or recommendation  for use.
                    11

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                          ABSTRACT

This program was undertaken to investigate methods to increase the
corrosion resistance, increase the strength, and reduce the permeabil-
ity of concrete used in sewer line applications by impregnating the
concrete pipe with relatively low cost resins such as asphalt,  coal tars,
linseed oil,  sulfur, urea-formaldehyde, and others.

Methods to  accomplish this end were achieved and the materials, tech-
niques of application, test results  and economics are presented in this
report.  A large number of candidate impregnation materials were
obtained and carefully screened both in the laboratory and in limited
field tests.   Test specimens were  cut from commercial grades of con-
crete pipe and physical property tests were made on the treated specimens
both before and after they were subjected to degrading  environments
created to simulate,  but at an accelerated rate,  the environment that
concrete may be subjected to in sewer applications.  Specimens impreg-
nated with sulfur or 5. 0% hydrofluoric acid had  scaling rates  of 0. 0005
to 0. 00017 respectively as opposed to 0. 005 in. /day for the concrete
control when subjected to a three day exposure in 10%  sulfuric acid.
This indicates 10 to 30 times greater corrosion  resistance than untreated
concrete pipe.  Six other materials, including vinyl-vinylidene chloride,
vinyl acetate-acrylic, nitrile rubber latex, nitrile-phenolic rubber,  an
emulsified reclaimed rubber,  and  a  rubber base adhesive, although
failing to impregnate the concrete, formed surface coatings having ex-
ceptional resistance  to the 10% sulfuric  acid.

Sections of  commercial concrete sewer pipe were given applications of
these eight  different treatments and  placed in severe corrosive sewer
environments in sites provided by  the City of Harlingen,  Texas, the
City of San Antonio, Texas,  and a  site on Southwest Research Institute
grounds over the winter of 1970-71.  Preliminary results from these
tests  indicate that these eight different treatments are  functioning
effectively and are thus worthy of further long term evaluation.

This report was submitted in fulfillment of Program No. 11024 EQE,
Contract No. 14-12-835, under the sponsorship of the Water Quality
Office, Environmental Protection Agency.
Key Words:    Concrete Pipe, Impregnation, Hydrogen Sulfide Attack,
               Acid Attack, Sulfate Attack,  Coatings,  Chemical Resis-
               tance of Concrete.
                                111

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                             CONTENTS







Section                                                         Page





  I       Conclusions                                             1





  II      Recommendations                                       3




  III      Introduction                                             5





  IV      Background                                             7





  V      Literature Search                                      13




  VI      Initial Laboratory Screening of Materials                15




  VII     Optimization of Materials and  Procedures               33




  VIH    Preliminary Field  Tests                                41




  IX      Significance of Laboratory and Field Findings           45





  X      Economics                                             49




  XI      Acknowledgements                                     55




  XII     References                                            57




  XIII    Appendices                                            59

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                          LIST OF FIGURES

                                                                 Page
1.      Cross Section of Concrete Sewer Pipe Under Typical          8
       Corrosion Conditions.

2.      Corrosion of the Floor of a Concrete Lift Station.              10

3.      Preferential Acid Attack on Limestone Aggregate by          11
       Industrial Wastes.

4.      Water Absorption as  a Function of Time  Under Varying        16
       Conditions of Vacuum and Pressure for 18 in. Diameter
       Concrete  Pipe.

5.      Preferential Attack of Limestone Aggregate in Laboratory.    19

6.      Scaling of Concrete Pipe as a Function of Sulfuric Acid        20
       Concentration.

7.      Corrosion Caused by 1,  5, and 10% Sulfuric Acid Solutions    22
       After Three-Days' Exposure.

8.      Extended  Exposure of Concrete to  10% Sulfuric Acid.          23

9.      Treatment Plant Corrosion Caused by Citrus and Tomato      27
       Acid.

10.    Flexural Strength as  a Function of Pipe Age for  Sulfur Im-    36
       pregnated Concrete.

11.    Flexural Strength of Impregnated  Concrete as a  Function      37
       of Sulfur Temperature.

12.    Staining of Concrete by Sodium Sulfide Solution.                44

13.    Surface Attack of Sulfuric Acid.                               46

14.    Selling  Price as a Function of Pipe Diameter for Various      50
       Types of Sewer Pipe.
                                 VI

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                            TABLES
.No.                                                             Page

 1.      Properties and Corrosion Resistance of Promising          31
         Concrete Treatments

 2.      Performance of Selected Double-Treated Specimens         .35

 3.      Absorption and Strength of Sulfur Impregnated Concrete     39
         Pipe at 30 Psig Pressure

 4.      Relative Economics of Treating Concrete Pipe              52
                              Vll

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                            SECTION I

                         CONCLUSIONS

1.     Improvements in the corrosion resistance, impermeability and
      strength of concrete pipe can be  achieved by impregnation.   The
      importance of these improvements from an applications stand-
      point rank in the  order given.

2.    Although a number of materials improved the  corrosion resist-
      ance of cured concrete pipe,  (Appendix A) the most promising
      impregnation materials found were a 5% solution by weight  of
      hydrofluoric acid,  sulfur and a modified sulfur formulation.

          The concrete pipe  control specimen when subjected
          to sulfuric acid for 3 days suffered a scaling rate
          (wall loss) of 0. 005 in. /day.   The flexural strength
          of the concrete was found to be 1160 psi.
          The concrete specimen impregnated with  a 5%  solution
          of hydrofluoric acid when subjected to the same test
          as above suffered scaling of 0.00017 in. /day.  The
          flexural  strength was 1050 psi.

          A  concrete specimen impregnated with a modified
          sulfur formulation when subjected to the same test
          as above, suffered scaling of 0.0005 in./day. The
          flexural  strength was 2800 psi.  In addition,  the water
          absorption of the concrete was reduced from 5% to
          0% when impregnated with sulfur.

3.    Three  days submergence in 10% sulfuric  acid is  an extremely
      severe test for concrete. A solution of 10% sulfuric acid is the
      most corrosive concentration as shown below:

                Sulfuric Acid                  Scaling
                Concentration
                 (% by wt. )                    (in. /day)
                    0.1                        0.00025
                    0.5                       0.0008
                    1.0                        0.0015
                    5.0                       0.004
                   10.0                       0.0054
                   30.0                       0.0015
                   50.0                        0.0007
                   98.0                       0.0

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t.     Although maximum sulfuric acid concentrations of approximately
      5% have been determined in certain sewer lines, the maximum
      scaling rate uncovered in the literature has been 0. 5 in. /yr  or
      0. 0014 in. /day.  This is the same scaling rate obtained in the
      laboratory using a 1% sulfuric acid.  Thus, it would appear that
      1%  sulfuric  acid could simulate the most severe environment
      expected in the field.  This  should be examined further.

 5.    Before reliable predictions  can  be made on the durability of
      impregnated concrete pipe,  good correlations must be established
      between laboratory experiments and field performance.

 6.    Materials which failed to impregnate concrete,  but which formed
      good surface coatings included latexes of vinyl-vinylidene chloride,
      vinyl acetate-acrylic, nitrile-phenolic, nitrile rubber,  a  rubber
      base adhesive, and an emulsified  reclaimed rubber product.   Pre-
      dicting durability or service life of concrete treated with these
      coatings is  extremely difficult.  Pinholing, abrasion,  or mechanical
      damage will expose the concrete,  subjecting it to  corrosive attack.
      The use of these materials should be limited to areas where visual
      inspection and manual application  can or must be  performed.

 7.    Better coatings were obtained by using wetted rather than dry
      concrete specimens.  Dry specimens tended to generate gas bubbles
      which caused pinholing in the coating.  The fact that the walls in
      such appurtenances as wet wells and diversion boxes are damp, make
      the water base latexes of vinyl-vinylidene chloride, vinyl acetate-
      acrylic, nitrile rubber,  and emulsified reclaimed  rubber particularly
      attractive for such applications.  Materials' costs per square foot
      of treated area for coatings range between 6   8 cents.

 8.    The cost of impregnating concrete pipe with hydrofluoric acid will
      vary between 5 and 10 cents per  square foot, while impregnation
      with  sulfur  will vary between 8 and 15 cents per square  foot.   Typical
      costs for  epoxy-coal tar or plastic liners vary between  85 cents
      and one dollar per square foot.  Until service life  is established
      for impregnated pipe, a cost effectiveness comparison cannot be
      made.

 9.    The possibility that sewer lines  can be treated in  place, using hydro-
      fluoric acid in a manner  similar to that used in the oil industry for
      acidizing  oil and gas wells is of considerable interest and potential.

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                          SECTION II

                     RECOMMENDATIONS

1.     The use of 5% hydrofluoric acid, sulfur and modified sulfur form-
      ulations has proven successful in impregnating concrete pipe to
      improve corrosion resistance as measured in the laboratory.
      Field testing using these treatments,  supported by additional lab-
      oratory work should allow for the development of a good correlation
      between laboratory and field tests.  The fact that 1% sulfuric acid
      has been found to impart the same  scaling  rate as that of the most
      severe sewer line cases reported in the literature is encouraging
      and should be further pursued so that a valuable aid  can be develop-
      ed for laboratory evaluation.

2.    Pipe sections impregnated with hydrofluoric acid and sulfur along
      with a concrete control should be placed in test in domestic sewage
      lines  and in industrial waste lines which have a recorded history
      of severe concrete corrosion.   Preferably this should be accom-
      plished in several cities to insure measurable differences in a
      minimum of time.

3.    A representative sewer line  should be  selected and a portion should
      be treated in-place using 5% hydrofluoric acid.  The line should be
      monitored and a comparison made between the treated and non-
      treated sections to determine the success of in-place treatment.

4.    A facility such as  a wet well, diversion box,  treatment tank,  or
      junction box that is partially corroded  should be coated with one
      or more of the water base latexes.  A four walled structure would
      be ideal since vinyl- vinylidene  chloride, nitrile rubber, vinyl
      acetate-acrylic, and reclaimed rubber could be applied to each
      wall and be compared  directly with one another in the same instal-
      lation under the identical environmental conditions.

5.    The fact that Derated (a treating process using silicon tetrafluoride
      gas) concrete pipe is attacked by dilute sulfuric acid and yet report-
      edly performs  satisfactorily in  sewer service indicates that a re-
      evaluation of some of the  resins and treatments investigated on this
      program may be in order. The effect of any natural bactericidal
      effect or  that of added bactericides could conceivably control the
      bacteria population responsible  for the generation of  sulfuric acid
      and thereby allow  some of these materials  to provide adequate

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corrosion resistance in a sewer line application, even though
they would not pass the 10% sulfuric acid corrosion test in the
laboratory.

The best treatment methods as determined in the field tests
should be given a complete  process design and economic  analysis,
so that prospective users would have this material available to
them as an aid in making the decision with regard to installation
of such facilities.

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                          SECTION III

                        INTRODUCTION

Concrete is a low cost,  high strength material that is resistant to water
damage at normal temperatures.   Because of this, concrete is used ex-
tensively in water and sewer systems.  Corrosion of concrete in sewers
is not a new occurrence, but has been in evidence for years.   The sever-
ity of the problem has greatly  increased in recent years because of the
rapid expansion of the population,  industrial growth,  the use of garbage
disposal units, and a reduction in the amount of dilution of the sewage due
to tighter joints and to a reduction in the use of combined sewers.   In
sewer systems with a history of corrosion problems  a variety of conditions
occur regularly that cause the generation of sulfides  which are oxidized to
sulfuric acid and this aggressively attacks the  concrete.

Concrete is also attacked  by sulfates, particularly those contained in the
surrounding soil and water.  The sulfates react with  the tricalcium aluminate
and free lime in the cement and cause the concrete to deteriorate.   Sulfate
attack can also occur where there  is no native  sulfate,  in that  sulfate is
formed when concrete is attacked by sulfuric acid. Thus, attack attribut-
ed to sulfuric acid can actually be  a  combined attack  from both acid and
sulfate.  Impregnation of concrete pipe  used in water and sewer  systems
offers several potential  advantages.   The interior passages of the concrete
structure would be sealed. The permeability and porosity of the concrete
would be reduced.  The  physical and mechanical properties of the concrete
would be improved.  Realization of these advantages  at a  moderate  cost
would result in a longer service life  of installations and improved operat-
ional efficiency.

The  problem of corrosive attack of concrete in these  applications has
been the subject of extensive past research.  Some of the better known
developed control techniques included:

       1.     The use of forced air ventilation of the vapor spaces in
             sewer lines.

       2.     The running  of sewers liquid full.

       3.     The control of sewer pH.

       4.     The use of corrosion resistant  sewer pipe such as clay
             tile, or plastic pipe.

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       5.    The use of epoxy based coatings.

       6.    The use of complete or partial plastic liners.

       7-    The use of sacrificial coatings, (thick wall sections;
             concrete which contain high concentrations of limestone
             aggregate; etc. )

The objective of the subject program was to investigate a large number of
materials as potential impregnants for concrete sewer pipe to impart
corrosion resistance, reduce permeability, and improve strength.  Some
of the materials investigated failed to permeate the concrete  specimens,
but rather formed a surface  coating.

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                          SECTION IV

                         BACKGROUND

The quantity of concrete pipe used attests to the success that has been
achieved with it over a long period of time.  Continuous improvements
have been made over the years in its design and manufacture, particular-
ly with respect to the joints and the methods of sealing.  ASTM  Design-
ations:  C 14,  the Standard Specification for "Concrete Sewer, Storm Drain,
and Culvert Pipe", and C76,  "Reinforced Concrete Culvert,  Storm Drain,
and Sewer Pipe" detail tests for design,  strength, absorption, and per-
meability.   These tests form the basis on which much of this type of pipe
is purchased.

Corrosion of concrete pipe and other concrete structures used in sewers
is not a universal problem, but it is a serious problem in some  areas.
It results in leakage, infiltration, and overloading of treatment  facilities.
It also results in premature  failure of lines necessitating early  replace-
ment.  Corrosion of concrete in sewer applications has been the subject
of numerous investigations.   (1, 2,  3)  Conventional sewer corrosion
occurs above the liquid level and it does  not occur in lines that are run
liquid full unless some aggressive compound is being discharged to the
sewer,  usually from some industrial source.

The consensus of investigators regarding the mechanism of sewer cor-
rosion is that it is directly related to the presence  of hydrogen sulfide
in the vapor space of the  sewer and to a lesser extent to heavy sulfate
concentrations in the waters carried in the sewers  or in the  earth sur-
rounding the sewer.  The origin of hydrogen sulfide in sewage is from
the action of anaerobic bacteria on organic sulfur compounds, sulfates
and other inorganic  sulfur compounds.  They use sulfur instead of oxygen
as a hydrogen acceptor.  The quantity of hydrogen sulfide produced and
released to  the vapor space is considered to be a function of the amounts
of hydrogen sulfide producing elements in the  sewage, the time  of re-
action,  the temperature (minor up to 15 °C, increasing progressively
up to 38°C),  the pH (a maximum at a slightly alkaline condition), and
the degree of agitation  or turbulence experienced by the  sewage. The
hydrogen sulfide entering the vapor space dissolves in the condensed
moisture films on the exposed concrete surfaces and is oxidized to
sulfuric acid by aerobic bacteria.  One such bacteria, thiobacillus thio-
oxidans, is  capable of producing sulfuric acid in  concentrations up to
5%.  Figure  lisa sketch showing the mechanism of typical concrete
sewer pipe corrosion.

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  Condensate with large aerobic
bacteria population which oxidizes
 hydrogen sulfide to sulfuric acid
     which attacks  concrete.
Silt
 Accumulation
                                                                      Concrete
                                         Slime accumulation with large
                                         anaerobic bacteria population
                                        which convert sulfur compounds
                                       in sewage to hydrogen sulfide gas
                                     which is released to the vapor space.
      Figure 1.   Cross Section of Concrete  Sewer Pipe Under Typical
                          Corrosion Conditions.

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Figure 2 is a closeup photograph of the remains of a floor section of a
lift station and is characteristic of the type of deterioration encounter-
ed in concrete sewer appurtenances.  Note the exposure of the rein-
forcing steel.

The destructive action  of sulfates on concrete is primarily the result
of the reaction between the sulfates and the tricalcium aluminate and
free lime in the cured  concrete product.  The crystalline calcium
sulfate reaction product is larger in volume than the original constituents
and this causes cracking,  swelling, and spalling in the concrete which
becomes progressively weaker and finally disintegrates.

Numerous investigators (3,  4) have shown by extensive studies  of this
problem that sulfate  attack can be controlled in concrete by keeping the
tricalcium aluminate content of the cement used below 5. 5% or  by curing
the pipe with high pressure  steam or both.  It was also noted by earlier
investigators that the less permeable the pipe, the more sulfate resist-
ance it exhibited.   The use of sulfate resistant concrete does not impart
resistance to sulfuric and other acids.

Other mineral and organic acids  often  tend to react preferentially with
any limestone present  in the concrete.  An example of this is shown in
Figure 3.  This type of failure is more often encountered in industrial
wastes rather than in domestic sewage.  The section of pipe shown in
Figure 3 was the top of the line,  the bottom half having been completely
corroded away.  This is the reverse of what is found in sewers handling
domestic sewage.

When many users of  concrete pipe encounter or anticipate problems with
acid or sulfate attack they choose pipe other than  that made of concrete.
Often the other types of pipe are  more costly than concrete pipe.  The
premium price that these other types of pipe command and their wide-
spread use  are related to their superior chemical resistance in  problem
areas.

The following criteria  are thought to be the most  significant with respect
to the use of concrete pipe:

       1.      Concrete  pipe is subject to both acid and sulfate attack
             and there are locations where it can be subject to  both
             at the same time.  Infiltration into,  or seepage from,
             concrete  pipe can develop as a result of the deterioration
             of the pipe.

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Figure 2.  Corrosion of the Floor of a Concrete Lift Station

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Figure 3.  Preferential Acid Attack on Limestone Aggregate by Industrial Wastes
                                         11

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2.    Impregnation of concrete pipe can improve its resistance
      to acid and sulfate attack in that it  reduces the permeability
      of the concrete and thereby denies  the deleterious materials
      access to the interior structure of  the concrete and any
      steel reinforcing.  (Corrosion of steel can result in forces
      created during the formation of iron oxide sufficient to
      spall concrete).

3.    A protective process for concrete sewer pipe should not
      only impregnate the pipe and reduce its  permeability but
      it should also protect the interior and exterior surfaces
      from attack.

4.    Improvements in strength derived from  the protection
      system are significant and can be used to great advantage,
      however, strength improvements are not thought  to be  of
      the same significance as improvements  in corrosion
      resistance.

5.    The cost of the protective systems  should  be such as to
      offer a considerable savings over other  present day remedied
      actions such as the use  of clay tile, plastic liners, and the
      various coatings.
                            12

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                          SECTION V

                     LITERATURE SEARCH

This program was initiated with a literature search relating to impreg-
nation and treatment of concrete.  In addition to the library facilities
of the Institute,  the  computer abstracting service of the Highway Re-
search Information Service of the National Academy of Sciences was
employed.  Prior to the literature search, the authors were aware of
some very early work (5,  6) relating to the impregnation of concrete and
sandstone with sulfur as well as some recent work on impregnation of
concrete with polymer materials (7, 8,  9) being conducted at Brook-
haven National Laboratory by the Bureau of Reclamation, Atomic Energy
Commission and Office of Saline Water.   Limited investigations of impreg-
nating concrete  sewer pipe with sulfur (10) demonstrated the technical and
economic feasibility for improving  strength and reducing permeability.
One other known protective treatment for concrete sewer pipe was the
Dutch Ocrate process (11) wherein silicon tetrafluoride gas was impreg-
nated under pressure into concrete  pipe to improve its corrosion resist-
ance.

The literature search failed to uncover any additional treatments or
processes for impregnating  concrete as  relates to controlling corrosion
resistance.  Several good references  were uncovered,  however, on
coatings or treatments for waterproofing or protecting concrete in general.
(12,-14) These documents served as valuable guidelines insofar as materials
which showed any promise as simple waterproofing agents were generally
considered as potential impregnants.
                                   13

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                          SECTION VI

     INITIAL LABORATORY SCREENING OF MATERIALS

With the valuable literature  references,  the laboratory phase of the
program was initiated.

Impregnation Techniques

In addition to samples obtained from the local concrete pipe manu-
facturers, samples were also requested from various plants throughout
the United States.  However, most  of these contacts referred us to the
local manufacturers and as a result,  all of the data generated in this
program were obtained from pipe that was manufactured from plants in
San Antonio, and Harlingen, Texas.  The fact that concrete pipe is manu-
factured according to  rigid ASTM standards should insure that the concrete
pipe is a fairly uniform product.  This was confirmed by representatives
of the American Concrete Pipe Association and from our limited labora-
tory tests.

The impregnation procedure used throughout this program was as follows:

      Concrete specimens predried at 250°F for 12 hours were
      completely submerged in the  impregnating solution.  The
      vessel containing the specimens and solution was then
      placed inside a larger pressure vessel.  Depending upon
      the particular solution, a vacuum of bet-ween 26 and 28
      inches of mercury was then applied, followed immediately
      by a positive air pressure with  the specimens  still submerged
      in the impregnating liquid.

In initial experiments, specimens from 4, 6,  12,  and 27 in. diameter
pipe were first dried and then submerged in water and subjected to 28
in. of mercury vacuum.  The weight gain for all of the  specimens sub-
jected to vacuum for 10 minutes varied between 5. 5 and 6. 5%.  When
subjected to vacuum for 15 minutes  followed by 30 psig for 10 minutes,
the weight gain varied between  6 and 7%.  No major  absorption differ-
ences were found among the various diameter pipe.   Eighteen in.  diameter
pipe was selected for test work because  of its relatively thick wall.

Sections of 18 in. diameter pipe were  submerged and subjected to pressures
varying from 10 to 50 psig for timed intervals. The results of these tests
are shown in Figure 4.  It was found that the bulk of the absorption takes
place in the first 10 minutes of  submersion and above 10 psi the absorption

                                   15

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10L
 6_
28 in. Vac.
     O
28 in. Vac/
  30 psig

     O
                                                  28 in.  Vac/
                                              O  100 psig
                         28 in. Vac/
                           30 psig
                             o
                       50 psi
            10
                20
                                   30
                40
50
60
                                                                                      120
                                                                                          130
                                        Total Immersion Time
                                              (min)
      Figure 4.  Water Absorption as a Function of Time  Under Varying Conditions of Vacuum and
                                  Pressure for 18 in.  Diameter Concrete Pipe

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is relatively independent of pressure.  Next,  specimens were impreg-
nated under vacuum only and then vacuum followed by pressure.  Specimens
were submerged under vacuum only for 10 minutes, under vacuum for 15
minutes followed by 30 psig for  15 minutes (total immersion time of 30
minutes), under vacuum for 20 minutes followed by 100 psig for 20 min-
utes, and under vacuum for 1 hour followed by 30 psig for 1 hour.  These
data are also shown in Figure 4.  The standard procedure adopted for
preparing test  specimens was to subject the specimens to a 28 in. mercury
vacuum for 30  minutes followed by 30 psig pressure for 30 minutes for
a total immersion time of one hour, with some allowance being made for
some of the more viscous impregnants.

Specimens were submerged in various impregnating solutions in  separate
containers.  Several of these containers were then placed in a large
pressure vessel and in this manner,  a number of materials could be run
at one time.

Mechanical Properties

A common problem in any type of screening program conducted in the
laboratory is the selection of appropriate tests that relate to field per-
formance.   For strength determinations flexural strength was selected
since specimens for this test could easily be  prepared by cutting the
cured concrete pipe with a diamond bladed saw.   Tensile strength may
have been a better test, however, preparing  suitable specimens from
cured concrete pipe was not practical. The standard D-load test where-
in concrete pipe is placed horizontally and then subjected to a compressive
load along its horizontal axis is used extensively in industry.  If  ring
sections had been used instead of flexural specimens, it would have re-
quired large volumes  of impregnating materials, large impregnating
vessels, and the specimens would have been less convenient to handle.
In addition, the resulting data from a D-load  test is not easily related to
a fundamental  stress property which is dependent on specimen dimensions.
This was important since the  specimen dimensions changed after exposure
to the corrosive media.

The flexure  specimens were prepared from non-reinforced  6 in.  concrete
pipe and were approximately 0. 5 in.  x 1 in. x 5 in.  Each specimen -was
carefully measured with a vernier caliper and broken in flexure.  The
average flexural strength or modulus of rupture for the untreated pipe
was approximately 1160 psi.  Specimens with a number of larger  pieces
of aggregate in the broken cross section tended to be lower  than this
                                   17

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(690 psi) while specimens without large aggregate in the broken cross
section tended to be higher  (1360 psi).  Asa result,  differences in
flexural strength were not viewed as significant unless they were orders
of magnitude different.

Corrosion Tests
Selection of the corrosive media was based on the fact that sulfuric
acid is the most prevalent type of corrosive attack encountered.  Pre-
liminary laboratory tests showed that attack by dilute sulfuric acid
was immediate, being measurable after several days, whereas sulfate
salts took considerably longer.  Also,  from laboratory experiments it
was observed that dilute sulfuric acid attacked the mortar preferentially
to the limestone aggregate such that ultimate attack was very similar to
prolonged sulfate attack.  The normal attack of other acids, including
concentrated sulfuric acid,  is preferential attack on the limestone
aggregate which leaves depressions in specimens as indicated in Figure
5 and almost identical to  that shown in Figure 3.

Scaling rate as used throughout this report to determine corrosion rate,
is a measure of the erosion of the  concrete pipe wall reported as  in. /day.
Laboratory experiments were conducted wherein different acid con-
centrations were evaluated for a 3-day exposure period.  Figure 6 plots
the scaling rate versus sulfuric acid concentrations and shows a maximum
rate of approximately 10% concentration of sulfuric acid.  Although the
98% sulfuric acid attacked the limestone aggregate, it did not attack the
mortar.  The 0.5,  1, 10,  30,  and 50% solutions preferentially attacked
the mortar, whereas the  0.1% sulfuric acid attacked both the limestone
aggregate and mortar at about the  same rate.

Asa final consideration,  ASTM "Standard Methods of Testing Clay Pipe"
(C 301-68)  requires a 48 hour exposure of the clay pipe to a IN solution
of hydrochloric, nitric,  sulfuric, or acetic acid.  For sulfuric acid this
is equivalent to a 5% weight solution.  The maximum concentration of
acid measured in working sewer lines has been approximately 5%.

For the laboratory tests, the most severe acid attack was desirable so
that corrosion would occur in a minimum  period of time.  Thus 10%
sulfuric acid was selected as the preliminary screening corrosive media
because it was more  severe  than the 5% reported in sewers, the scaling
rate was easily measurable after 3 days,  and there was never any
indication that the 10% sulfuric acid was attacking or  charring any of the
                                   18

-------
            10% HC1      10% HNO3       98%
Figure 5.   Preferential Attack of Limestone Aggregate in Laboratory

-------
     01
                                                                I    I '
OJ
4->
rt
.OOll
   000 ll
             _i	i  i
                            .  1
                                              1.0

                                   Sulfuric Acid Concentration

                                            (Wt. %)
10
100
           Figure 6.  Scaling of Concrete  Pipe as a Function of Sulfuric Acid Concentration

-------
treatments.  More concentrated solutions of sulfuric acid have been
known to char hydrocarbon materials.  Typical 3-day attack of 1, 5,
and 10% sulfuric acid on concrete is shown in Figure 7.

Figure 8 shows the typical performance of the  concrete pipe used
throughout this study for an extended period  of time in 10% sulfuric
acid.  Most of the large aggregate protruding is limestone, whereas
the mortar is principally silica sand and cement.  As already explained,
this phenomenon has been recognized and is  the principal  reason why
some pipe manufacturers are considering switching to high limestone
aggregate concrete in sewer pipe production.

Types of Protective Systems

Generally speaking, there are three principal ways  of protecting cured
concrete pipe from corrosive attack.  One way that  has been  of principal
interest in this program has been the impregnation or saturation of the
voids -within the concrete pipe with  an inert or  noncorrosive material.
Preferably this material is  a good film-former as well as a good wetting
agent for the concrete constituents.  While simply blocking the pores or
void spaces within the concrete should slow down and limit attack to the
surface only,  unless the material readily wets  the concrete particles and
forms an impermeable barrier,  corrosion will occur.

A  second means of protecting the concrete is to initiate a  chemical
change in the  concrete itself, whereby the soluble and/or  more reactive
constituents are insolubilized or  changed to a less reactive species.
Because of the complex nature of concrete itself, as well  as the complex-
ities that can  occur with the resultant chemical reactions, this particular
means of protecting concrete is usually better  evaluated by performance
studies.  This area includes steam curing of concrete, the silicate  and
fluosilicate treatments,  fluoride  treatments, carbonating, etc.  This
approach is potentially as attractive as impregnation, particularly if
more than a surface treatment can  be obtained.  Unfortunately, most of
these treatments afford only surface protection, or  form gels which
provide some protection under very mild acid conditions,  but not against
typical sewer acid concentrations.  These treatments have been used
principally as surface hardening, or water proofing applications in  the
past.

The third means  of protecting concrete from attack  is by the use of'
coatings.  This area has received by far the  most attention in the past.
While there are commercial coatings available which are  currently used
in  sewer applications, the most successful are usually relatively thick

                                    21

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Figure 7.  Corrosion Caused by 1, 5, and 10% Sulfuric Acid Solutions
                        After Three-Days' Exposure

-------
uo
                  Figure 8.  Extended Exposure of Concrete to 10% Sulfuric Acid

-------
coatings,  applied after the pipe is cured,  or liners of polyvinyl chloride
which are made part of the pipe or fixture during casting.  The principal
drawback to the most successful of these  liners is generally cost.  They
normally  cost between $0. 80 to $1. 00 per square foot of coating and
increase the cost of concrete pipe to the point where clay pipe or other
more expensive pipe is competitive.   The problems associated with most
coatings relate to pinholes,  bonding,  or blistering or peeling of the
coating from the interior surface.

Of these three ways of protecting cured concrete pipe, it must be
emphasized that principal consideration was given to impregnation, even
though the latter two ways are a degree of impregnation.  For a material
to chemically react with the concrete in depth, it must be able to pene-
trate,  otherwise only a surface change will occur.   A coating  can be
thought of as an inefficient impregnating technique.   Predicting before-
hand, however,  which materials would  or would not impregnate was not
possible.   Even with the materials that did not penetrate,  but  simply
coated, attempts were made to modify the material  with surfactants or
diluents in order to allow for better penetration.

Evaluation of Materials

Thus materials  investigated in this study  were first screened  for their
ability to impregnate concrete.  The standard test method consisted of
submerging predried concrete specimens in the impregnating  material
and then applying 28 in.  of vacuum for 30 minutes followed by 30  psi
pressure for 30 minutes,  removing the specimens and recording  the
weight increase.  The specimens were  allowed to air dry for three days
at room temperature.  Certain specimens,  depending on the treatment
they received,  were oven dried.  One specimen was then tested in flexure,
while the duplicate was submerged in 10% sulfuric acid for  three days.
The weight loss and scaling were determined and then the specimen was
also tested in flexure.

From the weight increase as well as inspection of the failed flexural
specimens, it was  easily determined which materials failed to penetrate,
but nevertheless did offer a protective surface film.   These particular
materials were then further investigated  as coatings.  With many of
these materials, particularly the latex  emulsions,  various techniques
and approaches were investigated in attempts to improve the  impregnation.
Use of surfactants  and diluents,  as well as variation of the impregnating
conditions, usually failed  to improve impregnation as such, although
bonding to the concrete was, in most cases,  improved.
                                    24

-------
Materials which reacted with the concrete were also observed after
the impregnation procedure.  Usually these materials underwent a
surface reaction which was destroyed in the 10%  sulfuric acid.  The
more promising materials, however, penetrated in depth and caused a
chemical reaction throughout the concrete.

By comparing the weight loss and scaling rate of the treated  specimens
against that of the concrete control, several promising materials were
singled out and  further evaluations were conducted.

A  complete list of materials evaluated and their performance is included
as Appendix A.   A brief description of the performance  of the various
types of treatments  will be discussed,  with further elaboration on some
of the more promising materials.

During the course of this program approximately 100 different chemicals
or materials were evaluated.  The general classes of materials can be
broken down into water soluble salts or acids, water base latexes,  solvent
base latexes,  liquid resins,  and hot melts. One principal problem en-
countered with all of the materials -which coated the surface of the specimen
was drainage  of the  material from sharp edges.  This left a relatively
thin coating in these areas which the acid rapidly penetrated.  A brief
review of each class of materials follows.

Water Soluble Salts  and Acids
This class of materials included silicates, fluosilicates, fluorides,
phosphates,  and oxalates.  The silicates and fluosilicates required a
series of treatments, wherein dilute solutions were followed by more
concentrated solutions.  These materials did not give adequate protection
for the intended application.  This is not surprising since others  have
found that these treatments are usually poor waterproofing agents as
well.  (15)

Several experiments using varying concentrations of hydrofluosilicic
acid were conducted since it was expected that a treatment similar to
that of the Ocrate process would be obtained.  The resistance to  sulfuric
acid was poor, -whereas Ocrated concrete  is reported to give good corrosion
resistance in sewer applications.  In checking the literature,  (16) it was
found that sulfuric acid does attack Ocrated concrete, although its success
in sewer applications is related to a reported bacterial  effect which
inhibits the  formation of sulfuric acid on the concrete walls. (16,  17)
                                    25

-------
The only materials from this group which appeared encouraging were
a commercial product by the name of SP-4 (Patented Product of Road-
ways International, Baton Rouge, Louisiana) and a dilute solution of
hydrofluoric acid.  According to the label, SP-4 also included hydro-
fluoric acid.  The fact that  the hydrofluoric acid does impart corrosion
resistance is unexpected since it is usually recognized  as a corrosive
material to concrete.  Specimen numbers 1 and 3 in Appendix A  give
the specific data on these treatments.  The treated specimens suffered
a weight loss of from  2. 3 to 2. 7 grams as  compared  to 9. 2 for the con-
crete control.  In addition,  a scaling rate of 0  to 0. 00017 was  obtained
as compared to 0. 0054 in. /day for the control.
Water Base Latexes

This class of materials  included copolymers of vinyl chloride and
vinylidene chloride, acrylics and vinyl acetate; polyvinyl acetate and
copolymers of vinyl acetate and acrylics; copolymers of acrylonitrite
and butadiene-styrene; natural  rubber emulsions; and reclaimed rubber
emulsions.   None of these materials impregnated the concrete, but
rather gelled or formed a coating on the concrete surface.  Gelling was
more pronounced  on dry concrete specimens.  The use of water wetted
specimens did not improve penetration.  By far the most promising
materials of this group were  the vinyl chloride-vinylidene chloride
copolymers, a vinyl acetate-acrylic copolymer,  a nitrile rubber,  and
a reclaimed rubber emulsion.  Even these materials, however,  if not
applied in sufficient thickness,  allowed  acid to pass by way of pinholes.
If properly  applied, these coatings completely protected the concrete
from acid attack.   The principal applications  envisioned for this class
of materials are the protection of manholes,  junction boxes,  wet wells,
treatment tanks, and other concrete structures which lend themselves
to easy visual  inspection,  wherein failed sections can easily be detected
and repaired.  A typical potential application  is shown in Figure 9.  The
bulk of this damage occurred when the pH of the  sewage dropped to 2
during one canning season for citrus and tomatoes in Harlingen, Texas.

The fact that these are water emulsions makes them attractive from an
application  point of view because of essentially no toxic odors or fumes,
good adherence to damp concrete walls,  as well  as easy clean-up of
                                    26

-------
Figure 9.  Treatment Plant Corrosion Caused by Citrus and Tomato Acid

-------
equipment with water.  Although slightly more expensive,  the re-
claimed rubber product is particularly attractive since it is a re-
claimed product of a pollution problem itself -- old tires.

Solvent Base Latexes
The third class of materials included latexes of nitrile-phenolic
copolymers, chloronated polyethylene, vinyl chloride-vinylidene chloride
copolymers, a rubber base adhesive, and reclaimed rubber.  Impregnation
was achieved if sufficiently dilute solutions were used.   Because of the
relatively large amount of solvent present, however,  a good film coating
was not obtained on the specimen surface and as a consequence, good
corrosion resistance was not achieved.   Repeated impregnations would
probably offer  a solution although this approach was not considered
practical.  Asa result this class was also considered for multiple coatings.
As  with the water base latexes, the film  thickness had to be sufficient to
eliminate pinholes.  These materials appeared to have  excellent resistance
to the dilute sulfuric  acid.  Because of solvent  vapors and  fumes, as well
as the increased cost, they are not  as attractive for inplace treatments
as the water base latexes.  Nevertheless, this  class of materials should
find limited application in sewer systems.

Liquid Resins

The fourth class of materials included a  number of materials in both
water and solvent systems, as well as undiluted resin systems.  Urea-
formaldehyde,  urea-formaldehyde-alkyds,  melamine-alkyds, phenolics,
furans,  and epoxies are but several of the materials investigated.

Linseed oil,  perhaps  one  of the oldest concrete treatments,  impregnated
the concrete in depth, but unfortunately failed to impart any acid resist-
ance.  The phenolic and furan resins were somewhat better than the urea-
formaldehyde,  but even so were only  marginally better than the concrete
control.  The urea-formaldehyde-alkyd resin investigated  was considerably
better than the straight urea-formaldehydes, but the melamine-alkyd was
superior to either of  these materials.  The principal problem encountered
with the melamine-alkyd,  however, was  the drainage from sharp edges.
This same problem was encountered with the epoxies.  With few excep-
tions, the viscosity of the  epoxies was too great to allow penetration.
The practical problem of pot  life makes most epoxies unattractive as
impregnants.  From  the large number of epoxies investigated as coatings,
only one (#125) exhibited outstanding acid resistance,  and even here, the
edges suffered damage.  While  the  epoxy coatings themselves had good


                                   28

-------
resistance to the sulfuric acid, pinholes in the coating allowed the acid
to pass.   Once behind the coating, the acid attacked the concrete to the
point that after three days' exposure, the epoxy coating usually re-
mained intact but simply separated from the specimen.  Thicker coat-
ings or fillers in the epoxy gave mixed  results.

The principal difficulty encountered with the resins in this class
appears  related to the film-forming abilities of the resins.  With few
exceptions, acid attack on the treated specimens appeared uniform across
the surface of the specimen indicating acid penetration through the coat-
ing.  Of  this entire group,  certain selected epoxies,  the melamine-alkyd,
and urea-formaldehyde-alkyd, appeared the most promising, although
performance was not as good as for materials  from the other classes.

Hot Melts
The last class of materials considered was that of the hot melts,  in-
cluding sulfur, asphalts, coal tars, polyethylene waxes,  paraffin, and
a gilsonite-asphalt mix.  Although not hot melts as such,  cut-back
asphalt and coal tar pipe dips are also included here,  since they were
applied heated as well as at room temperature. Impregnation with the
hot melts was much better than that of any of the other groups, generally
speaking.  Inspection of the broken specimens  usually revealed complete
penetration.   The interesting point, however, is the fact that even though
impregnation was achieved, with few  exceptions,  the corrosive attack was
about the same or worse than that  of the concrete  control.  Surprisingly,
for the degree of penetration obtained by the asphalts, coal tars,  and
paraffin,  the corrosion resistance was poor.  The corrosion  resistance
imparted by impregnation with sulfur was considerably better than that
of the  other hot melts.   Elemental sulfur and certain selected modified
sulfur treatments also imparted outstanding strength improvements.

The asphalts and coal tars performed better as coatings than as impreg-
nants, provided adequate thicknesses were  employed to  reduce pinholes.

Dicussion
In all fairness to the materials investigated and to the manufacturers
who supplied them,  it must be remembered that the nature of this program
was essentially one  of screening a large number of materials to select
those materials showing the greatest promise, before proceeding to
optimize materials and procedures.  The fact that most of the materials
investigated failed is not as much an indictment of those materials as it

                                   29

-------
is a demonstration of the severity of attack of 10% sulfuric acid.  In all
probability, continued investigations with each of the different materials
might lead to better selection,  modifications,  and ultimately an accept-
able material.   To do this, however, •would have  required time and
expenditures beyond those available.

To recapitulate, from these initial investigations the most promising
materials uncovered included HF, SP-4, vinyl-vinylidene chloride co-
polymer,  vinyl  acetate-acrylic copolymer,  nitrile rubber latex,  an
emulsified reclaimed rubber, nitrile-phenolic rubber, a rubber base
adhesive, a melamine-alkyd  resin,  one epoxy, and sulfur.  The specific
test results are summarized for these materials  in Table 1 and compared
against that of a concrete control.
                                   30

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                 TABLE 1

PROPERTIES AND CORROSION RESISTANCE
 OF PROMISING  CONCRETE TREATMENTS
Kesm
Specimen # Absorption
and Treatment (o/o)
Concrete Control
1 -
3 -
59

63
*81

62
#89

'111
45
HF (5%Sol'n)
SP-4
Vinyl - Vinylidene
Chloride Copolymer
1 '
Vinyl Acetate
Acrylic Copolymer
Nitrile Rubber Latex
Emulsified Re-
claimed Rubber

Nitrile -Phenolic
5.
5.

14.
1.

7.
6.

7.
3.
1.
7
7

4
7

5
3

4
8
2
i lexuraj.
Strength
(pal)
1160
1050
1030

1020
1260

760
1270

550
680
1260





Wt. Loss Scaling Flexural Strength
(g) (in/day) (psi)
9.
2.
2.

0
0

0
0

+ 1.
+ 1.
0
2
3
7







6
5

. 0054
0. 00017
0

0
0

0
0

0
0
0
1350
1290
1270

-
-

750
-

980
670
1330




#*
#*


**




     1250
     1160
                 +3.7
                                . 0007
    Rubber
 58 Nitrile-Phenolic     0. 9
    Rubber/Solvent
    (50% Sol'n)
126 Rubber Base Adhe-  1.0
    sive
105 Melamine-Alkyd     1.9
125 Epoxy               2. 5
 15 Sulphur              9. 7
 17 Modified Sulphur     8.8

 * Specimens prepared from 8" dia.  concrete pipe,  rather than 6" dia. pipe.

** No data taken
1280
1310
2970
2800
+ 1.3
+ 1. 1
6.9
5. 1
0
0
0
. 0005
1360

1250 (heat cured)
1270
2890
1770

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                          SECTION VII

      OPTIMIZATION OF MATERIALS AND PROCEDURES

Although discussed  separately, the optimization of materials and
procedures was actually integrated into the program.  As the perform-
ance of the materials was being evaluated, manufacturers would supply
additional  materials, modifications would be made, or impregnating or
coating techniques would be varied in attempts to improve performance.
These materials or  modifications  of materials have been included in the
respective  sections  of Appendix A.

With the water soluble  salts and acids,  optimization included varying
concentrations, or combinations of materials.  With the water base
latexes, several anionic  surfactants were investigated, along with the
use of wet and dry specimens.  Although the use of the surfactants did
not necessarily improve the corrosion resistance,  the surfactants did
improve the bonding of some latexes to the concrete.  Dry concrete
specimens generally caused the gellation of a thicker  latex film than did
the wet specimens.   When applying the latexes as  a coating over the  dry
specimens, there appeared to be more pinholing on the initial coat due
to the  escape  of the  air, whereas with the wetted specimens,  this
problem was not as  pronounced.  This is of definite benefit when consider-
ing the coating of installations in-place since the walls in these instal-
lations are usually damp or wet from condensate or capillary water.

One technique that proved useful in the coating applications was the use
of multiple coatings for both the water base and solvent base latexes.
This included the use of a primer  coat followed by  one or more layers
of the  latex coat.  In most cases a primer  coat of nitrile-phenolic latex
improved adhesion of the finish coat. With the multiple coatings, two
layers were better than one,  and three appeared to be the optimum.  While
the corrosive attack with single coatings was not always measurable, pin-
holes did appear, whereas additional coatings  eliminated them completely.

One other  technique that improved the performance of some coatings was
the use of  filler material, particularly plate-shaped particles such as
talc.

In addition to the techniques already mentioned, when using the hot melts,
particularly asphalt and coal tar, heated and room temperature specimens
were employed.  The heated specimens allowed for more drainage and
thus thinner coatings, particularly at the sharp edges. As a  result the

                                    33

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room temperature  specimens had thicker coatings and better corrosion
resistance.

A double treatment employing two promising systems -was also investi-
gated.  Hence, specimens treated with HF were also impregnated with
sulfur and coal tar.  Other specimens were impregnated with sulfur
for the strength improvement and then coated with latex.  The double
treatment, although more costly than a  single treatment, was definitely
better and should be considered where  extremely severe conditions
might be expected.  Table 2 lists the most promising double treatments
investigated.

Of the materials investigated on this program, sulfur was the most
promising material that imparted considerable strength improvement to
the concrete.  Since both sulfur and  the concrete pipe must be heated in
order to obtain impregnation, experiments were conducted wherein the
optimum times, temperatures and conditions were determined for optimum
strength.

The first consideration when heating concrete to elevated temperatures
is the age  of the concrete itself. Even though concrete pipe  has cured
sufficiently in one day to be handled  and moved, the  strength continues
to grow with time.   Usually the nominal strength is obtained within several
days  as shown in Figure 10.  It  is interesting to note that even though the
strength of the pipe has plateaued at about five days,  considerably better
strengths were obtained by impregnating with sulfur only after 20 days.
The specimens used for the 180 day test are from a different batch of
pipe, however,  from the data, this appears to be of little significance.

The second consideration was that of the temperature at which impregna-
tion would be  carried out.  Previous investigations using elemental sulfur
(18,  19) have shown that the time   temperature history of the sulfur is
very important in obtaining optimum mechanical properties.  For example,
in one study it was found that the maximum tensile strength was obtained
from specimens prepared at approximately 150 °C.  This phenomenon has
been related to the allotropic modifications of sulfur under these temper-
ature conditions.  To determine the  effects of temperature on the impreg-
nated concrete,  the temperature of the sulfur was varied between 130°C
(slightly above the  melting  point of sulfur) and 160°C  (the temperature at
which sulfur becomes very viscous. ) This data is presented in Figure 11.
The maximum strength is obtained at approximately 150 °C.

The final consideration of impregnating with sulfur is the process conditions
necessary for impregnation.  The use of vacuum or  partial vacuum

                                    34

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                                   TABLE 2
         PERFORMANCE OF SELECTED DOUBLE-TREATED SPECIMENS
                                        After Exposure to 10%
     Specimen
  68 HF Impregnated
     followed by Coal Tar
     Impregnation

  69 HF Impregnated
     followed by Sulfur
     Impr e gnation

 131 Sulfur Impregnated
     coated with Vinyl-
     Vinylidene Chloride

 132 Sulfur Impregnated
     coated with Nitrile-
     Phenolic  Latex

 133 Sulfur Impregnated
     coated with Rubber
     Adhesive

 134 Sulfur Impregnated
     coated with Reclaimed
     Rubber Emulsion

 135 Coal Tar over Primer
     Coat
Wt. Loss
   (g)

  + 1.9 *
  + 2.6
  + 2. 5
 Scaling
(in. /day)

    0
Flexural Strength
	(psi)	
                                2300
                                2080
 * Plus Sign Indicates Wt.  Gain
'<=* Dash Line Indicates No  Data Taken
                                        35

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   3000






   2800





   2600






   2400






   2200


«
Q.

~  2000
a;
^

3


v  1800






   1600






   1400





   1200






   1000





    800






    600
-A'
                                                                                Impregnated with Sulfur
                                                                                Concrete air dried
          J	L
                           J	L
                                            J	1	1	1	1	\	1
     10    20    30   40    50    60    70



           Figure 10.  Flexural Strength as a Function of Pipe Age for Sulfur Impregnated Concrete.
                                                   80   90    100   110   120   130   140  150   160   170   180
                                                      Time (days)

-------
to
             CO


             —
             
-------
necessarily limits a process to a batch type operation.  Pressure, how-
ever, can be related to a liquid pressure head, and if one envisions a
deep vat filled with impregnating liquid, the pipe can be submerged to
an appropriate depth for a specific period of time and be automatically
placed and removed, as with a conveyor belt.  To determine the effect
of pressure only,  specimens were  submerged under liquid sulfur and
then an air pressure of 30 psig was applied for time periods ranging
from 5 to 30 minutes.   The quantity of sulfur impregnated into the
concrete as well as the flexural strength was then determined and is
reported in Table  3.  From the data,  although there was a continual
increase in sulfur  absorbed by the concrete, the strength is fairly
constant, indicating that 5 to 10 minutes under this pressure is sufficient.
For operation at a lower pressure  head, a longer impregnation would no
doubt be required.
                                  38

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                      TABLE 3
    ABSORPTION AND STRENGTH OF SULFUR IMPREGNATED
        CONCRETE PIPE AT 30 psig PRESSURE
Time         Absorption            Flexural Strength
(min. )             (%)               	(psi)

  5               7.4                     2120

  10               7.4                     1730

  15               7.7                     2080

  20               8.0                     2020

  25               8.4                     1810

  30               8.9                     2530
                              39

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                          SECTION VIII

                 PRELIMINARY  FIELD TESTS

Once several promising materials had been developed, it was decided
that  limited experiments would be conducted in active sewer lines.  While
acid attack was readily simulated in the laboratory on an accelerated rate,
correlation with that experienced in a sewer line is difficult.  For example,
films and coatings  can be totally impermeable to liquids, but not to gases.
Thus it was possible that even though the coatings investigated showed
excellent resistance to sulfuric acid,  when  subjected to a sewer environ-
ment the hydrogen  sulfide,  water vapor, and air,  could penetrate these
coatings and cause corrosion behind the coating.  Another unknown -was
the effect that bacteria •would have on the treatments,  particularly sulfur
and the latex coatings.

Eight specimens were prepared and placed  in an influent diversion box at
Harlingen, Texas on November 6, 1970. The gases in this diversion box
are extremely corrosive and this particular box had just been rebuilt
because of failure by concrete corrosion.  The eight specimens placed in
Harlingen -were prepared from six inch inside diameter concrete pipe
and were each approximately six inches in length.  The weights were re-
corded before being suspended in the  diversion box.  A brief description
of each specimen follows:

      A.     Control

      B.     Coated with a water emulsified reclaimed rubber

      C,     Coated with nitrile-phenolic rubber diluted 30% with toluene

      D.     Coated with a synthetic rubber adhesive in a solvent system

      E.     Coated with a vinyl acetate-acrylic copolymer in a water
             emulsion.

      F.     Coated with a vinyl chloride-vinylidene chloride copolymer
             in a water emulsion

      G.     Impregnated with elemental sulfur

      H.     Chemically treated with a 5% hydrofluoric acid solution
                                    41

-------
On February 15,  1971 one additional specimen was placed in Harlingen.
This specimen was impregnated -with sulfur containing 0. 5% by weight
sodium pentachlorophenate,  an effective bactericide for sulfur. (20)

On December 8,  nine specimens were placed in a siphon station in the
southeast part of San Antonio which has had a long history of hydrogen
sulfide  corrosion.  The  concrete interior of this station is  badly corroded
from the corrosive gases.  The specimens were placed  on  a walkway
above the liquid level but condensate collects  readily on the walls, the
walkway, and the specimens.  The nine specimens placed in San Antonio
were prepared from 6-in. inside diameter concrete pipe and were each
approximately 6 in.  in length, and with  the exception of  the ninth  specimen,
were identical to those prepared for the Harlingen site.

     A.     Control

      B.     Coated with a water emulsified  reclaimed rubber

      C.     Coated with nitrile-phenolic rubber diluted 30% with toluene

      D.     Coated with a synthetic rubber adhesive in a solvent system

      E.     Coated with a vinyl acetate-acrylic copolymer in a water
             emulsion

      F.     Coated with a vinyl chloride-vinylidene chloride copolymer
             in a water  emulsion.

      G.     Impregnated with elemental sulfur

      H.     Chemically treated with a  5% hydrofluoric  acid solution

     I.      Coated with a reclaimed rubber-solvent system

Also, on December 8, 1970,  three specimens were submerged in one of
the active septic  tanks on the Institute grounds.   These specimens were
prepared from 6-in. inside diameter concrete pipe and were approximately
3 in. in length.  The first specimen was a control, the  second specimen
was  impregnated with elemental sulfur,  while the third specimen was
impregnated with elemental  sulfur containing  0. 5% by weight of the bac-
tericide sodium pentachlorophenate.  The purpose of these  tests was' to
determine the relative attack of the bacteria  on  concrete impregnated
with sulfur and the effect of bactericide in a sulfur system.  It would appear


                                    42

-------
that a bactericide is a simple solution to the bacterial attack on sulfur
experienced in the past.  (20-22)

Within one week,  the concrete control in the septic tank began to
discolor,  indicating a chemical reaction occurring between constituents
in the concrete and the sewage.  A check of the specimens in the  siphon
station in San Antonio indicated this  same reaction with the concrete
control was occurring in the air space,  although not as severe. Subsequent
inspection revealed identical  staining of the control specimen in Harlingen.
Hydrogen sulfide or soluble sulfide salts were  suspected and subsequent
laboratory experiments confirmed this.  Concrete  specimens were sub-
jected to a 10% solution of sodium sulfide as well as to  a hydrogen sulfide
gas atmosphere.  The discoloration  or  staining was observed in each
instance and is attributed to a reaction  between the sulfide and iron present
in the cement.  When submerged in a 10% sodium sulfide solution for 3
days, discoloration occurred throughout the  specimen.   When suspended
in a hydrogen sulfide gas atmosphere for one week, staining had penetrated
to an average depth of 0.12 in. ,  but in some areas  as much as 0. 25 in.
To test the theory that an impregnant, by blocking  the voids,  should
eliminate penetration of liquid or gas, one specimen impregnated with
sulfur was submerged one week in a 10% solution of sodium sulfide.  Cut-
ting the specimen revealed that only the surface of the  specimen was dis-
colored, and penetration of the liquid had not taken place.   Likewise a
specimen impregnated with sulfur  suspended in a hydrogen sulfide gas
atmosphere showed only slight discoloration on the surface but no penetra-
tion.  Figure  12 is a photograph showing the  staining and protection afford-
ed by impregnation, when subjected  to a 10% sodium sulfide  solution.  The
specimen on the left is a concrete  control, while the center  specimen,
which is the concrete control submerged in sulfide solution, shows the
discoloration  throughout the cross-sectional area.  The specimen on the
right shows a surface staining but  the cross-sectional area is unstained,
indicating  that the sulfur blocked the pores and eliminated penetration.

Although the specimens were exposed in the field tests  for approximately
four months,  they were winter months when acid generation is at a min-
imum.  The concrete control specimen in Harlingen is  beginning  to show
signs of corrosion.  The entire specimen is covered with a white, frangible
efflorescent coating typical of sulfate formation.  The control in the siphon
station in San Antonio is  showing slight efflorescence and one specimen
coated with the vinyl-vinylidene  chloride emulsion  has  several pinholes.
All other  specimens in San Antonio and Harlingen are showing no signs of
corrosion.
                                    43

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Figure  12.  Staining of Concrete by Sodium Sulfide Solution

-------
                          SECTION IX

    SIGNIFICANCE OF LABORATORY AND FIELD FINDINGS

As  described in detail earlier,  10% sulfuric acid causes the most severe
attack on concrete.  Typical maximum concentrations of approximately
5%  as found in sewers are also severe.   As severe as this  attack is,
however, it is tempered by the fact that  although maximum concentra-
tions of 5% have been measured in sewers,  during the cooler months this
concentration drops considerably so that the most severe attack reported
(3)  in sewers is approximately  1/2 in. /yr. (0. 0014 in. /day) wall loss,
very nearly the same as that of limited laboratory tests of  a 1% solution
of sulfuric acid with scaling rates of approximately 0. 0015  in. /day.  If
further correlation studies can indeed verify that a 1% sulfuric acid
solution can  simulate the most  severe attack encountered in sewer lines,
then a very valuable laboratory tool will have been established for deter-
mining and predicting sewer pipe life.

The second interesting point as relates to sulfuric acid attack in labor-
atory tests is the  fact that for all concentrations the attack is limited to
the surface.   Attempts using vacuum and pressure failed to cause any
sulfuric acid to penetrate the concrete any deeper than 1/8  in. from the
surface.  This is  attributed to the fact that the sulfate and  sulfo-aluminate
products have larger crystal volumes than the reactants and as such tend
to seal or block the passages.  As this protective coating falls away,  the
attack progresses into the specimen.  Figure 13  shows the  surface attack
typical of sulfuric acid action in the laboratory test.  Limited specimens
taken from sewers indicate this type of attack is also typical  of the attack
found in some concrete sanitary sewers.

Hydrogen sulfide  or sulfide solutions  readily penetrate concrete. To
what extent this plays in the corrosion process has not been determined.
References to this occurance have not been uncovered in the literature.
The fact that sulfuric acid seals the surface,  may eliminate or minimize
attack in this manner.  The fact that impregnated specimens  were not
penetrated by the  sulfides is most encouraging.

Another point of major significance relates to the performance of the most
promising systems developed.  The scaling rate as determined for the
various  systems is a valuable aid  since  it not only gives an indication of
the relative performance of the different systems, it also allows for a
prediction of the life of the treated pipe  of known wall thickness.  While
the hazards of predicting pipe life based only on the laboratory findings


                                    45

-------
Figure 13. Surface Attack of Sulfuric Acid

-------
are fully realized, it is recognized that the acid test conditions of the
laboratory are much more severe than those encountered in the field.
It must be emphasized that considerably more field data have to be
obtained for good correlations, however, some conservative estimates
can still be made.  As already pointed out,  the most severe corrosion
measured in a sewer line  has been as much as 1/2  in. /yr,   or approx-
imately 0. 0014 in. /day. Thus a pipe having a wall thickness of 1 inch
would be consumed in 2 years.   This rate of attack is obtained in the
laboratory with a 1% solution of sulfuric  acid.  When using 10% solutions
of sulfuric acid,  the scaling rate for the concrete control averages
0. 0054 in. /day or approximately 3. 8 times greater than the most severe
cases found in sewer lines.

Although most of the better treatments did not have a measurable scaling
rate,  as indicated in Tables 1 and 2, continued exposure should produce
a measurable rate after an extended time.  For the coating alone,  once
the coating  has failed,  corrosion of the underlying  concrete  should pro-
ceed at the  same rate as unprotected concrete, hence the useful life of
the coating  systems is difficult to assess.  For the materials with measur-
able scaling rates, however, estimates of useful life can be made.

From Table 1, specimen No. 17,  which was impregnated with modified
sulfur,  had a  laboratory scaling rate of 0. 0005 in.  /day.  The concrete
control has a  laboratory scaling rate of 0. 0054 in.  /day.  Thus, the sulfur
impregnated pipe is approximately 10 times better  than concrete according
to the laboratory tests.  Thus,  as a  conservative estimate,  impregnated
pipe with a -wall thickness  of 1 inch would be consumed in 20 years rather
than 2 years.   If the fact is considered that the laboratory tests are 3. 8
times more severe than that of actually measured  sewer values, then it
would take 76 years to consume  the pipe.

As another  example, from Table 1, specimen No. 1,  which was impreg-
nated with hydrofluoric acid, has a measurable laboratory scaling rate
of 0. 00017 in. /day or  approximately 30 times better  than the laboratory
scaling rate of concrete.  Thus a pipe of 1 inch wall thickness would be
consumed in 60 years as a conservative  estimate,  or 228 years using
the factor of 3.8.

Pipe with wall thicknesses greater than one inch would  take  proportionately
longer to be consumed.  The fact that many of the better  systems had
scaling rates  of 0 after 3 days in 10% sulfuric acid  indicates that their
ultimate scaling  rate might be better than those used in the two examples
above.


                                   47

-------
The final point of significance from this program's findings is the
possibility of in-service treating of lines using the hydrofluoric acid
treatment.  Essentially this would  entail a low pressure acidizing
process  very similar to oil and gas well acidizing which is carried out
routinely in the petroleum  industry.
                                   48

-------
                          SECTION X

                          ECONOMICS

It is estimated that nearly 90 million linear feet of concrete pipe are
manufactured annually.  Its  low cost, ease by which it can be manu-
factured and its attractive physical properties  all play a role in its
popularity.   Whenever pipe other than concrete is used in sewer app-
lications, the additional cost is usually justified because of the  improved
corrosion resistance of the other type pipe, although weight consider-
ations can sometimes be  important. Figure 14 is a graph showing San
Antonio selling prices for the various types of sewer pipes available.
While  selling prices may vary somewhat from locality to locality, these
figures are representative of the relationships between the different
types of sewer pipe.  All of  the prices reflected in Figure 14 were
obtained from local manufacturers  or suppliers, except for  the vinyl
chloride lined/epoxy-coal tar lined pipe.  This curve  area was calculated
by adding to the cost of reinforced concrete pipe $0. 60 to  $0. 75  for
materials cost and $0. 15  to $0. 25 for labor per square foot of treated
concrete pipe.  The material and labor costs were obtained  from lining
and pipe manufacturers and  reflect typical additional costs.  Thus, in
order  for impregnated concrete pipe to be accepted, it must have a cost
effectiveness better than the  other types of pipe.

In discussing the economics of potential treatment systems the predicted
treatment costs are general figures since further processing studies are
needed to generate firmer economic figures.   Nevertheless, these estimates
give a good indication of the relative economics.

To impregnate or treat sewer pipe,  two extreme cases have been select-
ed and the economics calculated.  The first case envisions a rather  simple
automated process, requiring a minimum of hand labor.   In this process
the impregnation vat would operate at atmospheric pressure on a contin-
uous automated basis.  For  the hot melts, this vat would in many ways
resemble a typical sulfur melter or Frasch sulfur mine relay station.
The  rectangular pit or tank of steel or concrete would be  lined with  steam
heating coils  of Schedule  80  black steel pipe.   Material make-up to the pit
would  be supplied from either a molten storage tank or by melting material
on site.  One simple design  for a sulfur melter consists of laying steam
piping on a  concrete apron sloped into the pit.   Sulfur or the other materials
would  be stockpiled on the apron.  When additional material is required,
steam is circulated through  the pipes and the melted material drains into
the pit.  Temperature of the  molten material would be automatically


                                    49

-------
Ul
o
          40

          36


          32


          28

          24
        £ 20
        00
        c
        3 16
          12
             04     8    12    16    20    24    28    32    36    40    44   48    52    56   60     64    68    72
                                                            Pipe Diameter
                                                               (in.)
                     Figure 14. Selling Price as a Function of Pipe Diameter for Various Types of Sewer Pipe

-------
controlled by regulating the steam pressure.  Conveyors could be used
for moving the pipe into and out of the pit.   For impregnation materials
not requiring heat, the steam lines would be eliminated.  This type
of operation  should represent a very low impregnation cost.

The second process assumes almost exclusive hand labor such as
required in autoclaving the pipe on a batch basis.  Typical labor costs
are generally a maximum of $0. 25/ft^ of treated surface.  This  cost
was used  in calculating the costs under the hand labor columns in
Table 4.  The cost of impregnating concrete pipe with sulfur is report-
ed for both types of processes. The automated column assumes that the
pipe could be handled and treated for  essentially the same costs  that
the Frasch sulfur producers can mine the sulfur by heating with  super-
heated water a massive limestone  formation several thousand  feet
below ground surface, melt the sulfur,  pump it to the surface, store
it,  and finally sell it at a profit for $0. 01/lb.  This cost should reflect
the projected minimum cost.  The maximum projected cost is represent-
ed by having to use hand labor methods of a batch process.

The hydrofluoric acid treatment was viewed essentially as a materials
handling process since heat is not  required.  The typical selling price
for crushed aggregate is approximately $2. OO/yd^.  This includes mining
or blasting,  crushing, washing, and screening to specifications.  As
seen in Table 4,  the  hydrofluoric acid impregnation costs are  slightly
less but of the same  magnitude as  those for sulfur impregnation.

The coating costs as represented by the latexes assume hand labor with
spray equipment similar to that currently used in lining concrete pipe,
and were  computed for actual film, thicknesses used in the laboratory  for
adequate acid protection.  As can be seen, the labor accounts  for the
major portion of the  cost.  These types of  coatings, however,  should  find
acceptance more readily in treating in-place structures such as  treat-
ment tanks, junction boxes, wet wells,  etc.  More  detailed calculations
are  reported in Appendix B.

From an economic point of view,  impregnation or treatment of concrete
pipe with  either sulfur or hydrofluoric acid appears very attractive with
substantial savings over other types of pipe as well as lined concrete  pipe.
From the laboratory studies and preliminary field studies, the projected
service life of these  two treatments is certainly encouraging.  Because
of these facts, the next major step in this program should be one of
extended field tests,  paralleled by continued laboratory study to  further
develop a correlation between the laboratory and field data, so that

                                   51

-------
                                                      TABLE 4








                                   Relative Economics of Treating Concrete  Pipe








                                   	Cost Differential Above the Cost of Concrete Pipe ($/Linear ft. )
Impregnation
Pipe
Diameter
(in.)

18
24
30
36
48
60
Hand Labor
Costs for
Current Coatings
($ /linear ft)
1. 18
1.57
1.96
2.36
3. 14
3.92
Clay/
Poly ester -Glass
Fiber

3. 50
8. 00
11. 00
13. 00
20. 00
12. 00 *
Sulphur
at $0. 01/tb


Automated Hand Labor

.35
. 55
. 76
1.05
1.72
2.59

1. 35
1. 85
2.34
2. 88
4. 00
5. 22
HF
(5% Solution at)
at $0. 015/lb

. 22
. 35
.47
.65
1. 08
1. 62
Coating
Vinyl-
Vinylidene
Chloride
at $0. 18/lb
1. 18
1.89
2.36
2. 84
3.79
4. 73
Reclaimed
Rubber
at $0.40/lb

1. 30
2. 08
2. 60
3. 13
4. 16
5. 20
Plastic Lined Concrete

-------
optimum treatment systems can be developed with predictable service
lives.  Once an optimum system is determined, a specific process
design can be  undertaken and the economics can be established on a
very accurate basis.
                                   53

-------
                         SECTION XI

                    ACKNOWLEDGEMENTS

Test sites provided  by the City of Harlingen, Texas and the City of
San Antonio, Texas  are gratefully acknowledged.  Special appreciation
is due Messrs. L. N.  Rice,  City Engineer,  Harlingen,  Texas, H. C.
Norris, Sewer Engineer, City of San Antonio, Donald Carrell, Mission
Concrete Pipe Company,  San Antonio, Texas, and Harry T. Peck,
Gifford-Hill Pipe Company,  Dallas, Texas for their interest and tech-
nical contributions.  Finally, grateful acknowledgment is made to the
many manufacturers and suppliers who provided sample quantities of
their materials for inclusion in this program.

Key Personnel

Allen C. Ludwig, Project Manager and Principal Investigator
Southwest Research Institute
8500 Culebra Road
San Antonio, Texas  78228
Tel: 512  684-2000

John M. Dale,  Manager, Systems Development Section
Southwest Research Institute
8500 Culebra Road
San Antonio, Texas  78228
Tel: 512 684-2000

Frank  Condon, EPA Headquarters,  Project Manager
Combined Sewer  Pollution Control Branch
Environmental Protection Agency
Washington, D. C.   20242
Tel: 703  557-7390

George J. Putnicki,  Project  Officer
Environmental Protection Agency
1402 Elm Street
Dallas, Texas 75202
Tel: 212  749-2161

Robert  L. Hiller
Environmental Protection Agency
1402 Elm Street
Dallas, Texas 75202
Tel: 212  749-3842
                                   55

-------
                          SECTION XII

                         REFERENCES

 1.    Munger,  C.G. , "Sewer Corrosion and Protective Coatings",
      Civil Engineering. May I960, pp.  57-59.

 2.    South African Council of Scientific and Industrial Research,
      "Corrosion of Concrete Sewers", Series DR 12, 1958.

 3.    Lea,  F. M. and Desch,  C.H. , "The  Chemistry of Cement and
      Concrete", revised ed.  Edward Arnold Lts. , London, 1956.

 4.    Hansen, W. C. , "Attack on Portland Cement Concrete by Alkali
      Soils and Waters  - A Critical Review", Highway Research Record
      No.  113, Highway Research Board, 1966.

 5.    Kobbe, W- H. , "New Uses for Sulfur in Industry", Ind. and Eng.
      Chem. , Vol. 16,  No. 10, October 1924, p. 1026.

 6.    Kessler,  D. W. ,  "Sulphur Impregnated Sandstone", Stone,  Vol.
      XLV,  No. 6, June 1924, p. 347.

 7.    Steinberg, M. , et. al. , "Concrete-Polymer Materials,  First
      Topical Report",  BNL  SO134(T-509). December 1968.

 8.    Steinberg, M. , et. al. , "Concrete-Polymer Materials,  Second
      Topical Report",  BNL  50218(T-560), December 1969.

 9.    Kukacka, L. E. , Steinberg,  M. , and Manowitz,  B. , "Preliminary
      Cost Estimate for the Radiation-Induced Plastic Impregnation of
      Concrete", BNL-11263.  April 1967.

10.    Ludwig, A. C. , "Utilization of Sulphur and Sulphur Ores as
      Construction Materials  in Guatemala",  United Nations Report
      No.  TAO/GUA/4, July 1969.

11.    Ocrate Journal, N. 5,  January 1965.

12.    ACI Committee 515, "Guide for the Protection of Concrete Against
      Chemical Attack by Means of Coatings and Other Corrosion-
      Resistant Materials", Proc.  J. A. C.  I. ,  Vol.  63,  No.  12, December
      1966.

                                    57

-------
13.    Jumper,  C.H. ,  "Tests of Integral and Surface Waterproofings
      for Concrete",  Bur. Standards J. Research, Vol. 7, 1931,
      pp.  1147-77.

14.    Kessler, D. W. , "Experiments on Exterior Waterproofing Materials
      for Masonry",  J. Res. Nat'l. Bureau Standards, Vol. 14,  1935
      pp.  317-43.

15.    Meyer,  A. H. ,  and  Ledbetter, W. B. ,  "Sulfuric Acid Attack on
      Concrete Sewer Pipe", J.  of Sanitary Engr. Div. , ASCE, October
      1970, pp. 1167-82.

16.    Schremmer,  H. , "Attacking of Concrete by Hydrogen Sulphide",
      Derate Journal, No. 5, January 1965.

17.    Caudy, A. F. , Jr.,  "Studies on the Resistance to Corrosion of
      Ocrated Concrete", Project Report, A. F. Gaudy, Jr. and Associates,
      Stillwater,  Oklahoma.

18.    Dale,  J. M. ,  and Ludwig, A. C. ,   "Mechanical Properties of Sulfur
      Allotropes",  Materials Research and Standards,  Vol.  5, No.  8,
      August 1965,  pp. 411-417.

19.    Ludwig, A. C. , and Dale, J. M. ,   "Determination of the Mechanism
      Whereby S\i Affects the Mechanical Properties of Sulphur", Final
      Report, Southwest Research Institute,  San Antonio,  Texas.

20.   Frederick, L. R. ,  and Starkey,  R. L. ,  "Bacterial Oxidation of
      Sulfur in Pipe Sealing Mixtures", J. Amer.  Water Wks. Assoc. ,
      Vol. 40,  No. 7, July  1948, pp. 729-36.

21.    Duecker, W. W. , et.  al. , "Studies of Properties of Sulfur  Jointing
      Compounds", J. Amer. Water Wks. Assoc. ,  Vol. 40,  No. 7,
      July 1948, pp. 715-28.

22.   Bates,  P. H. , "The Use of Sulfur in Rendering Cement  Drain Tile
      Resistant to the Attack of Alkali", Ind. and Eng.  Chem. , Vol.  18,
      No. 3,  March 1926, pp. 309-10.
                                   58

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                          SECTION XIII


                          APPENDICES

                                                                Page

A.     Part A  - Water Soluble Salts and Acids                     61

       Part B  - Water Base Latexes                               62

       Part C  - Solvent Base Latexes                              65

       Part D  - Resins                                           66

       Part E   Hot Melts                                         69

B.     Detailed Materials Cost and Impregnation                   73
          or Coating Costs
                                    59

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           APPENDIX  A






Properties and Corrosion Resistance of





        Impregnated Concrete
                      60

-------
                                 Part A - Water Soluble Salts and Acids
Properties and Corrosion Resistance
Resin
Absorption
Specimen #* (%)
Control 	
1

2

3
4
19
21
22
23

29
48

49

50

52
53
56
80
127

128

129

Hydrofluoric
Acid (5%)
Hydrofluo silicic
Acid (2. 7%)
SP-4
Sodium Silicate
10% H3PO4
10% Zn Si F&
10% MgSI Ffc
5%/5% Zn/Mg
(Si F6)2
Oxalic Acid
10% H3PO4
(500°C Cure)
10% Sodium
Fluoride
10% Sodium Hexa-
metaphosphate
5. 5% Superbond
Superbond
10% Boric Acid
98% H2S04
Hydrofluo silicic
Acid (1%)
Hydrofluo silicic
Acid (0.5%)
Hydrofluo silicic
Acid (0. 1%)

5.

0.
5.
1.
2.
4.
2.

3.
4.

-2.

5.

3.
4.
7.
6.


0.

1.

1.

7

54
7
5
4
3
7

5
2

4

6

8
9
3
6
Attacked

9

8

9
Flexural
Strength
(psi)
1160

1050

1090
1030
1130
1520
1140
1330

1390
1210

1140

1400

2160
1110
1360
1300
Aggregate Only

1030

825

1080
of Impregnated Concrete
After exposure to 10% H2SO4
Wt. Loss
(K)
9.

2.

10.
2.
8.
12.
8.
8.

8.
9.

9.

7.

11.
10.
7.
5.


9.

8.

10.
2

3

7
7
1
2
2
2

6
0

2

2

4
2
7
3


2

2

6
Scaling
(in. /day)
. 005

.00017

. 007
0
.004
. 006
.0018
. 0018

. 0008
. 0008

.0063

. 001

. 0003
. 0027
.0013
. 0017
0

005

. 003

. 003
Flexural Strength
Room Cured
(psi)
1350

1290

1010
1270
**
1150
1170
1320

1240
1190

730

1280

1320
1170
1080
1140
--

1060

1410

1000
 *Specimen number as permanently recorded in the laboratory notebook.
##Dashed line indicates data not taken.

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                                                           Part B - Water Base Latexes
M

Resin
Absorption
Specimen # (%)
41 Silicone Latex 5.3
42 Butadiene /Styrene
Latex 6. 2
44 Natural Rubber
Latex 4.3
59 Vinyl Chloride-
Vinylidene
Chloride 14.4
60 Vinyl Chloride-
Acrylic 8.5
61 Vinyl Chloride-
Acrylic 5.8
62 Nitrile Rubber
Latex 6.3
63 Vinyl Chloride-
Vinylidene
Chloride 1.7
77 Acrylonitrile
Latex 1.7
78 Acrylonitrile
Latex 2. 2
79 Vinyl Chloride -
Acrylic 3.2
81 Vinyl Acetate -
Acrylic 7. 5
82 Vinyl Acetate -
Acrylic 6. 2
83 Polyvinyl Acetate 3.7

Flexural
Strength
(psi)
1480

1330

1030


1020

1070

1270

1270


1260

840

1200

880

760

710
930
After exposure to

Wt. Loss Scaling
(g) (in. /day)
6.3 .0023

9.7 .0013

8.9 .0009


0 0

0 0

12.0 .009

0 0


0 0

3.2 .0015

+1.7* .0007

17.2 .0018

0 0

0 0
+ 1.3 0
10% H2SO4
Flexural Strength
Room Cured
(psi)
1290

1290

12ZO




1010

1030




--

1190

1190

890

750

700
810
                     *(+ sign indicates wt. or dimension gain)

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                                     Part B - Water Base Latexes (cont'd)
                                                             After exposure to 10% H2SO4
Resin
Absorption
Specimen # (%)
84
85

86


87

88
89
110


111

112
Acrylic
Vinyl Chloride-
Acrylic
Vinyl Chloride-
Vinylidene
Chloride
Vinyl Chloride-
Acrylic
Acrylonitrile
Reclaimed Rubber
Vinyl- Vinylidene
Chloride and
Surfactant
Reclaimed
Rubber
Reclaimed Rubber
3.

1.


2.

1.
2.
7.


9.

3.

3

9


1

3
4
4


6

8

Flexural
Strength
(psi)
740

710


500

980
290
550


1050

680

Wt. Loss
(e)
0

+ 2.


+4.

8.
+ 1.
+ 1.


+ 1.

+ 1.


8


7

0
0
6


4

5

Scaling
(in. /day)
.0026

.0008


+ .005

.0017
0
0


+ 0. 005

0

Flexural Strength
Room Cured
(psi)
790

870


750

950
710
980


1170

670

(over nitrile-phenolic
     tack coat)        7. 7
114 Vinyl Acetate-
    Acrylic (over
    nitr ile - phenolic
    tack coat)        2. 2
115 Vinyl Chloride-
    Vinylidene Chloride
    (over nitrile-phenolic
     tack coat)        1. 3
790
875
965
+ 2.3
+3.7
                                                                                       715
720
850

-------
Part B - Water Base Latexes (cont'd)
                       After exposure to 10%
Resin
Absorption
Specimen # (%)
116
120
Nitrile Latex
8.8
Vinyl Chloride-
Vinylidene Chloride
and Surfactant 5. 2
Flexural Flexural Strength
Strength Wt. Loss Scaling Room Cured
(psi) (g) (in. /day) (psi)
765 13.3 .0027 1070
1560 1.1 .0021 960
123 Reclaimed Rubber

130

(Water base)
Modified Vinyl-
Vinylidene
Chloride
2. 1

5.7
1090 +2. 1 0 1050

+ 4.0 +.007 850

-------
                                         Part C - Solvent Base Latexes
 Specimen #
                        Resin
                      Absorption
 43  Nitrile-Phenolic
    Rubber              0.8
 45  Nitrile-Phenolic
    Rubber (Brushed on) 1.2
 54  50% Nitrile-Phenolic
    Rubber/Solvent      0.9
 58  50% Nitrile-Phenolic
    Rubber/Solvent
     (Oven dried)         0. 9
 64  Nitrile-Phenolic     0.9
 65  Rubber in            1.6
 66  50% Solution of      2.4
    methyl ethyl
 67  ketone               3.5
 71  Chloronated Poly-
    ethylene             1. 8
124  Reclaimed Rubber
    (Solvent base)        0. 7
126  Rubber Adhesive     1.0
137  30% Solution of
    Vinyl-Vinylidene
    Chloride in Toluene
138  30% Solution of
    Vinyl-Vinylidene Chloride
    in Toluene with 2% Talc
Flexural
Strength
 (psi)
  1710

  1260

  1050
  1250
 1 coat
2 coats
3 coats

4 coats

  1500

  1250
  1160
1 coat
2 coats
3 coats
1 coat
2 coats
3 coats
Wt. Loss
  (g)
          After exposure to 10% H2SO4	
                              Flexural Strength
    0
    0
    0
    0

    0

  11. 1

   6.4
  + 3.7
     Scaling
     (in. /day)
      Room Cured
       (psi)
7.6
0
5. 1
. 0005
0
. 0022
1360
1330
1160
      , 007
Moderate resistance
Good  resistance
Extremely good resistance

Extremely good resistance

       1180
      .001
      . 0007
Poor  Resistance
Poor  Resistance
Fair Resistance
Fair Resistance
Fair Resistance
Excellent Resistance
       1100
       1360

-------
Part D -  Resins
After exposure to 10% H2SO4
Resin
Absorption
Specimen # (%)
5

6
7
8
9
10
11
12
13
14
24
25

26
27

28
31

39
40
46

47

Urea Formalde-
hyde
Silicone
Silicone
Furan Resin
Linseed Oil
Urea -Formaldehyde
Urea -Formaldehyde
Phenolic Resin
Urea -Formaldehyde
Urea -Formaldehyde
Acrylic
Alkyd Traffic
Marking Paint
Acrylic Wax
Modified Urea-
Formaldehyde
Tung Oil
Modified Phenolic
Resin
Resin Oil A
Resin Oil B
Resin Oil B
(Oven dried)
Resin Oil A
(Oven dried)

1.
7.
4.
2.
2.
5.
1.
1.
0.
0.
1.

3.
1.

4.
1.

1.
4.
1.

0.

1.

4
1
8
6
6
7
0
2
94
66
8

8
0

8
9

3
2
6

8

5-
Flexural
Strength
(pei)

1170
1340
1095
950
1380
1290
1600
1880
1570
1670
1590

1540
1280

1560
1560

1640
1380
1560

1230

1090
Wt. Loss
W

7.
8.
9.
9.
11.
11.
8.
4.
8.
6.
7.

7.
8.

9.
11.

7.
8.
9.

9.

6.

6
1
6
7
9
5
1
8
1
7
3

4
7

4
2

2
7
8

2

6
Flexural Strength
Scaling Room Cured
(in. /day) (psi)

. 0013
. 0047
. 0067
. 0015
. 0067
. 0068
. 0047
. 0012
.0073
. 003
. 005

.0019
. 004

. 0008
. 0007

. 002
. 0018
. 0028

. 0033

. 0033

1080
1400
1260
1110
1510
--
990
1530
1400
1300
1580

1250
1350

1190
1160

1410
1210
1420

--

--
Flexural Strength
Heat Cured
(psi)

1190
--

1080
1820
1250
1260
1580
1420
1830
--

--
--

--
--

--
--
--

1120

1180

-------
Part D - Resins (cont'd)
After exposure to 10% H2SO4
Resin Flexural FLexural Strength Flexural Strength
Absorption Strength Wt. Loss Scaling Room Cured Heat Cured
Specimen # (%) (psi) (g) (in. /day) (psi) (psi)
55 50% Urea Form-
aldehyde inToleune
57 Flexible Epoxy
74 Alkyd Resin
90 Rigid Epoxy
91 Flexible Epoxy
92 Rigid Epoxy
93 Flexible Epoxy
94 Rigid Epoxy
95 Flexible Epoxy
96 Rigid Epoxy
97 Flexible Epoxy
98 Epoxy
99 Epoxy
100 Epoxy
101 Epoxy
102 Epoxy
103 Furan
104 Furan
105 Melamine-Alkyd
(coating only)
107 Melamine-Alkyd
109 Melamine-Alkyd
(coating only)
117 Butadiene-Furfural
118 Urea-Formaldehyde-
Alkyd

3.0
5. 3
1.8
4.9
9.5
No
No
1.9
2.4
5.5
8.3
3.8
7. 1
1.5
2. 7

7.9
4.6

1.9
2. 7

1.3
1.9

2. 2

3030
1360
1420
1330
1020
penetration
penetration
1660
1330
3150
2560
1180
1360
1230
1010
Solution
685
915

1280
1380

1300
730

1410

9. 1
8.9
20. 5
+ 2.7
13. 2


+ 0. 5
14. 0
+ 1. 5
21. 7
+ 5.6
+ 7. 2
5.0
5. 1
boiled over
0
0. 6

+ 1.3
12. 1

3. 4
10.4

7.4

. 003
. 005
. 006
+0. 002
. 0037


+0. 0017
0. 0013
+0. 0027
0. 0023
+ . 0043
. 0007
. 0017
0. 0015
- - No penetration
0. 0013
0. 0022

0
0. 0013

0.0022
0

. 0008

1380
1310
1370
1310
880


1280
1170
2480
1460
1310
920
1000
765

1000
1000

--
--

900
--



--
--
--
--
--


--
--
--
--

--
--
--


--

1250
1200

--
965

1330

-------
                 Specimen #
                     Part D - Resins (cont'd)

                      	After exposure to  10% H2SO4	
   Resin    Flexural                       Flexural Strength  Flexural Strength
Absorption  Strength  Wt. Loss   Scaling     Room Cured        Heat Cured
   (%)         (psi)        (g)     (in. /day)     (psi)	        (psi)	
                 1 19 Urea-Formalde-
                     hyde-Alkyd (coat-
                     ing only)            2. 0        1115        3.7        . 003
                 121 Urea-Formalde-
                     hyde-Alky d (coat-
                     ing only)            1.6        1090       11.4        . 007
                 122 Urea-Formalde-
                     hyde-Alkyd (coat-
                     ing only)            1.5        1010       13.4        . 005
                 125 Epoxy               2.5        1310       +1.1         0
                                                1150
                                                1270
                                                                    1000
                                                                     945
00

-------
                                                           Part  E - Hot Melts
v£>
               Specimen #
                                      Resin
                                    Absorption
15 Sulfur               9.7
16 Cut back Asphalt     5.0
17 Plasticized Sulfur    8.8
18 Modified Sulfur      6. 6
ZO Paraffin             4.0
30 Asphalt              0.75
32 Modified Sulfur      9.8
33 Modified Sulfur      7.8
34 Polyethylene Wax    1.1
35 Same as 33 with
   coating              9. 0
36 Polyethylene Wax/
   Paraffin             1.9
37 Coal Tar Pipe Dip   4.8
38 Coal Tar Roofing
   Pitch                4.3
51 Paraffin/Polyiso-
   butylene             4.7
68 Coal Tar Roofing
   over HF Treatment  5.3
69 Sulfur over HF
   Treatment           4. 7
70 Modified Paraffin    5.0
72 Modified Paraffin    2.7
73a Coal Tar - Hot
     Specimen           3. 8
  b  Coal  Tar - Cold
     Specimen         23. 6

Flexural
Strength
(psi)
2970
1590
2800
1650
2030
1730
2690
1970
1350
2570
1720
1700


Wt. Loss
(K)
6.9
16.2
5. 1
5.7
9.4
9. 1
7. 0
7. 1
7.9
6,4
9.2
10. 1
After exposure to

Scaling
(in. /day)
0
.0097
. 0005
. 0008
.006
. 003
.0015
. 0017
.0018
.002
.0025
.0016
10% H2SO4
Flexural Strength
Room Cured
(psi)
2890
1690
1770
2230
1720
1300
I960
2260
1320
2310
1290
1310
                                                        2040

                                                        1700
                                                        2000
                                                        1370
13.9

14.0

 1.9

+2.6
 8.6
20. 2

15.6
.0023

.0037

 0

 0
. 006
.013
1730

1130
2300
1520
1080

-------
Part E - Hot Melts (cont'd)
After exposure to 10% H^SO4
Resin
Absorption
Specimen # (%)
75a Asphalt - Hot
Specimen
b Asphalt - Cold
Specimen
76a Cut back Asphalt
Hot Specimen
b Cut back Asphalt
Cold Specimen
106 Paraffin Emulsion
(Coating only)
108 Paraffin Emulsion
1 13 Coal Tar (over

16.

25.

1.

3.

1.
2.


0

0

8

5

4
6

Flexural
Strength
(psi)

--

--

Tacky

Tacky

700
740

Wt. Loss Scaling
(g) (in. /day)

0. 8 0

0.2 0

- Never set

- Never set

17.5 0.0023
14.8 0.0017

Flexural Strength
R oom Cured
(psi)









685
650

     nit rile-phenolic
     tack coat)            16. 4
131  Sulfur impregnated,
    then coated with
    Vinyl-Vinyli dene
     Chloride              7. 8
132  Sulfur impregnated,
     then coated with
     Nit rile-Phenolic
     Latex               10.8
133  Sulfur impregnated,
     then coated with
     Rubber Adhesive     13.0
134  Sulfur impregnated,
     then coated with
     Reclaimed Rubber   13.0
 745
                0. 7
               + 2. 5
               + 2.6
 835
2080

-------
                                        Part E - Hot Melts (cont'd)

                                                                After exposure to 10% H2SO4
                        Resin          Flexural                                      Flexural Strength
                     Absorption        Strength       Wt. Loss        Scaling           Room Cured
Specimen #	       (%)              (psi)           (g)            (in. /day)       	(psi)	

135  Coal tar Pitch       16.0                              0             0
     over Special
     Primer
136  Asphalt-Gilsonite    16.0               --            18.1           0.011
     Product

-------
               APPENDIX  B





Detailed Materials'  Cost and Impregnation or




                Coating Costs
                          72

-------
                                       DETAILED MATERIALS COST AND IMPREGNATION OR COATING COSTS
                                          Sulfur at a Cost of $0. 01 /lb
                                                                              5% HFSolution at $0. 015/lb
00
Pipe
Diameter
Class B (in.
18
24
30
36
48
60
Pipe
Density
) (lb/ft)
173
276
375
524
860
1295
Impregnated Cost
Sulfur ($/ft)
at 10% (lb)
17.3
27.6
37.5
52,4
86.0
129.5
. 173
. 276
.375
. 524
.860
1. 295
Internal
Surface
Area/ft
4.72
6. 28
7.85
9.42
12. 56
15. 7
Hand Labor
Cost at
$0. 25 /ft2
($/ft)
1. 18
1.57
1.96
2.36
3. 14
3.92
Automated
Process
at 2x Sulfur
Cost ($/ft)
0. 35
0. 55
.75
1.05
1.72
2.59
Hand Labor
Materials 81
Labor
($/ft)
1.35
1. 85
2. 34
2. 88
4. 00
5.22
HF Cost Handling
Req'd for 5% ($/ft) Cost at
(lb) $0.0005/lb
($/ft)
8. 7
13.8
18.8
26. 2
43.0
64.7
. 13
0.21
0. 28
0. 39
0. 65
0. 97
.09
0. 14
0. 19
0. 26
0.43
0. 65
Total Cost
($/ft)
0. 22
0.35
0.47
0. 65
1.08
1.62
COATINGS
Based on a 15. 4g/17. 2 in2 coating

       Vinyl Vinylidene Chloride
 at  $0. 18/lb    50% Solution
     $0.37/lb    Dry basis
       180 Vinyl Acetate/Acrylic
 at $0. 16/lb    55% Solution
    Based on a  ll.Og/17.2 in2 coating

Reclaimed Rubber Emulsion at $0.40/lb
              of Nitrile-phenolic resin
             at $0.40/lb

Dia.
18
24
30
36
48
60

ft2
4.
6.
7.
9.
12.
15.
Wt/ft2
/ft (lb/ft*)
72 . 285
28
85
42
56
7
Wt/ft
(lb/ft)
1.35
1.79
2.24
2.68
3.58
4.48
Material
Cost
($/ft)
0.24
0.32
0.40
0.48
0. 65
0.81
Labor Cost Total
at 0. 25/ft2 Cost

1. 18
1.57
1.96
2.36
3. 14
3.92
$/ft
1.42
1.89
2.36
2.84
3.79
4.73
Wt/ft2 Wt/ft
(lb/ft2) (lb/ft)

. 204
1.
1.
1.
2.
3.

96
28
60
92
56
20
Material
Cost
($/ft)_
0. 38
0. 51
0. 64
0.77
1.02
1.28
Labor
Cost at
$0
1.
1.
1.
2.
3.
3.
. 25/ft
18
57
96
36
14
92
Total Cost
($/ft)

1.56
2. 08
2. 60
3. 13
4. 16
5. 20

-------
    Access/on Number
                          Subject Field & Group
                              08G
                                             SELECTED WATER  RESOURCES ABSTRACTS
                                                   INPUT TRANSACTION FORM
    Organization
                         Research Institute
              San Antonio, Texas
    Title
              IMPREGNATION OF CONCRETE PIPE,
1 Q Authors)
Ludwig, Allen C.
Dale, John M.
16

21
Project Designation
Contract #14-12-835
Program 11024 EQE
Note
 22
    Citation
    Descriptors (Starred First)
                      Concrete* Concrete pipes,  Corrosion,  Corrosion control,
                      Protective coatingsf Sewers, Sulfur, Hydrogen sulfide,
                      Resins
23
 25
    Identifiers (Starred First)
                                  Xc                   &               ty
                     Impregnation, Hydrofluoric acid, Acid resistance,  Bacterial
                      action, Sulfate resistance'
 27
   Abstract
             Methods to increase the corrosion resistance, increase the strength,
      and reduce the permeability of concrete used in sewer line applications by im-
      pregnating the concrete pipe with relatively low cost resins such as asphalt,
      coal tars, linseed oil,  sulfur,  urea-formaldehyde, and others were investigated.
             The materials, techniques of application, test results and economics
      are presented.  A large number of candidate impregnation materials were ob-
      tained and screened both in the laboratory and in limited field tests.  Dilute
      hydrofluoric  acid, sulfur and modified sulfur were found to impart the best
      corrosion resistance by impregnation.  Other materials including vinyl-
      vinylidene chloride, vinyl acetate-acrylic,  nitrile rubber  latex, nitrile phenolic
      rubber, an emulsified reclaimed rubber and a rubber base adhesive, although
      failing to. impregnate the concrete, formed surface coatings having exceptional
      corrosion resistance.
             This  report was submitted in fulfillment of Program No.  11024 EQE,
      Contract No.  14-12-835 under  the sponsorship of the Water Quality Office,
      Environmental Protection Agency.  (Ludwig-Southwest Research Institute)
Abstractor
   A. C.  Ludwig
                             Institution
                                     Southwest Research Institute
 WR:t02 (REV. JULV 1969)
 WRSIC
                                            SEND TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                                   U.S. DEPARTMENTOFTHEINTERIOR       «.=." I tH
                                                   WASHINGTON. D. C. 20340
                                                                            * SPO: 1969-359-339

-------
Continued from inside front cover....
11022 	 08/67

11023 	 09/67

11020 	 12/67

11023 	 05/68

11031 	 08/68
11030 DNS 01/69
11020 DIH 06/69
11020 DES 06/69
11020 	 06/69
11020 EXV 07/69

11020 DIG 08/69
11023 DPI 08/69
11020 DGZ 10/69
11020 EKO 10/69
11020 	 10/69
11024 FKN 11/69

11020 DWF 12/69
11000 	 01/70

11020 FKI 01/70

11024 DDK 02/70
11023 FDD 03/70

11024 DMS 05/70

11023 EVO 06/70
11024 	 06/70
11034 FKL 07/70
11022 DMU 07/70
11024 EJC 07/70

11020 	 08/70
11022 DMU 08/70

11023 	 08/70
11023 FIX 08/70
11024 EXF 08/70
Phase I - Feasibility of a Periodic  Flushing System for
Combined Sewer Cleaning
Demonstrate Feasibility of the Use of Ultrasonic  Filtration
in Treating the Overflows from Combined  and/or  Storm Sewers
Problems of Combined Sewer Facilities and  Overflows,  1967
(WP-20-11)
Feasibility of a Stabilization-Retention Basin  in Lake  Erie
at Cleveland, Ohio
The Beneficial Use of Storm Water
Water Pollution Aspects of Urban Runoff, (WP-20-15)
Improved Sealants for Infiltration Control,  (WP-20-18)
Selected Urban Storm Water Runoff Abstracts,  (WP-20-21)
Sewer Infiltration Reduction by Zone Pumping, (DAST-9)
Strainer/Filter Treatment of Combined Sewer  Overflows,
(WP-20-16)
Polymers for Sewer Flow Control, (WP-20-22)
Rapid-Flow Filter for Sewer Overflows
Design of a Combined Sewer Fluidic Regulator, (DAST-13)
Combined Sewer Separation Using Pressure Sewers,  (ORD-4)
Crazed Resin Filtration of Combined  Sewer  Overflows,  (DAST-4)
Stream Pollution and Abatement from  Combined  Sewer  Overflows •
Bucyrus, Ohio, (DAST-32)
Control of Pollution by Underwater Storage
Storm and Combined Sewer Demonstration Projects -
January 1970
Dissolved Air Flotation Treatment of Combined Sewer
Overflows, (WP-20-17)
Proposed Combined Sewer Control by Electrode Potential
Rotary Vibratory Fine Screening of Combined  Sewer Overflows,
(DAST-5)
Engineering Investigation of Sewer Overflow Problem -
Roanoke, Virginia
Microstraining and Disinfection of Combined  Sewer Overflows
Combined Sewer Overflow Abatement Technology
Storm Water Pollution from Urban Land Activity
Combined Sewer Regulator Overflow Facilities
Selected Urban Storm Water Abstracts, July 1968 -
June 1970
Combined Sewer Overflow Seminar Papers
Combined Sewer Regulation and Management - A Manual of
Practice
Retention Basin Control of Combined  Sewer  Overflows
Conceptual Engineering Report - Kingman  Lake  Project
Combined Sewer Overflow Abatement Alternatives  -
Washington, D.C.

-------