600284015 PROPERTY OF
REIWEWAl. RESPONSE
PB84-139732
COMPATIBILITY OF GROUTS WITH HAZARDOUS WASTES
JRB Associates, Inc.,
McLean, Virginia
Jan 84
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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PROPERTY OF THE
OFFICE OF SUPERFUN0
EPA-600/2-84-015
January 1984
COMPATIBILITY OF GROUTS WITH HAZARDOUS WASTES
by
P.A. Spooner, G.E. Hunt,
V.E. Hodge, and P.M. Wagner
JRB Associates
McLean, Virginia 22102
EPA Contract Number: 68-03-3113
Task: 40-3
Project Officer
H.R. Pahren
Solid and Hazardous Waste Research Division
Municipal Environmental Research Laboratory
Cincinnati, Ohio 45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
REPRODUCED BY
NATIONAL TECHNICAL
INFORMATION SERVICE
US. DEPARTMENT OF COMMERCE
SPRINGFIELD, VA. 22161
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TECHNICAL REPORT DATA
(Pleat read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-84-015
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
COMPATIBILITY OF GROUTS WITH HAZARDOUS WASTES
[8. REPORT DATE
January 1934
6. PERFORMING ORGANIZATION CODE
AUTHOR(S)
P. A. Spooner, G. E. Hunt
V. E. Hodge and P. H. Hagner
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
EJYL
9. PERFORMING ORGANIZATION NAME AND AOORESS
JRB Associates
8499 Westpark Drive
McLean, VA 22102
TEjYIA
. CQNTRAC1
11. CONTRACT/GRANT NO.
68-03-3113
12. SPONSORING AGENCY NAME AND AOORESS
Municipal Environmental Research Laboratory—Cin., OH
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT ANO PERIOD COVERED
1 Final
14. SPONSORING AGENCY CODE
EPA 600/14
IS. SUPPLEMENTARY MOTES
Project Officer: Herbert R. Pahren (513)684-7871
--£>
i/>
a
16. ABSTRACT
A study was conducted to determine the known information on the
compatibility of grouts with different classes of chemicals. The information
gathered here can be used as a basis for testing and selecting grouts to be
used at specific waste disposal sites with various leachates..
Twelve different types of grouts are included in this study; their
inclusion is based on'their availability and use in waterproofing and soil
consolidation projects. These grouts are bitumen, Portland cement type I,
Portland cement types II and V, clay, clay-cement, silicate, acrylamide,
phenolic, urethane, urea-formaldehyde, epoxy, and polyester. Sixteen general
classes of organic and inorganic compounds are also identified that include
the types of chemicals which most probably would be found in leachate from a
hazardous waste disposal site. The known effects of each chemical class on
the setting time and durability of each grout are identified and presented in
a matrix. These data were based on a review of the available literature and
contact with knowledgeable persons in industries, universities, and government
agencies. The physical and chemical properties, reaction theory, and known
chemical compatibility of each grout type are discussed.
17.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
bJDENTIFIERS/OFEN ENDED TERMS C. COSATI Field/C/OUp
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS /This Report!
UNCLASSIFIED
20- SeCURITY CLASS/TTiu page)
. SECURITY CLASS {
UNCLASSIFIED
EPA f»t» 2220.1 (R«». 4-77) »««viou> COITION it OMOLCTC
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DISCLAIMER
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under Contract No.
68-03-3113 to JRB Associates. It has been subject to the Agency's peer and
administrative review and has been approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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FOREWORD
The U.S. Environmental Protection Agency was created because of
increasing public and government concern about the nation's environment and
its effect on the health and welfare of the American people. Noxious air,
foul water, and spoiled land are tragic testimonies to the deterioration of
our natural environment. The complexity of that environment and the inter-
play of its components require a concentrated and integrated attack on the
problem.
Research and development is that necessary first step in problem
solution; it involves defining the problem, measuring its impact, and
searching for solutions. The Municipal Environmental Research Laboratory
develops new and improved technology and systems to prevent, treat, and
manage wastewater and solid and hazardous waste pollutant discharges from
municipal and community sources, to preserve and treat public drinking water
supplies, and to minimize the adverse economic, social, health, and aesthetic
effects of pollution. This publication is one of the products of that
research and provides a most vital communications link between the researcher
and the user community.
The report provides a summary of information on the predicted
compatibility of various types of grouts with different classes of chemicals.
In certain instances grouts may be used to seal ground masses around
uncontrolled hazardous waste sites. Information in the report may be used to
provide guidance on the testing, selection, or use of grouts at a particular
site.
Francis T. Mayo, Director
Municipal Environmental Research
Laboratory
111
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ABSTRACT
A study was conducted to determine the known information on the compat-
ibility of grouts with different classes of chemicals. The information
gathered here can be used as a basis for testing and selecting grouts to be
used at specific waste disposal sites with various leachates.
Twelve different types of grouts are included in this study; their
inclusion is based on their availability and use in waterproofing and soil
consolidation projects. These grouts are bitumen, Portland cement type I,
Portland cement types II and V, clay, clay-cement, silicate, acrylamide,
phenolic, urethane, urea-formaldehyde, epoxy, and polyester. Sixteen general
classes of organic and inorganic compounds are also identified that include
the types of chemicals which most probably would be found in leachate from a
hazardous waste disposal site. The known effects of each chemical class on
the setting time and durability of each grout are identified and presented in
a matrix. These data were based on a review of the available literature and
contact with knowledgeable persons in industries, universities, and govern-
ment agencies. The physical and chemical properties, reaction theory, and
known chemical compatibility of each grout type are discussed.
Since compatibility data are not complete for each grout type, predic-
tions are made, where possible, for the silicate and organic polymer grouts
based on their reaction theory. These results are also presented in a
matrix.
To establish the compatibility of chemicals with grouts, a series of
laboratory tests should be performed. The two grout properties that must be
addressed are permeability of the grouted soil and set time of the grout.
No established testing procedures are identified in the literature for
determining the effects of chemicals on these grout properties. Fixed-wall
and triaxial permeameters, which are used for soil testing, can be utilized
for measuring the effects of chemicals on permeability. For set time, there
is no single procedure that applies to all grout types for determining set
time. Visual observation is the easiest method, though somewhat subjective.
Preceding page blank
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The selection of a grout for a specific waste site depends on its
injectability, durability, and strength. These factors relate site
hydrology, geochemistry, and geology to grout physical and chemical
properties.
This report was submitted in fulfillment of Contract No. 68-03-3113 by
JRB Associates under the sponsorship of the U.S. Environmental Protection
Agency. The report covers the period April 5, 1982, to November 2, 1982, and
work was completed as of November 2, 1982.
VI
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CONTENTS
Foreword iii
Abstract v
Figures ix
Tables x
Acknowledgement xi
1. Introduction 1
Application of report 2
2. Conclusions 3
3. Recommendations 5
4. Grouting Techniques 7
Grouting methods 7
Grout types 12
Site characteristics 14
5. Chemical and Physical Properties of Grouts 17
Properties of bitumen grouts 17
Properties of cement grouts 20
Properties of clay grouts 26
Properties of cement-bentonite grouts 32
Properties of silicate grouts 33
Properties of organic polymer grouts 36
Properties of other grouts 53
6. Compatibility of Grouts with Hazardous Wastes 57
Known compatibility of grouts with classes of chemicals . . 57
Predicted compatibility of grout with classes
of chemicals 74
7. Grout Compatibility Testing Procedures 83
Permeability of grouted sand 83
Effect of leachate on grout set time 95
Overview of compatibility tests 99
8. Grout Selection 101
Injectability ' . . 101
Durability 103
Other factors 106
Overview 106
VII
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9. Research Needs 109
Grout specifications and applications 109
Compatibility of grouts with chemicals 109
Long-range stability of grouts 110
Compatibility testing procedures 110
References . . HI
Bibliography . 119
Appendices
A. Annotated Bibliography „ 133
B. Grout Manufactures/Suppliers Information „ . 137
Vlll
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FIGURES
Figure Page
1 Grout Pipe Layout for Grout Curtain 8
2 Semicircular Grout Curtain Around Waste Site 9
3 Vibrating Beam Grout Injection 11
4 Jet Grouting 13
5 Interactions Between Grouts and Generic Chemical Classes 72
6 Interactions Between Grouts and Specific Chemical Groups 75
7 Predicted Grout Compatibilities 77
8 Constant Head Permeameter 85
9 Variable Head Permeameter 87
10 Constant Head and Variable Head Permeameters 89
11 Variable Head Consolidation Permeameter 90
12 Triaxial Permeameter with Back Pressure 92
13 Constant Head Triaxial Permeameter 93
14 Schematic of Grouting Test Apparatus 96
15 Rotational Viscometer 98
16 Grout Selection Process 102
17 Applicability of Different Classes of Grouts Based on Soil
Grain Size. 104
IX
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TABLES
Table Page
1 Materials Compatible with Cement 24
2 Materials Incompatible with Cement. 25
3 Effect on Permeability of Several Undiluted Organic
Chemicals on Selected Clays ......... 30
4 Soil/Bentonite Permeability Increases Due to Leaching With
Various Pollutants 31
5 Components of Acrylamide Grouts . . 38
6 Phenol Resin Grout Products ..... . . 42
7 Examples of Chemical Within Each of the Chemical Grouts ... 60
8 Constituents of the General Grout Classes . .... 73
9 Ranges of Values of Various Properties of Selected
Grout Types 105
10 Toxicity of Selected Grouts 107
11 Approximate Cost of Grout 108
x
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ACKNOWLEDGEMENT
The authors gratefully acknowledge the constructive contributions of the
following reviewers of this report:
Herbert Pahren U.S. EPA, MERL, Cincinnati, OH. Project Officer
Walter Grube U.S. EPA, MERL, Cincinnati, OH.
Richard Stanford U.S. EPA, OERR, Washington, D.C.
Kenneth StoHer U.S. EPA Region II, New York, NY.
Philip Malone U.S. Army Engineer Waterways Experiment Station,
Vicksburg, MS.
James May U.S. Army Engineer Waterways Experiment Station,
Vicksburg, MS.
Robert Larson U.S. Army Engineer Waterways Experiment Station,
Vicksburg, MS.
The technical contributions of the following individuals were greatly
appreciated.
George Alther International Minerals and Chemical Corporation,
IMCORE Division, Detroit, MI.
John Ayers GZA Corporation, Upper Newton Falls, MA.
Donald Hentz Federal Bentonite, Belle Fourche, SD.
Dr. Raymond Krizek Northwestern University, Chicago, IL.
Glen Schwartz Engineered Construction International, Inc.
Pittsburgh, PA.
Our appreciation is also extended to the numerous other individuals who
were contacted on matters related to this report.
XI
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SECTION 1
INTRODUCTION
The purpose of this project is to compile data on the compatibility and
durability of grouts in the presence of hazardous wastes and leachates, and
to summarize the test procedures available to measure durability.
Grouting has been used for years by the construction industry as a
technique for treating ground masses to consolidate and seal them. The
principal use for grouting has been for large dam and tunneling projects.
Although grouting is still very much an art rather than an exact engineering
discipline, a great deal has been published on the properties, applications,
and testing of grouts. But, nearly all of this information however, has
focused on the use of grout in construction rather than in remedial work at
hazardous waste disposal sites. In addition, the testing procedures in
current use are not yet standardized and do not deal directly with the
ability of grouts to set up in and withstand attack from hazardous wastes and
leachates.
Consequently, this study centered on collecting, organizing, and
analyzing existing published and unpublished information on the compatibility
and durability of grouts with various classes of chemicals. Published
literature was identified by undertaking a computer literature search as well
as tree searches. Universities were contacted in order to collect
information from research programs. Grout manufacturers, grout supply
companies and grout installation firms were contacted for information on
grout compatibility and the physical/chemical characteristics of the grouts
they manufactured or used. Information gained by contacting industry was
limited primarily due to the lack of specific compatibility information. In
a few cases, though, information was available but could not be released due
to its proprietary nature. Where sufficient information was not available,
compatibility determinations were based on the chemistry and reaction
theories of the various grouts and chemical classes.
This report reviews the properties of the grouts in use today and
summarizes their chemical compatibility. Included is an overview of grouting
and a discussion of grout compatibility testing procedures. Also addressed
are the factors to be considered in grout selection and the grout selection
process. The report also identifies areas that need more research for a full
evaluation of grout compatibility with hazardous materials. Appendix A
presents abstracts of key information resources, and Appendix B presents a
listing of grouts and the companies which manufacture them.
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APPLICATION OF REPORT
A key aspect of this report is a series of matrices presenting the known
and predicted effects of different chemical groups on the set time and
durability of the various grouts currently in use. The chemical groupings
used in these matrices contain most of the organic and inorganic compounds
found in hazardous wastes and associated leachate. For the purposes of this
report, the compounds contained in these wastes and leachates are assumed to
act independently. Since a detailed chemical characterization is assumed to
have been performed before containment systems are evaluated, the individual
components will be known.
This report presents the basic information for selecting grouts based
on their compatibility with chemicals, it does not specifically address the
stability of the grouts with respect to ground conditions, other factors that
affect durability, nor grout-specific properties that are ultimately
influential in the selection of grouts. These topics are briefly summarized
in the descriptions of grout properties, however.
The concentration of chemicals is an important factor in their compati-
bility with grouts, but much of the available data do not specify concentra-
tions. If concentrations are specified, they generally refer either to
dilute or high strength solutions without giving actual concentrations.
Furthermore, chemical compatibility data for the chemical grouts often
consisted of data for mortar or pipe-sealing applications rather than for
soil sealing applications. Though the compatibility would be comparable for
the different formulations, the chemical concentrations in contact with
mortar would be significantly higher than for soil grouts.
Other factors affecting the applicability of the compatibility data are
the variability of grouting formulations and the amount of conflicting data
on these formulations. The grouting formulations may be varied to meet
different needs and conditions through the addition of setting agents,
accelerators, retardants, and other chemicals. These additional materials
have a distinct impact on the properties of grout and its behavior during
setting as well as the chemical compatibility of the set grout. In
researching the grouts in use and their properties, much conflicting data
were encountered in the literature and in discussions with knowledgeable
people in this industry. This was particularly true regarding the types of
grouts actually in use, their constituent materials, and their properties.
Thus, this report consolidates the available information and presents a
general summary that represents the salient features of each grout type and
its properties.
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SECTION 2
CONCLUSIONS
This report permits the following conclusions regarding grouts in
general and their compatibility with hazardous wastes.
Little actual chemical compatibility testing has been performed on
grouts. Much of the data presented here have been taken from related uses of
similar materials and not specifically from the testing of grouts in contam-
inated soils. Significant data were collected, for example, from research in
waste solidification and encapsulation techniques. Furthermore, few
documented cases exist of the use of grouts and grouting technology for
hazardous waste site remediation.
Laboratory testing of grout/chemical compatibility centers on evaluating
two general factors: the effect of chemicals on grout set time and how long
the grout will remain effective after prolonged exposure to the chemicals.
Protocols for conducting these particular tests have yet to be developed.
Selection of a grout for a particular purpose depends primarily on site
characteristics and the grout's injectability, strength, permeability, and
durability. In addition, costs and toxicities of grouting materials are
major factors.
Suspension grouts (cement, clay, and cement/clay) are the most common,
accounting for approximately 95 percent of all grout used. Silicate grouts
are the most commonly used chemical grouts, followed by acrylamides and
urethanes. Other minor grout types are used in less than 1 percent of grout
applications.
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SECTION 3
RECOMMENDATIONS
Recommendations regarding information and concepts presented in this
report generally represent research that is needed to understand and quantify
further the grout and chemical compatibility issue. Briefly, these areas of
needed research include: grout specifications and applications, compatibili-
ty of grouts with chemicals, long-term grout stability, and compatibility
testing procedures. In addition to laboratory studies, pilot scale
evaluations of the most promising systems are recommended.
These research needs are specifically addressed in Section 9. Among the
recommended research topics are:
• Identification of specific grouting formulations and their properties
• Chemical effects on grout setting and durability
• Effects of various chemical concentrations on grouts
• Effect of chemical mixtures
• Effect of groundwater
• Long-range stability of grouts
• Selecting compatibility testing procedures.
Preceding page blank
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SECTION 4
GROUTING TECHNIQUES
Grouting is a process by which a fluid material is pressure injected
into soil, rock, or concrete to reduce fluid movement and/or to impart
increased strength. Grouts accomplish this through their ability to permeate
voids, and gel or set in place. This section provides an overview of
grouting methods and procedures that can be used at waste disposal sites,
general grout types and the site specific factors affecting grout selection.
GROUTING METHODS
Grouting in conjunction with waste disposal sites, while not common, can
be accomplished by several methods to meet various goals. In many cases,
more effective or cost-efficient alternatives are available. However, there
are specific applications for grouts in cases where alternatives, such as
slurry trenches, are not practical. Grouting methods that can be used
include:
• Curtain grouting
• Jet grouting
• Area grouting
• Contact grouting
• Large void sealing (Bowen 1981, Caron 1982).
Each of these methods and the procedures used are briefly discussed below.
Curtain Grouting
A grout curtain is an underground cut-off or barrier formed by injecting
grout through grout pipes in a specific pattern. The grout pipes are placed
down bore holes, typically in triple rows of primary and secondary holes (see
Figure 1). Starting with the primary holes, grout is injected in "pillows,"
working upward or downward in stages. This procedure forms rows of primary
columns which, when set, are tied together by injecting the secondary columns
(Hayward Baker Company et al. 1980). Grout curtains are keyed into
impermeable substrates. Figure 2 illustrates the wall or curtain formed by
the coalescing columns.
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Secondary Grout Column
Primary Grout Pipe
Source: Hayward-Baker, et al. 1980
Secondary Grout Pipe
Primary Grout Column
Figure 1. Grout Pipe Layout for Grout Curtain
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Semicircular
Grout Curtain.
Secondary
Grout Tubes
Primary
Grout Tubes
Source: JRB 1982
Figure 2. Semicircular Grout Curtain Around Waste Site
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There are several basic techniques that can be utilized to form a grout
curtain. These include:
• Stage-up method
• Stage-down method
• Grout-port method
• Vibrating beam method (Hayward Baker Company et al. 1980, Tiedemann
and Graver 1982).
In the stage-up method, the borehole is drilled to the full depth of the
wall prior to grout injection. The drill is then withdrawn one 'stage,1
leaving several feet of borehole exposed for injection of the desired volume
of grout. When injection is complete the drill is withdrawn further and the
next stage is injected (Hayward Baker Company et al. 1980).
The next technique, stage-down grouting, differs from stage-up grouting
in that the injections are made from the top down. Thus, the borehole is
drilled through the first zone that is to be grouted, the drill is withdrawn
and the grout injected. Upon completion of the injection, the borehole is
redrilled through the grouted layer into the next zone to be grouted and the
process is repeated (Hayward Baker Company et al. 1980).
The grout port method (also known as the tube a'manchettes) utilizes a
slotted injection pipe that has been sealed into the borehole with a brittle
Portland cement/clay mortar jacket. Rubber sleeves cover the outside of each
slit (or port), permitting grout to flow-only out of the pipe. The injection
process is started by isolating the grout port in the zone to be injected
with a double packer. A brief pulse of high pressure water is then injected
into the port, rupturing the mortar jacket. Grout is then pumped into the
double packer, it passes through the ports in the pipe, under the rubber
sleeve and out through the cracked mortar jacket into the soil. (Guertin and
McTigue 1982)
The vibrating beam is an alternate method of placing the grout in such a
way as to form a low permeability wall. In this method, a large I-beam is
worked vertically into the soil to the desired depth using a vibrating
hammer, then raised at a controlled rate. As the beam is lowered and raised,
a grout is pumped through a set of nozzles mounted in its leading edge,
filling the cavity formed. When the cavity is completely filled, the beam is
moved along the direction of the wall, leaving a suitable overlap to insure
continuity, and the process is repeated (Harr, Diamond, and Schmednecht
[not dated]). Figure 3 shows the steps involved in forming a vibrating beam
cut-off wall.
Jet Grouting
Jet grouting is a method of cutting an opening in soil or soft rock
using a high pressure nozzle (Caron 1982). Once an opening has been made,
using either water or grout as the cutting fluid, grout sets in the voids to
10
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Source: Soletanche (Unpublished)
Figure 3. Vibrating Beam Grout Injection
11
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form a low permeability zone, Figure 4. Using this technique, it is
theoretically possible to emplace a grout liner beneath a waste site.
Although this may require jetting through a hole drilled down through the
wastes, advances in directional drilling techniques may soon make this method
more practical.
Area Blanket Grouting
Area grouting is a low pressure technique used to form a grout "blanket"
in near surface soil materials. This is accomplished by injecting grout into
a series of closely spaced injection holes placed in a grid pattern. This is
usually performed to reduce infiltration, prevent erosion losses, or stabi-
lize soils for heavy machinery bases (Bowen 1981). Area grouting may be
adaptable to in situ waste immobilization by injecting into the wastes,
depending on the compatibility of the wastes with the grouts.
Contact Grouting
Contact grouting is low pressure injection of grout to seal surface
cracks or other voids. This technique may be used to patch cracked concrete
in dams or dikes or reduce leakage, and to seal the sides of excavations to
reduce water infiltration (Bowen 1981). Applications of contact grouting to
long term waste site remediation are limited.
Large Void Sealing
Grouts have long been used for sealing large voids in rock and other
materials, mainly in conjunction with dam or tunnel projects (Bowen 1981).
Adaptations of this method to waste disposal sites could include forming a
tie-in between a slurry wall and highly fractured or weathered bedrock, and
sealing leaks in aquitards resulting from exploration bore holes or
improperly installed wells. In sealing voids with a large water flow through
them, an extremely short and controllable set time may be required to avoid
washing the grout out before it seals (Sommerer and Kitchens 1980).
GROUT TYPES
There are three general classes of grout utilized today. These include:
• Suspension grouts
• Chemical grouts
• Bituminous grouts (Tiedemann and Graver 1982, Bowen 1981).
Suspension grouts are the most common type of grout and include coarse
grouts which contain particles in suspension. Cement, clay, and cement-clay
grouts are in this category. These- materials are usually the more viscous of
the available grouting materials and have the largest particle size. Thus,
these grouts are restricted to use in the grouting of fractured rock or
coarse grained material.
12
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Grout Pipe
Figure 4. Jet Grouting
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Chemical grouts rely on polymerization reactions to form hardened gels.
They have initially low viscosities and thus can be used in finer grained,
cohesionless soils as well as a secondary treatment for grouting of coarse
soils and rock fissures. Some chemical grouts such as some urathane, can be
suspentions which undergo polymerization to form a gel. This class of grouts
is comprised of two subclasses, silicates and organic polymer grouts.
Bituminous grouts can either be emulsions of bitumen in water or
asphalts. These grouts can be used to seal soils, fill rock cavities, or
construct thin cut-off walls.
SITE CHARACTERISTICS
The success of a grouting project depends on thorough investigation and
characterization of the site in question, and selection of a grout that is
suited to the particular site. The following is a discussion of the types of
geotechnical information required to plan a grouting project and how this
information can affect grouting.
Soil and Rock Characteristics
The nature of the earth materials at a site will influence greatly the
type of grout to be used. If soil materials are to be grouted, the
characteristics that must be determined include:
• Permeability
• Porosity
• Particle size distribution.
Permeability will influence the selection of grout type (particulate or
chemical) to be used, the allowable viscosity, and the required injection
pressures (Bowen 1981). The porosity, or voids ratio, will give an
indication of the amount of grout a unit volume of soil will "take," and how
rapidly grout may be injected (Herndon and Lenahan 1976a). The particle size
distribution indicates, among other things, the presence of large particles
which could interfere with grout injection. The type of grout recommenda-
tions for various grain uses sizes is discussed more specifically in Section
8.
To effectively seal voids in rock by grouting, the nature and extent of
the voids must be well characterized. The size, shape, and distribution of
cracks, solution channels, or other rock openings will determine allowable
grout viscosities, appropriate set time, and required grout volume. (Tallard
and Caron 1977b).
14
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Geochemical Characteristics
The geochemistry of a site, including that caused by waste disposal, can
be extremely important to the success of a grouting project. Among the
geochemical data that should be determined during a design phase site
investigation are the nature and extent of wastes and leachates at the site,
and presence of soil or rock layers (such as salt deposits) that may
significantly impact grout solution chemistry.
15
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SECTION 5
CHEMICAL AND PHYSICAL PROPERTIES OF GROUTS
The grouts used for soil consolidation and groundwater control are
emulsions, polymers, and particle suspensions. These materials are generally
water based solutions of sufficiently low viscosity to allow them to
penetrate rock and soil voids. Particulate grouts, composed of cements,
clays, or mixtures of the two, constitute approximately 95 percent of the
grout used. The remaining 5 percent is primarily silicate grout, although
bitumen and organic polymer grouts do see some limited use for water sealing.
Because of the unique characteristics of different grouts, these traditional
breakdowns of grout usage may not correspond to grout usage at hazardous
waste sites.
This section describes the properties of these grouts. The properties
include: chemical composition, reaction theory (gelation or set mechanisms),
physical nature, toxicity, and compatibility/incompatibility data. In
addition, situations where these grouts have been used are summarized.
PROPERTIES OF BITUMEN GROUTS
Bitumen grouts can be of several types including bitumen/water
emulsions, heated bitumen and mixtures of bitumen with other materials.
Bitumen or asphalt emulsions are direct emulsions in water, with water being
the major component. These emulsions have a variety of uses including
surface and subsurface waterproofing applications. Emulsions are typically
used for fine materials such as sand or in finely fissured materials. Hot
bitumen grout has been used in coarse soil formations, however, it is
difficult to use because it is necessary to preheat the ground with steam,
and the heating equipment for the grout require precise temperature
regulation (Tallard and Caron 1977a). Because of the preheating and
temperature control requirements as well as the short range of penetration in
fine soils, heated bitumenous materials appear to have limited use as grouts
(Tallard and Caron 1977a). Finally, bitumen can be mixed with other com-
pounds to yield a usable grout. A commercially available grout, ASPEMIX®,
used in conjunction with the vibrated beam injection technique is of this
type.
Chemical Composition and Reaction Theory
Bitumen or asphalt emulsions consist of bitumen, water, and an
emulsifier. Bitumens are viscoelastic materials containing high molecular
17
Preceding page blank
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weight hydrocarbons (Kirk-Othmer 1978a). When dispersed in water, bitumens
yield an emulsion with a low viscosity suitable for injection (Tallard and
Caron 1977a). Typical emulsions include bitumens; bitumen, soap, and casein;
and bitumen with fillers such as clays (Bowen 1981).
Emulsions are stabilized by the emulsifiers, which delay molecular
aggregation and increases in viscosity (Kirk-Othmer 1978a). The emulsifiers
are polar and determine whether the resulting emulsion is cationic or anionic
(Bowen 1981). For example, amine chains are often used as acid emulsifiers
to yield cationic emulsions (Bowen 1981, Kirk-Othmer 1978a). Further, the
emulsifiers for these emulsions should be water soluble so as to mix with the
emulsion and should properly balance the hydrophilic and lipophilic proper-
ties of the water and bitumen components of the emulsion, respectively
(Koehmstedt, Hartley, and Davis 1977).
As a grout, bitumen emulsions separate upon contact with earth
materials; the more viscous emulsion components settle and fill the pores and
fissures in the earth material. The breakdown of bitumen emulsions can occur
through loss of stabilizing agents, addition of destabilizing agents, or
adsorption of emulsifying water. In the first method, a stabilizing agent is
eliminated through decomposition or absorption by fine soil material. Direct
breakdown is difficult to control and often occurs too quickly or too slowly
(Tallard and Caron 1977a). In the second method, destabilizing agents
(electrolytes or hydrolyzable esters) may be added to the emulsion either
before or after it is injected to promote breakdown and flocculation of the
emulsion (Bowen 1981, Tallard and Caron 1977a). When destabilizing agents
are added, a one step method (addition of additives prior to injection) is
preferable (Tallard and Caron 1977a).
ASPEMIX®, a grout used with the vibrated beam injection method is a
bitumen mixture containing cement, asphalt emulsion, fly ash, sand and water.
This mixture is pumpable and once injected will set into a solid mass (Slurry
Systems (not dated)).
Bitumen Grout Properties
As described previously, bitumen alone is a viscous liquid. Upon
emulsification in water, a low viscosity emulsion is obtained (Tallard and
Caron 1977a); the viscosity is a little higher than that of water (Bowen
1981). The viscosity of the emulsion is primarily controlled through the
ratio of bitumen to water.
The set time of bitumen grout will vary depending on the method used to
achieve a breakdown of the emulsion. Set time is further controlled by the
emulsifer present in the grout (Koehmstedt, Hartley, and Davis 1977).
Bitumen grout is known to have long term stability (Tallard and Caron
1977a). Oxidation and aqueous leaching of oxidation products are the primary
causes of degradation; these mechanisms have largely been studied for
surficial applications of asphalt. Oxidative processes include microbial
action and sunlight; there is little evidence of anaerobic bacterial
18
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oxidation (Hartley et al. 1981). Upon aging, the viscosity of the bitumen
emulsion may increase due to increased rigidity (Kirk-Othmer 1978a).
The bitumen used as grout typically consists of a coal tar or asphalt
base (Tallard and Caron 1977a). These materials consist of high molecular
weight hydrocarbons which, if leached, could be toxic.
Grout/Chemical Interactions
Bitumen or asphalt is resistant to most chemicals. Inorganic chemicals
(except concentrated acids), dilute acids, lower alcohols, glycols, and
aldehydes will not affect bitumen. ASPEMIX, an asphalt-based slurry used in
vibrating beam constructed slurry walls, has been found in the short term to
be resistant to paint thinner and hazardous waste site leachate containing
various chemicals or brine (Slurry Systems 1982). In particular, ASPEMIX
appears to be resistant to coal tar, which contains dimethylnapthalene,
methylnapthalene, and pyrene.
Asphalt is not compatible with concentrated mineral acids. Most polar
and nonpolar solvents will dissolve asphalt as will chlorinated, aliphatic,
and aromatic hydrocarbons. Ketones will also affect asphalt and phenols may
slowly degrade asphalt. Salts and organic matter in the earth can prevent
proper formation of a seal between bitumen or asphalt and soil. In addition,
sea water will cause bitumen emulsions to effloresce and become powdery
(Ingles and Metcalf 1973).
Some liners for hazardous waste sites consist of an emulsified asphalt
membrane. In general, materials reported to be detrimental to emulsified
asphalt membranes include organic substances, highly ionic wastes, and waste
containing salts, strong acids, and strong bases (Haxo 1980).
Areas of Application
The primary application of bitumen grouts is to reduce the permeability
of fine sands, fine soils (clayey sand), or finely fissured masses. This
type of grout is not suitable for coarse soils because a poorly gelled grout
may draw away from the coarse material because of weak cohesion of the grout
to the soil material resulting in an ineffective seal (Tallard and Caron
1977a). Bitumen grout may be applied in combination with cement (Bowen
1981).
ASPEMIX®, has have been used to construct containment barriers at
several hazardous waste sites. This application is quite recent therefore
Puzinaurkas, V.P., Asphalt Institute, Washington, B.C. Verbal communication
with G. Hunt, JRB Associates, August 25, 1982.
2
Drozda, A.J., J.E. Brenneman Co., Philadelphia, PA. Written communication
with R. McGillen, Ecology and Environment, Pennsauken, NJ. September 24,
1981.
19
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long term evaluations are not available. In the short term, this material
has proven to be successful in containing leachate (Slurry Systems 1982).
PROPERTIES OF CEMENT GROUTS
Cement has been used prior to clays for grouting applications (Bowen
1981). Cement grouts utilize hydraulic cement which sets, hardens, and does
not disintegrate in water (Kirk-Othmer 1979). Because of their relatively
large particle size, cement grouts are suitable for rock rather than soil
applications (Bowen 1981). Additions of clay or chemical polymers can,
however, improve the range of usage.
Chemical Composition and Reaction Theory
Cement grouts consist of Portland cement and water. Several types of
Portland cement are available; the types used in soil grouting include Type I
(ordinary Portland cement), Type II (modified Portland cement, moderate
sulfate resistance), and Type V (low alumina, sulfate resistant). Fillers
such as clay, sand, ground slag, or pozzolans, and additives such as chemical
polymers may be mixed with the cement to change the characteristics of the
grouts and improve their resistance to deleterious chemicals (Littlejohn
1982, Bowen 1981).
When cement, water, and aggregate materials, such as sand and gravel are
mixed together in the proper proportions and allowed to harden, they form
concrete. The hardening process, during which the cement mixture changes
from a slurry to a solid, occurs as a result of the selective hydration of
the calcium silicates. This hydration causes an increase in the strength and
durability of the concrete. The increase in strength over time is referred
to as the curing process (Neville 1973).
Portland cement is made from calcium oxide, alumina, and silica. The
calcium oxide is derived from heated limestone. Clay or shale provide the
alumina and silica. Gypsum is added to the mixture to prevent excessively
rapid setting. When readily available, iron oxide or ground blast furnace
slag may also be added (Bowen 1981, Neville 1973). The chemical substances
found in Portland cement are tricalcium silicate (45 percent) and dicalcium
silicate (27 percent), as well as lesser amounts of tricalcium aluminate and
tetracalcium alumino-ferrite (Littlejohn 1982, Ingles and Metcalf 1973).
Magnesium oxide, free lime, and silica are also present in minor quantities
(Littlejohn 1982). The calcium silicates however, are the major cementitious
compounds in cement (Neville 1973).
Various materials (organic and inorganic) may be added to cement grout
to achieve special characteristics or to control grout properties. Special
additives include agents to prevent excessive bleeding, set time accelerators
and retarders, and expansion agents (Littlejohn 1982). Latexes or water
soluble polymers may be added to achieve special properties (Kirk-Othmer
1979). Calcium chloride may be added as an accelerator, however, it may
cause increased shrinkage upon drying (Littlejohn 1982). Sand may be added
20
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so that cement grouts may be used to seal coarse materials (Bowen 1981).
Clays can be added to stabilize the cement and reduce bleeding while
pozzolans or clay may be added to improve alkali resistance (LittleJohn 1982,
Bowen 1981). Polyhydric alcohols can be added to provide acid-resistance
(Farkas and Szwarc 1949). Protective colloids such as gelatin, agar, and
ammonium stearate may be added as stabilizers in cement grouts (Bowen 1981).
Upon addition of water, the silicates and aluminates in cement form
hydration products which have low water solubility (Neville 1973). The
calcium silicates form gels of mono- and di-calcium silicate hydrate. The
insoluble calcium silicate hydrate crystallizes to form a matrix within which
the remaining hydration products form (ingles and Metcalf 1973, Neville
1973). The resulting cement gel is considered to be a finely dispersed
physical mixture of copolymers of hydrates (Neville 1973).
Cement Grout Properties
The physical properties of both fresh and cured cement mixtures depend
primarily on the water-cement ratio, the degree of hydration of the cement,
and the types of additives used. In addition, the strength and durability of
the cured material are affected by the temperature and humidity conditions
during curing and the length of curing time allowed.
Viscosity—
The amount of water added to the cement controls the viscosity of the
cement grout. As the water-cement ratio increases from 0.4 to 0.7, the
viscosity decreases from 5,000 to 500 CentiPoise (cP). The viscosity can
also be reduced through the addition of certain organic admixtures (Kirk-
Othmer 1979).
Setting—
The setting process occurs in two stages. During the initial set, the
fluidity of the grout decreases until it is no longer pumpable. This is
considered the set time. The final set occurs as the grout hardens and
increases the strength. The time to achieve the final set is referred to as
the hardening time (Littlejohn 1982) .
The various components of cement grouts set at different rates. These
rates vary from a "flash set" (tricalcium aluminate) to several hours
(tricalcium silicate and dicalcium silicate) (Littlejohn 1982). Setting
normally takes approximately 6 hours, however, the presence of impure calcium
silicates can modify this (Kirk-Othmer 1979). Other cement types can set
much more rapidly. For example, resin gypsum cement sets in 30 to 90 minutes
(Bowen 1981).
In some instances, it is desirable to lengthen the time required for a
cement grout to set. A number of substances may be used to increase the set
time. These include: organic materials, silt, clay, coal, lignite, sulfates
and a number of salts of sodium and metals (Fung 1980, Thompson, Malone, and
Jones 1980). Set times may also be lengthened by increasing the water-cement
ratio. In addition, sugar or tartaric acid (0.04%) can be used to double the
21
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set time (Littlejohn 1982). Special additives such as calcium sulfate may be
added to control set time or to resolve setting problems (Kirk-Othmer 1979,
Neville 1973).
In excess, some of these materials may entirely prevent the cement grout
from setting.
Durability—
While cement mixtures are relatively durable under normal conditions,
they can be subject to deterioration as a result of deficiencies in grout
quality, drying conditions, chemical attack, and temperature fluctuations
(Littlejohn 1982).
Grout quality can be diminished by adding excessive amounts of water.
Increasing the water-cement ratio can greatly increase the permeability of
the concrete by increasing the number of capillary spaces thereby promoting
penetration of solutions (ACI Committee 515 1979, Kirk-Othmer 1979).
Further, all cement grouts expel bleed water, particularly those with high
water-cement ratios. The bleeding process can lead to accumulation of water
on the grout surface, a decrease in grout strength, and an increase in the
lateral permeability of the grout curtain (Bowen 1981).
Excessively rapid drying can decrease the quality of a grouted cut-off
wall. Rapid drying promotes cracking of concrete, soil cement, and cement
grouts. Soil cement which is a mixture of soil, cement, and water, tends to
shrink during drying. This shrinkage may be accompanied by cracking (Haxo
1982, Matrecon, Inc. 1980). Cement grouts may also shrink and this shrinkage
can lead to the formation of microfissures (Littlejohn 1982). However, moist
cured grout that remains moist will not shrink (Littlejohn 1982).
Cement mixtures are vulnerable to chemical attack because of their
alkalinity, reactivity, and permeability. Penetration of fluids may be
accompanied by chemical reaction of the fluid with cement constituents
(ACI Committee 551 1979). Cement mixtures may deteriorate due to exposure
to sulfates, chemical wastes, and organic acids (Tomlinson 1980). Further,
cement hydration compounds may leach from the matrix and this can also cause
deterioration (ACI Committee 515 1979).
Fluctuations in temperature during curing of cement mixtures may reduce
the quality of the finished product. This is not normally a problem when
using grouts in subsurface applications because ground temperatures are
relatively stable.
Toxicity—
Cement grouts are essentially nontoxic. The basic components of the
grout are Portland cement and water which are both nontoxic. Nonetheless,
substances such as chemical polymers (acrylamide) may be added to the grout
to modify its properties and these materials may be toxic.
22
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Grout/Chemical Interactions
Cement materials are compatible -with numerous substances. These are
listed in Table 1. In general, cement materials such as grout are compatible
with hydroxides, weak alkaline solutions, neutral salts, and heavy metals.
Special cements, such as high alumina or supersulfate, are also resistant to
acids. The compatibilities of specific chemicals with cement grout have not
been documented, however, the compatibilities of chemicals with the cement
materials listed in Table 1 should apply by analogy to cement grout.
A number of materials should not be used with cement grouts. These are
listed in Table 2. These substances may interfere with the setting time of
the cement or cause deterioration of the final product. Such deterioration
may be caused by reaction with components of the cement resulting in leaching
of the cement or disruption (cracking) of the grout matrix. For example,
sulfates can react with tricalcium aluminate to form calcium sulfo-aluminate
hydrate. This reaction causes swelling and cracking of the cement (Fung
1980, ACI Committee 515 1979). In addition, acids and some salt solutions
can react with calcium hydroxide in hydrated Portland cement to form a
solution of reaction products that can cause disintegration (ACI Committee
515 1979).
Areas of Application
Cement grouts have been used for many soil consolidation and water
cutoff applications. Because of the relatively large particle size of
cement, its use is restricted primarily to media of high porosity or
permeability. Typically, cement grout cannot be used in fine grained soils
with voids less than 0.1 mm wide because the large cement particles plug the
soil matrix and prevent grout penetration (Bowen 1981).
Cement grout may be applied to fractured rock that has voids of
sufficient size to ensure penetration of the grout. It may also be used for
underpinning and construction of a variety of structures (Bowen 1981, Kirk-
Othmer 1979). Type I Portland cement may be used for materials with large
voids. Resin gypsum cements are used by the oil well cementing industry for
rapid water seal-off applications. These cements set within 30 to 90 minutes
(Bowen 1981).
Various materials may be added to cement grouts to improve their
applicability. For example, a grout suitable for use in coarse soils may be
prepared by adding sand to Portland cement and water (Bowen 1981). Bentonite
may be added to improve the penetration of cement grouts in coarse grained
soils (Soletanche [no date]).
Some specific applications of cement grouts and concrete are:
• Soil cement (Portland cement, water, soil) as a liner for hazardous
waste landfills
• Cement stabilization of hazardous wastes
23
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TABLE 1. MATERIALS COMPATIBLE WITH CEMENT
TYPE OF CEMENT
COMPOUND
Cement mortar
(Portland, Portland/slag)
Cement mortar
(calcium aluminate)
Soil cement
NaOH, KOH. Mg(OH)7, Ca(OH)2
Hypochlorite (Na, Ca)
Other neutral salts except sulfates
Sulfates (Na, K, Ca, Mg)
Other neutral salts
Ca(OH)2.-M8°H
Dilute sulfuric acid (pH 4-7)
Alkali (moderate amount)
Organic matter (moderate amount)
Inorganic salts (moderate amount)
Oils
Concrete
High alumina cement
Supersulfate cement
Water
Petroleum oil (with/without aromatics)
Domestic sewage
Strong oxidizers (nitrates, chlorates)
Insoluble sulfates
Heavy metals
Common neutral salts (carbonates, nitrates,
fluorides, silicates, some chlorides)
Lime water
Weak alkaline solutions
Petroleum products (no fatty oil, acids)
Hydroxides «10%)
Acids (as low as pH 3.5)
Acids (as low as pH 3.5)
Source: ASTM 1982, Matrecon, Inc. 1980, Fung 1980, Tomlinson 1980, Malone,
Jones, and Larson 1980, ACI Committee 515 1979.
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TABLE 2. MATERIALS INCOMPATIBLE WITH CEMENT
TYPE OF CEMENT
COMPOUND
Cement mortar
(Portland, Portland/slag)
Cement mortar
(calcium aluminate)
Soil cements
Concrete
High alumina cement
Sulfates (Na, K, Ca, Mg)
Dilute H SO (pH 4-7)
Other dilute acids/acid salts (pH 4-7)
KOH, NaOH
Other dilute acids/acid salts (pH 4-7)*
Hypochlorite (Na, Ca)*
Organic soils (>l-2% organic material)
Sulfates
Excess salt
HNO-
Hignly ionic materials
Strong acids
Strong bases
Animal oils
Polyhydroxy organic compounds
Salt solutions
Mild acids
Oxidizing acids
Sulfates (Mg, Na, ammonium)
Organic acids
Halides
Organic solvents and oil
Organic materials
Metal salts (Mn, Cu, Pb, Sb, Zn)
Mineral acids
Strong alkali
*Questionable
Source: ASTM 1982, Ingles and Metcalf 1973, Matrecon, Inc. 1980, Haxo 1980,
Fung 1980, Tomlinson 1980, Malone, Jones, and Larson 1980, Thompson,
Malone, and Jones 1980, ACI Committee 515 1979.
25
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Waterstop applications in dam construction.
PROPERTIES OF CLAY GROUTS
Clays have been widely used as grouts and in mixtures of grout
materials. In general, coarse sands and gravels are initially grouted using
clay or clay-cement grout because these grouts are relatively inexpensive
(Guertin and McTigue 1982). Only certain types of clay minerals, possess the
physical and chemical characteristics favorable for use in grouting. The
important clay characteristics include the ability to swell in the presence
of water and formation of a gel structure at low solution concentrations.
Native clays can be utilized if they possess the necessary physical
properties.
Although many clay minerals display one or both of the necessary
properties to some degree, sodium montmorillonite is best. This mineral
swells up to 15 times its volume when wetted, while most other clays merely
double their volume (Grim 1968). In addition, sodium montmorillonite is
highly thixotropic.
Chemical Composition and Reaction Theory
A source of sodium montmorillonite is bentonite, which is derived from
the weathering of volcanic dust and ash deposits (Bowen 1981). Bentonites
are composed primarily of the clay minerals sodium and calcium montmorillo-
nite with about 10 percent impurities, such as iron oxides and native
sediments (Boyes 1975, Grim 1968).
Montmorillonite clay is composed of three distinct layers. The outer
layers are a tetrahedral arrangement of silicon and oxygen molecules with
some of the silicon replaced by aluminum. Sandwiched between these two
layers is a layer of aluminum atoms surrounded by six hydroxyls or oxygen
atoms in an octahedral configuration. Some of the aluminum atoms in this
layer have been replaced by magnesium. Because of the substitutions within
the three layers, unsatisfied bonds exist within the crystalline structure.
This results in a high net negative charge. To satisfy this charge, cations,
such as sodium and calcium are adsorbed on the internal and external surfaces
of the clay crystal. These cations cause the swelling of the montmorillonite
as they adsorb water molecules, thus expanding the lattice layers (Brady
1974). Because there are limited quantities of natural sodium bentonites,
some areas are forced to use specially treated calcium bentonites instead.
This occurs most frequently in Europe. These calcium bentonites are exposed
to sodium-containing materials such as sodium hydroxide to force some of the
calcium ions off of the exchange complex of the montmorillonite and then
replace them with sodium ions (Grim 1968). Sodium carbonate, which is less
expensive and more effective than sodium hydroxide, is also used on some
bentonites. As long as there is less than 30 percent calcium and at least
50 percent sodium on the exchange complex of the montmorillonite, the
material will act essentially like a sodium montmorillonite (Grim 1968).
26
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When hydrated bentonite particles are placed in suspension, they exhibit
the property of thixotropic gelation, a property common to many colloidal
systems (Tallard and Caron 1977b). Thixotrophy is the ability to form a gel
structure in the suspension. When this structure is formed, the viscosity of
the suspension becomes dependent on the rate of shear that is being applied
to the system. If a low shear is applied, the viscosity will increase and a
gel will form. If the rate of shear is high, as when the mixture is
disturbed, the suspension will become liquid, and can be easily pumped
(Tallard and Caron 1977b). This property allows a bentonite slurry to be
kept in a liquid state through mixing until it is injected into the ground,
where it will set into a weak gel upon the cessation of agitation (Leonard
and Dempsey 1963). Since the thixotropic reaction is totally reversible, the
bentonite will return to a fluid state if disturbed again (Xanthakos 1979) .
Sodium montmorillonite is a great deal more thixotropic than are most
clays. One indirect method of measuring thixotropy is by measuring the
amount of clay needed to produce a clay-water slurry of a given viscosity.
When using sodium montmorillonite, from 5 to 12 percent clay in water is
needed to produce a 15 centiPoise (cP) slurry. If kaolinitic or illinitic
native clays are used, from 25 to 36 percent clay is required to produced a
slurry of the same viscosity (Grim and Guven 1978).
Bentonite Grout Properties
An initial viscosity of a bentonite suspension is usually set at 15 cP +
5 cP. This ensures optimum injectability. Above this range, the suspension
is too viscous and injectability drops sharply; below this range there is a
risk of the bentonite settling out of suspension (Tallard and Caron 1977b).
Because of the varied properties of available bentonites, the quantity
necessary to reach this viscosity will range from 35 to 95 kg of bentonite
per cubic meter of water (Tallard and Caron 1977b). This corresponds to
between 5 and 12 percent bentonite and 88 to 92 percent water (Case 1982).
The use of silicates as rigidifying agents in bentonite grouts allows less
bentonite to be used and thus a lower viscosity is obtained. In one
formulation, an initial viscosity of 3 to 4 cP is obtained (Tallard and Caron
1977b).
The setting time of bentonite grouts containing only clay is difficult
to regulate since no setting agent is used (Tallard and Caron 1977b). The
grout will start to set as soon as the injection pressures is decreased due
to the formation of, a gel structure within the soil pores. Once this process
starts, the viscosity and the gel strength will increase with time. The
final strength of the gel will depend on the setting time, colloid
concentration, and composition of the suspending fluid (Xanthakos 1979). The
final strength obtained, though, is very low compared to the strength of
cement and other grouts (Tallard and Caron 1977b). If silicates are used as
rigidifying agents, the set time of the grout can be controlled from a few
minutes to five hours (Bowen 1981).
The shear strength of a bentonite gel is very low, thus, it cannot
withstand steep hydraulic gradients unless filler materials are added.
27
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Cement or chemical additives, such as silicates, can be used to increase the
strength of the final gel (Greenwood and Raffle 1963). In clay-cement
mixtures, the gelling ability of the bentonite can assist in stabilizing the
cement. Chemicals, such as sodium silicate or acrylic resins, can also be
added to bentonite to increase the rigidity of the gel (Bowen 1981, Tallard
and Caron 1977b).
Because of bentonite1s slow set time and low strength, it can be suscep-
tible to wash out or erosion under water pressure (Tallard and Caron 1977b,
Greenwood and Raffle 1963). In soils of high permeability, 10"1 cm/sec
water gradients of only 3 to 4 units can remove bentonite immediately after
injection (Greenwood and Raffle 1963). This is much more likely to occur in
coarse textured materials, such as open gravels where the grout must fill
large open areas. In finer textured geologic units, wash-out is much less
likely, particularly if filler materials are added to the bentonite grout.
The filler will act to block the pore spaces, thus allowing the bentonite to
set.
The basic ingredient in this type of grout, bentonite, is essentially
nontoxic. The toxicity of most of the additives, such as sodium silicate,
are also low, though gelling agents used to gel the sodium silicate could
pose a risk (Tallard and Caron 1977b). These are discussed in more detail in
the section on silicates.
Grout/Chemical Interactions
The presence of organic or inorganic compounds in the groundwater can
have a detrimental effect on the ability of grout cut-off walls to contain
pollutants. These chemicals can affect the physical/chemical properties of
the bentonite used in construction of the wall. This can result in floccula-
tion of the bentonite, reduced swelling of the bentonite, or the destruction
of the bentonite mineral structure.
If the bentonite is injected into groundwater which contains high
concentrations of electrolytes, such as sodium, calcium, and heavy metals,
the bentonite could flocculate. This will result in particles that can
exceed 10 microns in diameter, thus hampering the grout's ability to
penetrate into the soil structure (Tallard and Caron 1977b, Matrecon, Inc.
1980, Alther 1981b).
Various organic and inorganic compounds can increase or decrease the
amount of swelling that bentonite particles have undergone (Alther 1981b).
This can lead to increased permeability of the in-place grout wall possibly
resulting in breaching of the wall. For example, a decrease in the amount
that hydrated bentonite has swelled increases the amount of pore space, thus
increasing the permeability of the wall. All of the mechanisms that cause
bentonite clay particles to shrink or swell will affect the quantity of water
contained within the interspatial layers of the clay structure. Inorganic
salts such as calcium can reduce the effective use of double layer of
partially bound water surrounding the hydrated bentonite, thus reducing the
effective size of the clay particles (D'Appolonia and Ryan 1979). Upon
28
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dissociation, organic bases can be sorbed into the internal surfaces of clay
particles thus affecting the interlayer spacings (Anderson and Brown 1981).
Neutral-nonpolar and neutral polar compounds can replace the water contained
in the clay particle interlayers, thus affecting the size of the bentonite
particle (Anderson and Brown 1981). For example, one study (Anderson, Brown,
and Green 1982) found that undiluted acetone, a neutral polar compound,
caused a significant increase in the permeability of four types of clay as
shown in Table 3. A 1,000-fold permeability increase was found for one type
of montmorillonite. After contact with the acetone, the clays showed exten-
sive shrinkage and cracking. Such clay shrinkage is usually associated with
dehydration, indicating that acetone extracted water from the soil surfaces.
This study also showed that clays exposed to concentrated xylene, a neutral
non-polar compound, had a 100-fold increase in permeability. The xylene
treated clays showed s.igns of structural changes that led to the permeability
increase (Anderson, Brown, and Green 1982). It should be noted that most
laboratory studies on bentonite-chemical compatibilities subject the bento-
nite samples to much higher concentrations of chemicals than are common in
actual site conditions. Additionally, laboratory test procedures have not
been standardized nor have many of the results been verified. For this
reason, the results should be used merely as indications of the general
effects of the chemicals on the bentonite rather than as exact predictions of
the overall effects.
Strong organic and inorganic acids and bases can dissolve or alter the
bentonite leading to large permeability increases (D'Appolonia and Ryan 1979,
Alther 1981b). Aluminum and silica, two of the major components of
bentonite, are readily dissolved by strong acids or bases, respectively
(D'Appolonia and Ryan 1979, Matrecon, Inc. 1980). For example, when four
types of clays were exposed to acetic acid, significant soil piping occurred
due to the dissolution of the soil components as shown in Table 3 (Anderson,
Brown, and Green 1982). This led to a increase in permeability in most of
the clay types, though strong bases usually produce a greater increase in
permeability than acids (D'Appolonia and Ryan 1979).
Recent laboratory studies have shown the effects of a variety of
inorganic and inorganic compounds on soil-bentonite mixtures containing one
percent bentonite (D'Appolonia and Ryan 1979, D'Appolonia 1980a). Table 4
illustrates the results of these studies. As can be seen, strong acids and
bases will increase the mixture's permeability through dissolution.
Undiluted alcohol will increase the permeability, probably through extracting
water from the clay interlayers, thus reducing the amount of particle
swelling. High concentrations of calcium will also increase permeability,
probably by exchanging with the sodium ions on the bentonite, thus reducing
the amount of particle swelling.
The surface of bentonite clay particles can be chemically modified to
increase the bentonites' resistance to the detrimental effects of various
types of chemicals. These bentonites are specially treated with proprietary
29
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TABLE 3. EFFECT ON PERMEABILITY OF SEVERAL UNDILUTED
ORGANIC CHEMICALS OH SELECTED CLAYS
CHEMICAL SODIUM-SATURATED CALCIUM-SATURATED
MONTMORILLONITE MONTMORILLONITE KAOLINITE ILLITE
Effect on Magnitude of. Effect on Magnitude Effect on Magnitude Effect on Magnitude
Permeability Change Permeability of Change Permeability of Change Permeability of Change
Acetic acid I <10 D
Aniline I 100 I
Ethylene glycol I 100 I
Acetone I 1,000 I
Methanol I 1,000 I
Xylene I 1,000 I
10-100 D 1,000 D <10
<10 I 10 I 10-100
<10 D 10 D <10
<10 I 10-100 I 100
100 I 10-100 I 100
10-100 I 100 I 1000
I: Increase
D: Decrease
Source: Anderson, Brown, and Green 1982
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TABLE 4. SOIL/BENTONITE PERMEABILITY INCREASES
DUE TO LEACHING WITH VARIOUS POLLUTANTS
Pollutant Backfill
Ca or Mg @ 1,000 ppm N
Ca++ or Mg"1"1" @ 10,000 ppm M
NH4N03 @ 10,000 ppm M
Acid (pH>l) N
Strong acid (pHll) M/H*
HC1 (1%) N
H2S04 (1%) N
HC1 (5%) M/H*
NaOH (1%) M
CaOH (1%) M
NaOH (5%) M/H*
Benzene N
Phenol solution N
Sea water N/M
Brine (SG=1.2) M
Acid mine drainage (FeSO,, pH 3) N
Lignin (in Ca solution) N
Organic residues from pesticide
manufacture N
Alcohol M/H
N - No significant effect; permeability increase by about a factor of 2 or
less at steady state.
M - Moderate effect; permeability increase by factor of 2 to 5 at steady
state.
H - Permeability increase by factor of 5 to 10.
* - Significant dissolution likely.
+ - Silty or clayey sand, 30 to 40% fines.
Source: D'Appolonia 1980a, D'Appolonia and Ryan 1979.
31
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compounds consisting of organic and inorganic polymers.* This type of
bentonite was developed for use in the construction of liners for lagoons and
landfills and there were no references found as to its current use in
grouting.
Areas of Application
Bentonite grouts alone can be used as1 waterproofing in coarse sands with
an hydraulic conductivity of more than 10 cm/sec. Bentonite-chemical
grouts canbe used on medium to fine sands with an hydraulic conductivity
between 10 cm/sec and 10 cm/sec. Both of these grout types can also be
utilized to seal small rock fissures (Guertin and McTigue 1982). All
bentonite grouts can only be used for waterproofing due to their low gel
strength (Tallard and Caron 1977b).
PROPERTIES OF CEMENT-BENTONITE GROUTS
A suspension of bentonite and Portland cement can be used for grouting
in situations that require both low permeability and resistance to moderately
high hydraulic pressure. In general, the mixture contains about 6 percent
bentonite, 18 percent cement, and 76 percent water (jefferis 1981).
Chemical Composition and Reaction Theory
The chemical composition of both the Portland cement and the bentonite
used in cement-bentonite grouts was described earlier in this section. The
reactions that occur during mixing and hardening of these grouts and the
procedures used during mixing are described below.
To obtain a satisfactory cement bentonite grout, the bentonite must be
carefully mixed with water and allowed to fully hydrate (i.e., reach a
constant viscosity) prior to the addition of the cement. This is because the
calcium in the cement adversely affects the properties of the sodium
montmorillonite in the bentonite by replacing the exchangeable sodium, thus
reducing the radius of the bentonite particles and causing partial
flocculation (Jefferis 1981). The tnontraorillonite would then fail to swell
properly and would lose its thixotropic properties (Case 1982). If the
bentonite is allowed to hydrate fully first, however, these effects are
minimized.
When the bentonite suspension and the cement are mixed, flash stiffening
occurs. If the mixture is rapidly and continuously agitated, the initial
stiffening softens and a pasty suspension is formed (Jefferis 1981).
This grout remains workable for several hours, after which set up begins
(Case 1982). If agitated, the grout will remain workable longer but it may
lose its ability to set if agitated longer than several days (Jefferis 1981).
*Hentz, D.A., Federal Bentonite, Belle Fourche, SD. Verbal communication
with G. Hunt, JRB Associates, June 3, 1982.
32
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Cement-Bentonite Grout Properties
Unlike bentonite grouts, cement-bentonite grouts have the ability to
withstand significant hydraulic gradients, however cement bentonite grouts
are more permeable than are bentonite grouts. Once a properly formulated
cement-bentonite grout has cured, it is expected to have a strength on the
order of 15 to 55 psi (Case 1982; Millet and Perez 1981). Cement-bentonite
mixtures have been used to withstand with hydraulic gradients well in excess
of 200 units without damage (Jefferis 1981).
Grout/Chemical Interactions
The compatibility between cement-bentonite grouts and various chemical
constituents can be considered to be a combination of the individual compati-
bilities and incompatibilities of cement and bentonite. The chemicals that
degrade bentonite in a bentonite grout can be expected to degrade the exposed
bentonite in a bentonite-cement grout. Similarly, the cement will be
attacked by cement-degrading chemicals, only the damage is likely to be less
substantial due to the protective influence of the bentonite. Chemicals that
enhance or disrupt cement grouts were listed in Tables 1 and 2, respectively.
Chemicals that affect the permeability of water barriers composed of
bentonite were listed in Table 3.
Areas of Application
Cement-bentonite grouts can be emplaced both horizontally and vertically
to inhibit subsurface water movement. In addition, the material can be used
to partially stabilize soil materials during some types of excavation
activities.
An example of the use of cement-bentonite grout is in a subway station
excavation for a that needed dewatering. To accomplish this, a cement-
bentonite slurry cut-off wall was planned. The wall planned, however, did
not extend to a sufficient depth to completely divert water movement. For
this reason, cement-bentonite grout was injected vertically into the fairly
granular soil and rock material below the base of the wall. The floor of the
proposed subway station was also susceptible to seepage. To prevent this,
area grouting was conducted using additional cement-bentonite grout (Guertin
and McTigue 1982).
PROPERTIES OF SILICATE GROUTS
Alkali silicates are the most widely used class of grouts in the
chemical grout category. Sodium, potassium, and lithium silicates are used
with sodium silicates being used most often. Chemical grouts (silicates and
organic polymers) constitute less than 5 percent of the grouting in the
United States. In Europe, these grouts represent almost 50 percent of the
grouts used (Kirk-Othmer 1979).
33
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As early as 1886, a German patent was assigned for use of silica gel to
fill voids (Tallard and Caron 1977a). One of the earliest uses of silicates
as grouts was in 1915 when silicate was used in conjunction with cement
grout. Soon after, the Joosten two-shot method (sodium silicate and calcium
chloride) was developed and used to grout deep foundations. In addition to
their use as grout, sodium silicates may be used as additives to other grouts
such as Portland cement to improve strength and durability (Hurley and
Thornburn 1971).
Chemical Composition and Reaction Theory
Silicate grouts consist of alkali silicates, water, and a gelling or
setting agent. Typically, sodium silicate is used in the grout, however,
potassium silicate may be substituted. The gelling or setting agent varies
depending on the desired properties of the gel. In general, acids,
acid-forming compounds, polyvalent cations, and some organics, may be used as
setting or gelling agents (Kirk-Othmer 1979, Hurley and Thornburn 1971). The
grout may also include an accelerator. Accelerators consist of chlorides,
aluminates, or bicarbonates (Johnson 1979). Other substances, such as
organic esters, may be added to delay gelling time (Bowen 1981).
Grout materials vary with the grouting method to be used. In the
Joosten method, calcium chloride is the most commonly used setting agent.
Other salts (magnesium chloride, aluminum sulfate) and gel-forming gases
(carbon dioxide) may also be used. The Siroc (one shot) method typically
uses formamide although other substances (bicarbonate, sodium aluminate,
calcium chloride, dilute hydrochloric acid, copper sulfate) may be used
(Bowen 1981, Sommerer and Kitchens 1980, Office of the Chief of Engineers
1973). Sometimes the Siroc method uses two reactants with the second
reactant serving as an accelerator (Office of the Chief of Engineers 1973).
In Europe, most silicate grouts use only organic reactants (Karol 1982a). It
should be noted that each company may use different reactants, thus the
grouting compositions vary considerably and are often proprietary (Herndon
and Lenahan 1976a).
The gelling process is a two step reaction that generally involves
neutralization of the basic silicate and involves a lowering of the pH of the
silicate. A decrease in the electric charge on the silicate ions followed by
polymerization of silicates with the reagent, forms a three dimensional
network of chains of silicate micelles (Sommerer and Kitchens 1980,
Kirk-Othmer 1979, Hurley and Thornburn 1971). The network is established
through hydrogen bonding and silicon-oxygen bonding (Sommerer and Kitchens
1980, Hurley and Thornburn 1971). Where metal salts are used, a colloidal
mixture is achieved through precipitation of a metal silicate. The mechanism
for formation of such an amorphous precipitate is due to either the
adsorption of metal ions on gelatinous silica or the mutual coagulation of
colloidal metal hydroxide (positive charge) and colloidal silica (negative
charge) (Hurley and Thornburn 1971).
34
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Silicate Grout Properties
The viscosity of sodium silicate grouts varies from 1.5 to 50 cP and may
be as high as 260 cP (Sommerer and Kitchens 1980, Tallard and Caron 1977a).
Silicate grouts used in the Joosten method have a high viscosity while other
silicate grouts have a moderate viscosity (Karol 1982b). The viscosity of
the grout depends on the ratio of Si02 to Na 0 and the water content. The
higher the ratio of silica to sodium, the lower the viscosity. The water
content will also control the grouts viscosity. The higher the water content
the lower the viscosity. For waterproofing gels a dilution of 70 to 90
percent is commonly used (Tallard and Caron 1977a and b).
The set time of the silicate grouts varies from less than a minute to
several hours (2 to 10). The Joosten method has almost instantaneous set
while the Siroc method is more variable (Sommerer and Kitchens 1980, Kirk-
Othmer 1979, Tallard and Caron 1977a, Tallard and Caron 1977b). Factors
affecting the set time include silicate concentration, setting agent concen-
tration, and temperature. Increasing any of these three factors will
decrease the set time (Tallard and Caron 1977a). The accelerator concentra-
tion may also be varied to control set time. In either case, the set time is
controlled by the rate of acid formation because this controls the neutrali-
zation or polymerization process (Karol 1982a). Soil conditions can also
affect the set time with acid soils reducing gel time and alkaline soils
reducing or preventing gel formation (Office of the Chief of Engineers 1973).
Tallard and Caron (1977a) report that silicate grout is quite durable
and silicate treated areas have not lost their watertightness and strength
characteristics after some time. However, long-term strength and imperme-
ability are of concern because silicate grouts are subject to deterioration
via syneresis (water expulsion), shrinkage (dessication), and solution
erosion by groundwater (Hurley and Thornburn 1971). Silica gels may lose as
much as 20 to 60 percent of their water (by weight) within two months due to
synersis (Hurley and Thornburn 1971). In syneresis, salt-charged water is
expelled through the polycondensation of silicic acid (Karol 1982a). Shorter
gel times mitigate this problem and syneresis has less effect in fine soils
(Karol 1982a). Further, silica gels may shrink and crack upon aging (Hurley
and Thornburn 1971). In an excess of water, leaching may occur. This will
dissolve the silica gel's soluble salts and the gel may revert to soluble
material (Kirk-Othmer 1979, Tallard and Caron 1977b). Gels formed from more
viscous grout mixes tend to shrink excessively. This shrinkage process can
continue for some time and can lead to disintegration of the gel (Williams
1966). In addition, any unreacted sodium in the grout will pass into the
cure water and may attack the polysilicic acid (grout matrix) (Tallard and
Caron 1977b).
Sodium silicate grouts are essentially nontoxic. The set grout has a
relatively low toxicity (oral) having an LDsn of 15 g/kg in laboratory
animals, while sodium silicate has an LD,-n {oral) of 1,100 mg/kg. .Amides
frequently used in formulating the grout are skin irritants (Tallard and
Caron 1977b). Other organic substances, such as formamide, are toxic,
possibly carcinogenic, and require special precautions when preparing and
35
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injecting the grout (Karol 1982a, Kirk-Othmer 1979, Tallard and Caron 1977a).
Heavy metal salts, which may be used as gelling agents, are also toxic and
have the potential to be leached from the gel. In addition, sodium salts may
be expelled from the grout and under certain circumstances they may be an
environmental hazard (Karol 1982a).
Grout/Chemical Interactions
Silicate grouts, when set, are resistant to moderate amounts of acids or
alkali (Kirk-Othmer 1979). These grouts are also resistant to high
concentrations of chromic, nitric, and sulfuric acid (Boova 1977). Organic
esters have little effect on silicate grout (Bowen 1981). Silicate mortar is
similar to silicate grout but also contains fillers such as silica, quartz,
or ganister. This mortar is resistant to most acids (except hydrofluoric
acid) as well as neutral salt solutions (ASTM 1982).
Gelation of silicate grouts occurs through the action of acids or acid
salts. Hurley and Thornburn (1971) and Karol (1982a) report that the setting
time of silicate grouts is significantly decreased in the presence of soils
or groundwater with an appreciable salt content. These effects may be
mitigated by using groundwater to mix the grout. Acidic soils may also
decrease the gel time (Karol 1982a).
Silicate grouts are not compatible with a number of materials that may
be found in hazardous waste sites. Gel time and grout strength may be
affected by large amounts of acid or alkali (Kirk-Othmer 1979).
Additionally, organic materials and high concentrations of some metals, will
slow the setting time (Malone, Jones, and Larson 1980).
Areas of Application
Silicate grouts are used for both soil consolidation and waterproofing
applications. These grouts are suitable for blocking water migration in
soils with a permeability of less than 10~2 cm/sec. Silicate grouts are not
suitable for open fissures or highly permeable materials (due to syneresis)
unless they are preceded by cement grouting (Karol 1982a, Sommerer and
Kitchens 1980). The Joosten method has been used for both fine sands and
gravels while the Siroc method has been used to waterproof sands (Kirk-Othmer
1979, Tallard and Caron 1977a). Tests by the U.S. Army Corps of Engineers,
Waterways Experiment Station, however, found silicate grouts to be
ineffective in waterproofing fine grained soils (Hurley and Thornburn 1971).
Currently, silicate-based grout is under study for use in controlling
hazardous chemical spills (Soramerer and Kitchens 1980)
PROPERTIES OF ORGANIC POLYMER GROUTS
Organic polymer grouts represent only a small fraction of the grouts in
use. These grouts consist of organic chemicals (monomers) that polymerize
and crosslink to form an insoluble gel. This section addresses acrylamide,
36
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phenolic, urethane, urea-formaldehyde, epoxy, and polyester grouts, and their
properties.
Properties of Acrylamide Grouts
Acrylamide grouts have been in use for 30 years. These grouts were the
first of the organic chemical polymer grouts to be developed. Acrylamide
grouts have the largest use among the organic polymer grouts. They are the
second most widely used chemical grout (Karol 1982a). They may be used alone
or in combination with other grouts such as silicates, bitumens, clay, or
cement (Tallard and Caron 1977a).
AM-9 was the first acrylamide grout developed; it was removed from the
market in 1978 because of the problems involved with the toxicity of the
accelerator in AM-9 (Karol 1982a). There are only a few acrylamide or
acrylamide-based grout products available and most of them are imported.
These grouts include acrylates, polyacrylamides, and acrylamide derivatives.
Some grouts, such as Rocagil 1295, are not used in the United States (Karol
1982a). Although AM-9 was removed from the market, it has been used as
recently as 1980 in water cut-off applications (Berry 1982). A number of
acrylamide grouts that were copies of AM-9 have been imported and marketed
after AM-9's removal (Karol 1982). AM-9 is probably the most studied of the
acrylamide grouts. Because of the similarity of the materials and the
reaction mechanisms, much of the AM-9 data is valid for other acrylamide
grouts (Karol 1982a). Thus, the data are included in the following
discussions of acrylamide grout properties.
Chemical Composition and Reaction Theory—
Acrylamide grouts consist of a base material (typically a monomer or
mixture of monomers), a crosslinking agent, an initiator or catalyst, and an
accelerator or activator. Persulfates or peroxides, typically ammonium
persulfate, are used as the initiator. Accelerators/activators include
dimethylaminopropionitrile, diethylaminopropionitrile, or triethanolamine
(Tallard and Caron 1977a). The substances used vary with the particular
product. Table 5 summarizes the components of the major acrylamide grouts.
Two of these grouts, AC-400 and Injectite-80, do not utilize acrylamide but
instead use a related compound or a pre-polymer. These substances have a
lower toxicity. AM-9, while discontinued, is included because of the
presence of similar products on the market.
Polymerization occurs through a reduction/oxidation (redox) reaction.
Acrylamide contains two reactive sites: a double bond and an amide.
Reaction at the double bond creates a polymerization similar to vinyl
compounds. The resulting linear polymers are soluble in water. To obtain an
insoluble polymer, crosslinking or reticulating agents are used to form
bridges between the linear polymers. This is accomplished at the amide group
through a condensation reaction with aldehydes (formaldehyde, glyoxal, etc.).
The degree of crosslinking will determine the polymer properties (Tallard and
Caron 1977a). During polymerization, water becomes trapped in the gel matrix
(Karol 1982a, Berry 1982).
37
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TABLE 5. COMPONENTS OF ACRYLAMIDE GROUTS
PRODUCT
AM-9
Q-Seal
AV-100
AC-400
Injectite -80
BASE MATERIAL
Acrylamide
Acrylamide
Acrylamide
Acrylate
Polyacrylamide
CROSS-LINKING
AGENT
Methylenebis-
acrylamide
N,N'-methylenebis-
acrylamide
unspecified
Methylenebis-
acrylamide
Glyoxal
INITIATOR/
CATALYST
Ammonium
persulfate
Ammonium
persulfate
Ammonium
persulfate
Ammonium
persulfate
Calcium hypo-
chlorite
ACCELERATOR/
ACTIVATOR
Dimethylamino-
propionitrile
Triethanolamine
Triethanolamine
Triethanolamine
Trisodium
phosphate
REFERENCES
Bowen 1981
Tallard and Caron 1977a
Cues, Inc. 1982
Avanti International,
1981
Clarke 1982
Geochemical Corporation
1982
Berry 1982
Jacques 1981
-------
Additional substances may be added to control the grout. Gel time may
be controlled through the addition of a reaction inhibitor, typically
potassium ferricyanide (Karol 1982a, Tallard and Caron 1977a). Buffers may
be required to maintain the pH of the grout solution around 8. Disodium
phosphate is added when no activator is used (Office of the Chief of
Engineers 1973).
Acrylamide Grout Properties—
Most of the acrylamide grouts (pre-gel) have a low viscosity; less than
2 cP. Their viscosity is approximately that of water (Karol 1982a,
Geochemical Corporation 1982, Cues, Inc. 1982, Avanti International 1982,
Tallard and Caron 1977b, Herndon and Lenahan 1976b). Injectite -80 is more
viscous and at normal grout concentrations (10%), has a viscosity of 50 cP
(Berry 1982). Addition of polymerization agents or cement will increase the
viscosity (Avanti International 1982, Tallard and Caron 1977b). Overall, the
viscosity will remain constant until gelation occurs (Karol 1982a, Avanti
International 1982).
The set time, or gelation, can vary from a few seconds to several hours
(12 to 48) (Karol 1982a, Cues, Inc. 1982, Tallard and Caron 1977a, Office of
the Chief of Engineers 1973). The factors primarily controlling set time are
reaction inhibitors and the proportions of catalyst and activator (Karol
1982a, Kirk-Othmer 1979, Tallard and Caron 1977a). In general, the set time
is lengthened by addition of inhibitors (potassium ferricyanide) or by
decreasing the amount of catalyst in the grout mixture (Karol 1982a, Tallard
and Caron 1977a). An acidic grout solution or acidic grouting conditions
(groundwater or earth material) can also lengthen the set time and may
prevent gelation (Office of the Chief of Engineers 1973). The set time may
be shortened through the action of metals, triethanolamine, or ammonium
persulfate; increasing the pH; or by increasing the dry matter in the grout
(Clarke 1982, Avanti International 1982, Tallard and Caron 1977a, Office of
the Chief of Engineers 1973).
Once the grout is set, it is chemically stable and is not subject to
slow deterioration or syneresis (Karol 1982a, Berry 1982, Avanti
International 1982, Tallard and Caron 1977a). A small portion of the grout
remains hydrolyzable even after setting and under certain conditions it may
rehydrolyze and become soluble (Tallard and Caron 1977a). Eventually, some
salts, unreacted material, and hydrolysis products may leach out (Karol,
1982a, Tallard and Caron 1977a). Further, acrylamide gels are approximately
90 percent water and they may shrink or swell due to exposure to water
fluctuations or subsurface forces acting on the gel (Karol 1982a, Kirk-Othmer
1979). After shrinkage, the gel can regain its original volume. Shrinkage
cracks may seal but not heal, i.e., the crosslinkages of the molecular chains
do not reform, resulting in greater permeability and less strength (Karol
1982a). The permeability may thus increase due to shrinkage cracks. In
addition, soluble salts may migrate through the water contained within the
gel's polymeric structure (Karol 1982a).
All of the acrylamide grout formulations contain substances that are
toxic and require special handling (Berry 1982, Geochemical Corporation 1982,
39
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Tallard and Garon 1977a). Acrylamide (solution or powder) is neurotoxic
(Karol 1982a) and, unreacted, has an LD5Q o£ 150 mg/kg (Berry 1982).
Methylenebisacrylamide, a common crosslinking agent, has an LD5n of
390 mg/kg, but is not neurotoxic (Geochemical Corporation 1982?" The
gelled grouts, however, or polymerized acrylamides are reported to be
nontoxic. Injectite -80 base material, a low molecular weight poly-
acrylamide, has an LDcn °f 5,000 mg/kg, which is higher than common table
salt (Berry 1982). AC-400, after gelation, also has an LD of 5,000 mg/kg
(Geochemical Corporation 1982, Clarke 1982). It should be noted that if the
polymerization process is not complete, unreacted toxic monomer or other
substances can leach from the grout matrix and has caused problems in the
past (Tallard and Caron 1977a).
Grout/Chemical Interactions—
Acrylamide grouts are resistant to the dilute chemicals found in sewer
systems. Normal groundwater conditions (dilute acids, alkali, salts) will
have little effect, particularly if groundwater is used to mix the grout
(Clarke 1982, Avanti International 1982, Kirk-Othmer 1979). Acrylamide
grouts are impermeable to gases and hydrocarbon solvents such as kerosene,
toluene, heptane, and dilute hydrochloric acid (2 percent) (Office of the
Chief of Engineers 1972, Berry 1982). They are also unaffected by 10 percent
solutions of alcohols, ketones, hydrocarbons, acids, and metal salts (Clarke
1982).
Salts and pH will affect the setting time of acrylamide grouts. (Caron
1963). Low pH conditions, «6.5), can prevent acrylamide grouts from
setting. Polymerization inhibitors such as sodium nitrates and metallic
salts can also delay gelation (Avanti International 1982, Office of the Chief
of Engineers 1973). Alkaline conditions or metal ions, such as iron, copper,
zinc, or tin, can shorten the gelation time (Avanti International 1982,
Tallard and Caron 1977a). Other gel time accelerators include hydrogen
sulfide and soluble salts (NaCl, CaCK, sulfates, phosphates) (Karol 1982a,
Office of the Chief of Engineers 19737.
The durability of acrylamide grout is affected by highly alkaline media
which can promote saponification of the grout, particularly the monomer
(Sommerer and Kitchens 1980, Tallard and Caron 1977a). This hydrolysis
reaction will affect the performance of the grout (Tallard and Caron 1977a).
Herndon and Lenahan (1976b) report that sulfides affect acrylamide
grout, but the effect is not specified. Strong or concentrated hydrating and
dehydrating agents will have the greatest impact on acrylamide grouts. For
example, acrylamide grouts will swell in the presence of sulfuric acid,
sodium chloride, sodium sulfite, sodium hydroxide, and laundry detergent.
Alcohols and glycols will cause the grout to shrink by drawing out the water
(Berry 1982).
Areas of Application—
Acrylamide and acrylamide-based grouts have greater use in the United
States than in Europe, where phenolic grouts find more use. Acrylic and
polyacrylamide grouts are typically used in ground surface treatment, ground
40
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treatment for oil well drilling, and subsurface applications (waterproofing
concrete structures). Acrylate grouts find greater use in ground surface
treatment than soil injection, where acrylamide grouts are frequently used.
Acrylamide applications include structural support and seepage control for
mines, soil consolidation for foundations of structures and dams, and water
control/soil consolidation for tunnels, wells, and mines (Tallard and Caron
1977a). Specific applications include grout curtains, stabilization of loose
sand, shut-off of artesian flow, and control of water seepage in jointed and
fissured rock (Office of the Chief of Engineers 1973). Based on AM-9
applications, acrylamide grouts may be used in a variety of soil materials
such as fine gravel; coarse, medium, or fine sand; coarse silt; and clay soil
(Herndon and Lenahan 1976b).
Properties of Phenolic Grouts
The use of phenolic resin grouts in underground and foundation construc-
tion began in the 1960's (Kirk-Othmer 1979, Tallard and Caron 1977a). These
grouts may be used in fine soils and sands in a variety of waste control and
ground treatment applications. Phenolic grouts however, are not widely used;
when used, they are typically employed in conjunction with other grouts
(Tallard and Caron 1977a).
Chemical Composition and Reaction Theory—
Phenolic grouts are commonly referred to as phenoplasts. They are
polycondensates of phenols and aldehydes (Sommerer and Kitchens 1980, Tallard
and Caron 1977a). A typical grout consists of a phenol, an aldehyde, water,
and a catalyst. Formaldehyde is used almost exclusively as the aldehyde
because of its high reactivity (Billmeyer 1971). The catalyst may be an acid
or a base (Tallard and Caron 1977a, Billmeyer 1971). Since soil conditions
are typically neutral or somewhat basic, an acid catalyst would preferenti-
ally react with soil materials rather than the grout (Tallard and Caron
1977a). Therefore, sodium hydroxide or other alkaline materials (hydroxides,
carbonates, phosphates) are typically used as catalysts to provide an
alkaline reaction medium and to control the pH (Karol 1982a, Tallard and
Caron 1977a).
Not all phenols can react in an alkaline medium. Resorcinol and
byproducts containing large amounts of resorcin (such as tannin extracts) can
undergo alkaline reactions and these materials constitute the majority of the
phenolic grouts (Karol 1982a, Tallard and Caron I977a). Table 6 summarizes
the major components of some of the commercial phenolic grouts.
Phenolic grouts may be mixed in a one or two solution system. The
proportions of phenol, formaldehyde, and catalyst are fixed by reaction
requirements so the only variable is the amount of water added (Tallard and
Caron 1977a). Polymerization begins as soon as the solutions or grout
components are mixed. In general, polyvalent cations from the alkali
catalyst initiate and promote polymerization (Chung 1973). The polymeriza-
tion (polycondensation) process results in the formation of a three dimen-
sional network of polymer chains (phenol) that are joined and crosslinked by
formaldehyde (Karol 1982a, Bowen 1981, Tallard and Caron 1977a). The
41
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TABLE 6. PHENOL RESIN GROUT PRODUCTS
Product Composition References
Rocagil Partially sulfonated tannin Sommerer and
Formaldehyde Kitchens 1980
Karol 1982a
Geoseal Tannin
Mimosa extract Bowen 1981
Phenolic precondensate Chung 1973
Formaldehyde/paraformaldehyde Karol 1982a
Salts
Catalyst (sodium hydroxide)
Terranier Low molecular weight polyphenolic Bowen 1981
polymers or lignosulfonate
Catalyst (formaldehyde) Chung 1973
Activator (modified metal salt— Karol 1982a
sodium dichromate)
42
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catalyst is also attached to the polymer resin and it may form secondary
linkages within the resin network or bond with the soil. The resulting resin
is insoluble and retains all constituent materials (Tallard and Caron 1977a).
Phenolic Grout Properties—
Phenolic grouts have low viscosity. Phenolic grouts made with
resorcinol and formaldehyde have viscosities between 1.2 and 3 cP for normal
field concentrations (Karol 1982a, Tallard and Caron 1977b). Commercial
products consisting of tannin or polyphenols typically have a higher
viscosity: Geoseal ranges from 2 to 12 cP; Terranier ranges from 4 to 10 cP;
Rocagil ranges from 5 to 10 cP (Bowen 1981, Tallard and Caron 1977a, Tallard
and Caron 1977b). The viscosity depends on the concentration of the grout
(Tallard and Caron 1977a). As with acrylamides, resorcinol-formaldehyde
grouts remain of constant viscosity until gelation occurs. With tannin-based
grouts, the viscosity gradually increases (after the components are mixed)
until set is achieved (Karol 1982a, Tallard and Caron 1977b).
The gel or set time of phenolic grouts may vary from several minutes to
several hours (Bowen 1981). The gel time is primarily controlled by the
diluteness of the grout with short gel times for concentrated grout solutions
and long gel times for dilute solutions (Karol 1982a, Tallard and Caron
1977a). With very dilute solutions, gelation may never occur and the grout
becomes unusable (Tallard and Caron 1977a). If all other factors remain
constant, the choice of catalyst will affect the set time because different
bases have different reactivities. Sodium hydroxide, the most common
catalyst, provides approximately a 20 minute gel time as do some carbonates
and calcium hydroxide. Other bases (hydroxides and carbonates) provide
longer set times (Tallard and Caron 1977b).
The length of set time affects the strength of the grout, with short set
times giving strong gels and long set times giving weak gels. Strong grouts
are not critical to waterproofing, but short set times are often important
(Karol 1982a). To decrease the set time, phenolic grouts may be combined
with another grout, such as a silicate, that has a shorter set time. This
other grout will set first and provide a "false set." The phenolic grout is
retained in the grout matrix and sets at its normal rate. The final proper-
ties of the grout mixture are determined by the phenolic grout (Tallard and
Caron 1977a).
Wet cured phenolic grouts (under the water table) are generally durable,
however, there may be a slight weakening over time due to gradual swelling of
the resin (Tallard and Caron 1977b). After setting is complete, the phenolic
resin contains water that is not chemically bound in the matrix. Under
drying conditions, this water can evaporate and the gel may shrink and crack
(Sommerer and Kitchens 1980, Tallard and Caron 1977a, Tallard and Caron
1977b). Unlike acrylamides and silicates, this dehydration is irreversible
and can lead to disintegration of the gel (Karol 1982a, Tallard and Caron
1977a).
Proper proportioning of phenol and formaldehyde in phenolic grout will
produce a complete reaction and the resulting gel is relatively insoluble and
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inert (Tallard and Caron 1977a, Tallard and Caron 1977b). If the materials
are not properly proportioned, excess materials may leach out of the resin.
In either case, some of the catalyst may remain partially soluble and leach
out of the matrix (Karol 1982a, Tallard and Caron 1977a, Tallard and Caron
1977b).
Phenolic grouts contain toxic and caustic materials which require
special handling (Karol 1982a, Tallard and Caron 1977b). The toxicity of
some of the grout components are summarized below (Tallard and Caron 1977b):
Chemical Oral LD-. Skin LD-.
Resorcin 301 mg/kg 2,050 mg/kg
Phenol 414 mg/kg 699 mg/kg
Formaldehyde 800 mg/kg 260 mg/kg
In handling these compounds, standard safety precautions as outlined in
the handling procedures provided with the grout should be followed including
the use of gloves, respirators, and protective garments. The hardened grout
is essentially nontoxic and noncaustic (Bowen 1981). If the constituents are
improperly proportioned however, excess (unreacted) material may leach from
the matrix (Tallard and Caron 1977b).
Grout/Chemical Interactions—
Phenol-formaldehyde resins are resistant to organic solvents (Billmeyer
1971). Phenolic resin mortars are recommended for use with organic acids,
wet gases (reducing), nonoxidizing and nonreducing gases, nonoxidizing
mineral acids (except hydrofluoric acid), and highly concentrated sulfuric
acid (>85%). These recommendations are based on immersion of the mortar in
these compounds (ASTM 1982).
Phenolic resins are not resistant to alkaline substances (Boova 1977).
Both strong acids and bases will attack phenol-formaldehyde resins (Billmeyer
1971). Phenolic resin mortars are not recommended for use with bleaches or
wet gases (oxidizing), but are recommended for limited use with oxidizing
mineral acids, inorganic alkali, and organic solvents (ASTM 1982).
Areas of Application—
Phenolic grouts are used in soils of low permeability such as fine
gravel and coarse, medium, and fine sand. (Sommerer and Kitchens 1980,
Herndon and Lenahan 1976b). These grouts have been used to stop leaks in
railway tunnels and for ground surface treatment (Flatau, Brockett, and Brown
1972, Tallard and Caron 1977a). Phenolic grouts find their greatest use in
combination with silicate grouts in treating fine sands and silts (Tallard
and Caron 1977a).
Different phenolic grout products have been formulated to meet different
needs. Geoseal MQ-4 was designed for resistance to saline groundwater while
Geoseal MQ-14 was designed for treating low permeability materials. In
addition, Terranier C was designed for grouting silts (Bowen 1981).
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Properties of Urethane Grouts
Urethane grouts are the second most commonly used organic polymer grouts
(Jacques 1981). Urethane grouts were developed in Germany for consolidation
applications, and are now used in Europe, South Africa, Australia, and
Japan*, (Sommerer and Kitchens 1980). These grouts are used for
waterproofing and soil applications, and can penetrate finely fissured
material.
Chemical Composition and Reaction Theory—
Urethane, or polyurethane, grout consists primarily of a polyisocyanate
and a polyol or other hydroxy compounds such as polyethers, polyesters, or
glycols (Karol 1982a, Vinson and Mitchell 1972). A diisocyanate is often
used as well (Vinson and Mitchell 1972). RokLok®, a polyurethane grout,
consists of polymethylene polyphenyl isocyanate (containing diphenylmethane
diisocyanate) and poly(oxyalkylene) polyether polyol resin (Mobay Chemical
Corporation 1982). Other substances may be added as catalysts, surfactants,
dilution agents, plasticizers, and stabilizers. These materials control the
reaction of the grout and its properties before and after setting.
Urethane grouts set through a multistep polymerization process. The
initial reaction occurs between excess isocyanate and the polyol compound to
form a polyurethane prepolymer (Jiacai et al. 1982, Karol 1982a). To
complete the reaction sequence, the prepolymer is reacted with water to form
polyurethane foam. Carboxylic acid and/or other hydroxyl-containing compo-
unds may be used in addition to or in place of water (Karol 1982a, Vinson and
Mitchell 1972). This foam consists of crosslinked polyurethane chains with
the crosslinking occurring through the formation of urea linkages accompanied
by the generation of carbon dioxide gas (Vinson and Mitchell 1972, Billmeyer
1971).
Rather than complete the entire reaction at one time, the reaction
sequence may be temporarily halted at the prepolymer formatin step with the
final reaction of the prepolymer to form urethane foam being completed later.
Many of the urethane grouts currently on the market consists only of the
prepolymer; the polyurethane is generated from the prepolymer at the time of
use.
In general, other materials may be added to the grout catalysts such as
tertiary amines (triethylamine, triethanolamine, triethylenediamine) or tin
salt to control the rate of gellation and foaming (Karol 1982a, Jiacai et al.
1982). Stabilizers and surfactants may be added to control the surface
tension of the grout as well as the size of the bubbles (Karol 1982a, Jiacai
et al. 1982). Since the prepolymer has a high viscosity, the grout may be
diluted with a solvent such as acetone, xylene, ethyl acetate, or dichloro-
methane. Plasticizers such as dibutylphthalate may also serve as dilution
agents (Jiacai et al. 1982).
*McCabe, K.W. Mobay Chemical Corporation, Pittsburgh, PA. Written
communication with G. Hunt, JRB Associates, August 3, 1982.
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Urethane Grout Properties—
Formulated urethane grouts range in viscosity from 20 to 200 cP (Karol
1982a, Sommerer and Kitchens 1980, Avanti International 1982). The type of
isocyanate and hydroxylated compounds used in the grout are major determi-
nants of viscosity (Tallard and Caron 1977a). The amount of diluent in the
grout also affects viscosity. With no diluent, the viscosity may be several
thousand cP; however, the viscosity is approximately 25 cP with 50 percent
dilution (Jiacai et al. 1982).
The set time varies from several seconds to several minutes or hours
(McCabe 1982, Avanti International 1982, Tallard and Caron 1977a). The set
time can be controlled with acids, amines, alcohols, water, or polyol size.
The set time can be shortened by increasing the water content, moving from a
primary to a secondary or tertiary alcohol, or increasing the catalyst
(amine) content (Vinson and Mitchell 1972, Tallard and Caron 1977a). It may
also be lengthened by decreasing the size of the polyol or by adding an acid
(Sommerer and Kitchens 1980, Vinson and Mitchell 1972).
If properly formulated, set urethane grouts resist most chemicals and
other degradative processes. Set urethane grouts are reported to have good
resistance to oxidation, shrinkage from drying, and biological agents. Some
shrinkage of the grout may occur however, in response to water table
fluctuations (Avanti International 1982, Billmeyer 1971).
The prepolymer used in urethane grouts is flammable. The prepolymer and
its components have low toxicity with an LD5Q of 5,000 mg/kg or more (Berry
1982, Avanti International 1982, Mobay Chemical Corporation 1982). Most of
the grouting formulations contain some free toluene diisocyanate. Special
handling and protective equipment are needed when working with the grout
materials because they are eye, skin, and respiratory irritants (Berry 1982,
Avanti International 1982).
Grout/Chemical Interactions—
Set polyurethane resins are reported to have good resistance to
oxidation and solvents (Billmeyer 1971). If properly formulated, CR-250 (a
polyurethane grout) resists most chemicals and solvents. Testing of this
grout indicated that no visible changes occurred when it was subjected to
dilute acetic acid, sulfuric acid, and hydrogen sulfide, as well as
concentrated organic solvents (Avanti International 1982). Further testing
of CR-250 indicated various amounts of shrinkage in response to hydrochloric
acid, ethylene glycol, methyl ethyl ketone, ammonium and potassium sulfate,
and sodium chloride. Swelling was noted in response to dilute hydroxides and
isopropanol (Avanti International 1982) .
Although the isocyanates in the grout react with water they can also
react with carboxylic groups as well as hydrogen and nitrogen ion such as
ammonia or ammonium hydroxide (Karol 1982a). The presence of these materials
may interfere with proper reaction and setting of the grout. Preliminary
results from a laboratory compatibility testing program undertaken by the
U.S. Army Corps of Engineers Waterways Experiment Station has shown that the
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urethane grout tested would not set in the presence of low levels of any of
the chemicals selected for their study.
Areas of Application—
Urethane grouts have been used in a number of waterproofing and soils
applications. Some formulations have been used for consolidation grouting in
coal mines and railroad tunnels (Mobay Chemical Corporation 1982). Other
formulations are primarily used for sewer grouting and pipe sealing (Avanti
International 1982). CR-250 has been used for potable water applications as
well as soil sealing and waterproofing (Jacques 1981).
TACSS, a urethane grout produced in Japan, has been used for sealing
voids in karst materials and for consolidating and waterproofing ground
through which large volumes of water circulate (Tallard and Caron 1977a).
Due to the high viscosity of this formulation (and by analogy, other urethane
grouts), it cannot be used to treat fine grained soils (Karol 1982a).
Properties of Urea-Formaldehyde Grouts
Urea-formaldehyde resins are frequently referred to as aminoplasts. The
idea for the use of these resins as grouts came from their use as glue. The
oil industry the first to use these resins for grouting (Tallard and Caron
1977a). Although urea-formaldehyde grouts have been available since the
1960s, they have found limited usage (Karol 1982b, Sommerer and Kitchens
1980).
Chemical Composition and Reaction Theory—
Urea-formaldehyde resin grouts consist of urea, formaldehyde, a
catalyst, and water. The urea-formaldehyde mixture may be in monomer or
prepolymer form. The catalyst is an organic acid, inorganic acid, or acid
salts. In Cyanaloc 62 (discontinued), the catalyst was sodium bisulfate
(Karol 1982a, Kirk-Othmer 1979, Tallard and Caron 1977a, Chung 1973).
The urea-formaldehyde resin is formed in a two step reaction process.
First, the urea and formaldehyde monomers react through methylolation or
hydroxymethylation, to form low molecular weight polymers. This reaction may
be either acid or base catalyzed (Kirk-Othmer 1978b). The second reaction
involves further polymerization through condensation of the polymers with
water being generated. This reaction will occur only with an acid catalyst
(Kirk-Othmer 1978b, Billmeyer 1971). The resulting resin is a stable network
of crosslinked urea-formaldehyde polymers (Tallard and Caron 1977a).
There are two mechanisms for achieving this reaction sequence. Where
the grout mixture uses urea and formaldehyde monomers, the two reactions
occur rapidly and the overall reaction is difficult to control (Karol 1982a).
The second mechanism involves stopping the reaction sequence after
methylolation. At this point, precondensates or prepolymers have formed
which are soluble in water and are prevented from further reaction through
the use of inhibitors or pH controls (Karol 1982a, Tallard and Caron 1977a).
Commercially, the methylolation reaction is base catalyzed (Kirk-Othmer
1978b, Tallard and Caron 1977a). The second reaction, polymerization, may be
47
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caused later by lowering the pH of the prepolymer solution. By introducing
an intermediate stage in the reaction, better gel time control is achieved
and sudden setting of the grout can be avoided (Karol 1982a, Tallard and
Caron 1977a).
In either case, an acid medium is required for final polymerization to
occur. For this reason, urea-formaldehyde resins cannot be used in alkaline
media. The acid catalyst will react with the media and be destroyed before
it can react with the grout (Sommerer and Kitchens 1980, Tallard and Caron
1977a, Rensvold 1968). In addition to pH control, the urea-formaldehyde
reaction is also controlled by the mole ratio of the reactants and dilution
of the mixture (Kirk-Othmer 1978b, Tallard and Caron 1977a).
Urea-Formaldehyde Grout Properties—
Urea-formaldehyde grouts have a low viscosity. Urea solutions
(unpolymerized) have viscosities similar to acrylamides and phenolics (Karol
1982a). Solutions of urea-formaldehyde prepolymers are more viscous, with
typical formulations having a viscosity of 10 to 13 cP (Karol 1982a, Sommerer
and Kitchens 1980).
The set time varies with the type of grout formulation and the type of
catalyst. Monomer grouts have a very short set time because the reaction is
abrupt. To achieve more control over the set time, prepolymer grouts are
used. This however, increases the viscosity of the grout and makes it
unsuitable for fine soils. Depending on the catalyst, the set time may vary
from several minutes (hydrochloric acid) to almost an hour (sulfuric acid).
The proportion of the catalyst and the dilution of the grout will also affect
the set time (Tallard and Caron 1977a).
For urea-formaldehyde grouts there is both a gel time and a cure time.
The gel time refers to the time to form a soft gel, similar to acrylamide.
Following gellation, the grout cures to a stiffer consistency. This occurs
over a few hours to as long as a day, with the rate dependent on the gel time
(Karol 1982a).
Urea-formaldehyde grouts are considered permanent, with good stability
(Karol 1982a). If the grout is properly formulated and a good poly-
condensation reaction is achieved, the resulting resin should be inert and
insoluble to most solvents, although it will contain some free formaldehyde
(Karol 1982a, Tallard and Caron 1977a). These grouts however, may quickly
break down when subjected to cyclic wet/dry or freeze/thaw cycles (Karol
1982a). Fung (1980) reports that some urea-formaldehyde resins are
biodegradable.
The grout solution is both toxic and corrosive because it contains
formaldehyde and an acid catalyst. However, grout solutions using
prepolymers have less free formaldehyde (Karol 1982a, Tallard and Caron
1977a). The cured resin has low toxicity. The resin is considered inert but
it contains some unreacted formaldehyde (Kirk-Othmer 1978b, Tallard and Caron
1977a).
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Grout/Chemical Interactions—
As mentioned above, if a good polymerization (condensation) reaction is
achieved, the resulting resin is inert and insoluble in most solvents. In
general, urea-formaldehyde grouts are compatible with acids, sulfates, and
halides (Malone, Jones, and Larson 1980).
The setting of urea-formaldehyde grouts may be slowed by organic
solvents and oils (Malone, Jones, and Larson 1980). Cement will prevent the
setting of these grouts (Kirk-Othmer 1979). In general, alkaline materials
will inhibit the polymerization reaction through destruction of the acid
catalyst.
Upon setting, oxidizing agents such as chlorine or peroxides may cause
the grout matrix to break down (Malone, Jones, and Larson 1980). Testing of
Cyanaloc 62 (discontinued) determined that this urea-formaldehyde grout
deteriorated and lost strength upon prolonged submergence in an acid solution
(Chung 1973).
Finally, the acidity of the grout may affect surrounding materials. For
example, the low pH of the grout can solubilize metal hydroxides (Malone,
Jones, and Larson 1980). This can increase the mobility of these heavy
metals.
Areas of Application—
Because of the acidity requirements, urea-formaldehyde grouts have
undergone little development (Tallard and Caron 1977a). They have been used
for ground stabilization and sealing coal mines but no long-term applications
have been reported (Karol 1982a, Tallard, and Caron 1977a). These grouts can
generally be used only in ground and groundwater with a pH less than 7.
Their development is further limited due to their toxic constituents and the
production of ammonia during condensation (Sommerer and Kitchens 1980).
Most of the descriptions of urea-formaldehyde grout applications come
from Eastern Europe, the USSR, and Japan. Products containing prepolymers
are used in Poland and Hungary. The USSR resolves the acid media problem
through injection of an acid solution to destroy carbonates before injection
of urea-formaldehyde. This technique, however, is not used outside of the
USSR, is costly, and increases the size of soil voids. Further, soil
instability may be created through destruction of soil components (Tallard
and Caron 1977a).
Properties of Epoxy Grouts
Epoxy grouts, like other glue-like grouts, have been in use since around
1960. These grouts have had limited use in soil grouting primarily because
of their high cost (Tallard and Caron 1977a).
Chemical Composition and Reaction Theory—
Epoxy grouts are resins that consist of an epoxide, a hydroxy compound,
and a hardener. The epoxide is typically epichlorohydrin, while the hydroxy
49
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compound is typically bis-phenol A (2,2-bis(4-hydroxyphenol) propane) (Modern
Plastics Encyclopedia 1981, Tallard and Caron 1977a, Billmeyer 1971).
Epoxies are generally cured through the addition of a hardener (Tallard
and Caron 1977a). These hardeners are crosslinking agents which react with
epoxy and hydroxyl groups (Modern Plastics Encyclopedia 1981). The resulting
epoxy resins are polyethers (Billmeyer 1971).
A number of hardeners may be used. Typically, amines, polycarboxylic
anhydrides, or monocarboxylic acids are used. Each hardener reacts differ-
ently, and imparts different properties to the resin. Different proportions
between the resin and the hardener will also provide different types of
resins. The resin-hardener ratio, however, cannot be varied greatly (Tallard
and Caron 1977a).
As a result of the amine hardening process, amine-terminated polyamide
resins are generated. These resins replace water on wet surfaces creating a
water-free interface between the resin and the material covered (Engineering
News-Record 1965). For this reason, epoxy resins are useful in applications
in wet areas or under water.
Epoxy Grout Properties—
The viscosity of epoxy grouts varies with the molecular weight
(Billmeyer 1971). The most fluid of these resins has a viscosity of at least
400 cP. This viscosity may be lowered to 100 cP through the addition of a
fluid hardener (Tallard and Caron 1977a). Organic solvents and reactive
dilution substances may also be used to alter the viscosity (Sommerer and
Kitchens 1980, Tallard and Caron 1977a). Ethers such as butyl glycidyl ether
can further decrease the viscosity of epoxy grouts to 20 cP (Tallard and
Caron 1977a).
The set time of epoxy grouts varies depending on the choice of hardener.
In general, the set time is difficult to regulate (Tallard and Caron 1977a).
Epoxy grouts have good durability. In the ground, their properties are
similar to those of the polyesters which may be subject to hydrolysis
(Tallard and Caron 1977a). Epoxy mortars tend to have little shrinkage and
limited water absorption (U.S. Grout Corporation 1981, Boova 1977).
Epoxy grouts consist of substances requiring special handling
precautions. If the grouts are properly formulated, resin formation should
incorporate all of the materials and the toxicity of the gel or its
components will be minimized (Tallard and Caron 1977a).
Grout/Chemical Interactions—
Chemical resistance and incompatibility data were available primarily
for epoxy resin mortars rather than grouts. These mortars are similar to the
grouts, although they often contain fillers which may alter the resistance of
the epoxy resin. The reported resistances are generally for immersion of the
resin in the media in question.
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In general, epoxy grouts are resistant to acids, alkalis, and organic
chemicals (Office of the Chief of Engineers 1973). Epoxy resin mortars are
recommended for nonoxidizing mineral acids (except sulfuric acid and hydro-
fluoric acid), inorganic alkalis, wet gases (reducing), and nonoxidizing and
nonreducing gases (except ammonia) (ASTM 1982). These mortars are also
recommended for ethyl alcohol, gasoline, hydrochloric acid, sodium chloride,
and sodium hydroxide (25%) (Boova 1977).
Epoxy resin mortars are not recommended for use with ammonia, wet gases
(oxidizing), glacial acetic acid, benzene, chromic acid (20%), hydrofluoric
acid, dichloroacetic acid (10%), sodium hypochlorite (10%) trichloroethylene,
and xylene (Boova 1977, ASTM 1982). ASTM (1982) reports limited application
of resin mortars in presence of oxidizing mineral acids, organic acids,
bleaches, and organic solvents.
Areas of Application—
Epoxy resins are infrequently used for soil grouting because of their
high cost (Tallard and Caron 1977a). Most of the applications reported in
the literature have addressed the use of epoxy resins in mortars used for
sealing cracks. Epoxy resins can adhere to and seal submerged concrete,
steel, or wood surfaces and are useful in waterproofing applications
(Engineering News-Record 1965). They have been used for grouting of cracked
concrete for structural repairs, and grouting fractured rock to improve its
strength (Office of the Chief of Engineers 1973).
Properties of Polyester Grouts
Polyester grouts have been in use since the 1960s, and have been used in
a variety of construction applications. These grouts, however, are generally
suitable only for very specific applications (Tallard and Caron 1977a).
Chemical Components and Reaction Theory—
Polyester grouts consist of a resin base and a catalyst (Office of the
Chief of Engineers 1973). The resin is unsaturated and consists of a poly-
ester produced from the reaction of a polyacid and polyalcohol. Typically,
this reaction involves the condensation of an unsaturated diacid (maleic acid
or fumaric acid) with a dialcohol. In commercial products, a reticulant is
included with the polyester resin. These products may contain 30 to 40 per-
cent reticulant, typically styrene (Tallard and Caron 1977a, Billmeyer 1971).
Polymerization is achieved through addition of the catalyst, which is
generally a peroxide. The catalyst causes the polyester resin to polymerize
as well as copolymerize with the reticulant. A gel forms which eventually
hardens to a solid material (Tallard and Caron 1977a, Office of the Chief of
Engineers 1973). The hardening process is accompanied by shrinkage of the
resin by as much as 10 percent (Office of the Chief of Engineers 1973).
Accelerators may be added to speed up the setting by facilitating the
decomposition of the catalyst into free radicals (Tallard and Caron 1977a,
Office of the Chief of Engineers 1973). Accelerators include cobalt,
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manganese, or vanadium salts; mercaptans; tertiary amines; and quaternary
ammonium salts (Tallard and Caron 1977a).
The quantity and type of polyester, reticulant, and catalyst may each be
varied and each variation will produce different resins with different
characteristics (Tallard and Caron 1977a).
Polyester Grout Properties—
Commercial polyesters vary in viscosity from several hundred to several
thousand cP. The minimum viscosity is between 200 to 250 cP. This,
however, is too high to grout even coarser earth materials such as sand. The
viscosity, though, can be reduced to 10 to 50 cP by adding a reactive diluent
(Tallard and Caron 1977a).
The set time of polyester grouts varies from a few minutes to several
days and the resins may contain volatile compounds that make long set times
uncertain (Tallard and Caron 1977a). The set time can be controlled through
resin volume, ambient temperature, catalyst selection, and heat dissipation
(polymerization is exothermic). In addition, excessive moisture may inhibit
the setting of polyester grouts (Office of the Chief of Engineers 1973).
The long-term behavior of polyester grouts is reported to be good,
however, there is a long-term risk of hydrolysis particularly in alkaline
media (Tallard and Caron 1977a). Further, these gels shrink during curing
and this shrinkage may be as high as 10 percent (Office of the Chief of
Engineers 1973).
The components of the polyester grouts are toxic and require special
handling during grout preparation. After polymerization, the risks are less
(Tallard and Caron 1977a). Unreacted constituents in the polymerized grout,
however, may be leached out.
Grout/Chemical Interactions—
Available information addressed the chemical resistance of polyester
resin mortars which are similar to polyester grout except that they contain
fillers (Boova 1977). These materials were rated based on immersion in the
chemicals.
Polyester resin mortars are recommended for chlorine dioxide, gasoline,
hydrochloric acid, nitric acid, sulfuric acid (50 percent), sodium chloride,
ethyl alcohol, lactic acid, phosphoric acid, sodium hydroxide (25 percent),
and sodium hypochlorite (10 percent) (Boova 1977). In general, these mortars
are resistant to nonoxidizing mineral acids (except for sulfuric acid
[>_ 85 percent] and hydrofluoric acid), bleaches, wet gases (oxidizing and
reducing), and nonoxidizing and nonreducing gases (ASTM 1982). They have
limited use for organic acids, oxidizing mineral acids, xylene, and
trichloroethylene (ASTM 1982, Boova 1977).
Polyester resin mortars are not recommended for use with glacial acetic
acid or benzene (Boova 1977). In general, these mortars are not recommended
for inorganic alkali or organic solvents (ASTM 1982).
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Areas of Application—
Polyester grouts have been used in a variety of construction applica-
tions, but are principally used to treat cracks in buildings and structures
(Tallard and Caron 1977a). These grouts have also been used in mines to
stabilize and strengthen porous and fissured rock (Tallard and Caron 1977a,
Office of the Chief of Engineers 1973). Polyester grouts have been used
infrequently to consolidate sand (Tallard and Caron 1977a).
In general, polyester grouts have limited suitability. They can be used
for injection, although they are not recommended for materials with large
voids due to shrinkage during curing (Tallard and Caron 1977a).
PROPERTIES OF OTHER GROUTS
There are a number of other grout types available that have either
limited or questionable use in soils, or are no longer used. These grouts
and their properties are briefly summarized.
Properties of Lignochrome Grouts
Lignochrome grouts are also referred to as lignosulfonate or chrome-
lignin grouts. This type of grout consists of a lignin-containing material
and a hexavalent chromium salt (Kirk-Othmer 1979, Ingles and Metcalf 1973).
Calcium lignosulfates provide better waterproofing and stability than sodium
lignosulfates (Rogoshewski et al. 1980). Ammonium lignosulfonate may also be
used (Sommerer and Kitchen 1980). Potassium dichromate may be used as the
hexavalent chromium salt (ingles and Metcalf 1973).
In the presence of an acid, the lignosulfate is oxidized by the hexa-
valent chrome to form a gel (Sommerer and Kitchens 1980, Bowen 1981, Ingles
and Metcalf 1973). During this reaction, hexavalent chromium is reduced to
the trivalent form (Rogoshewski et al. 1980). The set time is controlled by
the concentration of hexavalent chromium, acid, water, and the catalyst
(typically another metal salt) (Rogoshewski et al. 1980, Sommerer and
Kitchens 1980). During injection, the grout may be diluted by groundwater
and this can increase the set time (Office of the Chief of Engineers 1973).
Lignochrome grouts typically have low viscosities (2-15 cP) and
moderately short setting times (3-300 minutes). The durability of these
grouts is questionable, as their strength decreases over time in water-
saturated environments (Kirk-Othmer 1979). Also, chromium can be leached
from the set grout (Sommerer and Kitchens 1980). This process depends on the
age of the grout, the chrome-lignin ratio, the acidity (pH), and curing time
(Sommerer and Kitchens 1980, Office of the Chief of Engineers 1973).
The chromium salts used in lignochrome grouts are highly toxic. In
addition, the lignin materials can cause skin irritation (Kirk-Othmer 1979).
Little information was available regarding the compatibility of these
grouts with chemicals. Lignochrome grouts should not, however, be used with
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Portland cement because the pH of the materials conflict (Kirk-Othmer 1979)„
Further, lignochrome grouts are not compatible with fly ash because its
alkalinity can cause trivalent chromium to precipitate from the dichromate
catalyst (Chung 1973).
Lignochrome grouts have primarily been used for water cut-off and
consolidation of fine, granular soil (Office of the Chief of Engineers 1973).
They can be used in sands with a permeability between 10 and 10 cm/sec
(Sommerer and Kitchens 1980). Lignochrome grouts have been used in water
cut-off applications for dams (Engineering News-Record 1953). These grouts
appear to have little use at this time, and are currently not manufactured in
the United States.
Properties of Furan Grouts
Furan grouts consist of low polymers of furfuryl alcohol dissolved in
excess furfuryl alcohol. For furan mortar grouts, the liquid resin is mixed
with an inert powder filler (usually carbon) containing an acid catalyst.
This catalyst promotes further polymerization to form a crosslinked,
infusible material (Boova 1977).
Furan grouts have been referenced in the literature largely with respect
to their use as mortars. They provide a broad range of chemical resistance
to organic and inorganic acids, alkali, salts, greases, and solvents (Boova
1977). These grouts have excellent resistance to acids and almost all alkali
(Boova 1977). They are not recommended, however, for oxidizing acids in
general, as well as chromic acid (20%), nitric acid, sodium hypochlorite
(10%), or concentrated sulfuric acid (Boova 1977, ASTM 1982).
These resin grouts are used in applications where resistance to
corrosive media is important. They are also used for polymer concrete. This
concrete consists of alkali-free aggregate (silica or quartz) that is bonded
with furan resins and cured with an acidic catalyst. This concrete is
resistant to acids, salts, solvents, and bases (Modern Plastics Encyclopedia
1981).
Miscellaneous Grouts
Several other types of grouts have been referenced with regard to soil
applications. The majority of these materials are polymers. One such grout,
Polythixon FRDS is an oil-based unsaturated fatty acid polymer. It has low
viscosity (10-80 cP) and a gel time of 25 to 360 minutes. This grout is
recommended for high strength consolidation rather than waterproofing appli-
cations (Neelands and James 1963).
Another polymer grout is PWG sealant, a polymerized crosslinked gel
(unspecified polymer). This grout has very low viscosity (1.5 cP) and a very
short set time (several seconds to more than a minute). The set gel is
insoluble in water, kerosene, and oil, and is impermeable to water, oil, and
gases. If the gel dehydrates, it can rehydrate in the presence of water to
54
-------
regain its original size. In addition, this gel may undergo "wicking," i.e.,
if one "face" of the gel dehydrates, moisture can move from the hydrated
"face" to the dehydrated "face" (Lenahan 1973).
Aniline-furfural resins may be used for the stabilization of cohesion-
less sand. These resins are catalyzed by pentachlorophenol or ferric
chloride (Bowen 1981). Also, emulsions such as latex and salt water, styrene
butadiene latex, and pitch polyurethane mixtures may be used a grouts (Bowen
1981).
Base-cured materials have been investigated for use as grouts. These
materials do not, however, have low viscosity or other characteristics that
lend them to injection at pressures that will not disturb the formation
(Rensvold 1968).
55
-------
-------
SECTION 6
COMPATIBILITY OF GROUTS WITH HAZARDOUS WASTES
Through a detailed evaluation of available information on the effects of
chemicals on grout performance, a series of matrices were developed that
summarize and define the compatibilities of grouts with various chemical
groups. This information was gathered through contacts with representatives
from universities, industries, trade associations, and government agencies
along with a detailed review of the published literature. The literature
sources, listed in the bibliography, contained not only grouting related
publications but also references on waste fixation/solidification, cement
chemistry, landfill/lagoon linear performance, slurry wall construction, and
polymer chemistry as well as performance specifications for cement, coatings,
and tile grouts.
From the information obtained, three matrices were developed which
summarize and define the compatibilities of grouts with various chemical
groups. These matrices provide a step-wise analysis of the data, moving from
general to specific information that has been found. It must be noted,
though, that most of the information detailed the effects of pure chemicals
or did not specify a concentration. Thus, this data can be assumed to be
related to the effects of undiluted chemicals. While leachates generally
contain low levels of compounds, there can be instances where grouts will
come into contact with high concentrations of chemicals, such as organic
solvent lenses within the groundwater system.
The following subsections present the matrices along with a discussion
of matrix development, data sources, and limitations.
KNOWN COMPATIBILITY OF GROUTS WITH CLASSES OF CHEMICALS
The structure of the matrices is as follows: the types of grouts, on
the horizontal axis,"are correlated with the chemical groups on the vertical
axis. These two parameters are linked by codes that represent the type of
compatibility/incompatibility of the chemicals and grouts. An overview of
each of the grout types and chemical groups utilized in these matrices along
with the compatibility index is contained in the following discussions.
Preceding page blank
57
-------
Grout Classes
Based on the results of our information search, six categories of grouts
that potentially could be used for construction at hazardous waste sites
were selected for inclusion in our study. These categories are:
• Bitumen
• Portland Cement
- Type I
- Type II and V
• Clay (Bentonite)
• Clay-Cement
• Silicates
• Organic Polymers
- Acrylamide
- Phenolic
- Urethane
- Urea-formaldehyde
- Epoxy
- Polyester.
A detailed discussion of the chemical characteristics, reaction theory,
physical/chemical properties, and areas of application of each of these
grouts can be found in Section 3.
Chemical Groups
In order to reduce the complexity of the matrix, the chemical universe
was divided into 16 basic groups as follows:
• Alcohols and Glycols
• Aldehydes and Ketones
• Aliphatic and Aromatic Hydrocarbons
• Amines and' Amides
• Chlorinated Hydrocarbons
• Ether and Epoxides
• Heterocyclics
• Nitriles
• Organic Acids and Acid Chlorides
• Organo-metallics
58
-------
• Phenols
• Organic Esters
• Heavy Metal Salts and Complexes
• Inorganic Acids
• Inorganic Bases
• Inorganic Salts.
The choice of the 16 basic groups was not meant to be all inclusive, but
rather, a representative choice of the types of compounds found in landfills.
The organic categories were chosen by functional group or structural charac-
teristic; the inorganics are essentially divided into the classical acid/
base/salt categories. The functional grouping for the organics is useful
because, although their physical properties and solubilities may differ, the
interaction of a particular functional group with other groups remains the
same. For example, all amines may not be soluble in water, but they all can
be halogenated. In addition, one chemical may fit in more than one category
if it has more than one functional group. For example, p-aminobenzoic acid
is both an amine and an organic acid. The amine and acid moieties will
chemically act independently of one another although the reactivity may be
modified to some extent by the presence of the new group.
The following subsections outline the chemical structure and properties
that separate the different groups of chemicals. Examples of compounds
contained in each of the chemical groups are given in Table 7.
Alcohols and Glycols—
Alcohols and glycols both contain hydroxyl (-OH) groups and are grouped
together because of that common functionality. Alcohols are aliphatic or
aromatic compounds that contain a single hydroxyl (-OH) group. This group
excludes compounds where the hydroxyl group is attached directly to an
aromatic ring, because these compounds are phenols and have very different
properties and reactions than alcohols. The lower alcohols (containing small
aliphatic groups) are miscible with water and are capable of hydrogen
bonding. Higher alcohols (containing aromatic or large aliphatic groups) have
a much larger organic component and are much less miscible in water and less
able to form hydrogen bonds.
Glycols are dihydroxy alcohols. These substances are aliphatic or
aromatic compounds that contain two hydroxyl groups. As with alcohols, lower
glycols have a greater miscibility in water. Glycols containing as many as
7 carbon atoms are soluble in water.
Aldephydes and Ketones—
Aldehydes and ketones both contain a carbonyl group (C=0). In alde-
hydes, the carbonyl group is attached to one organic group (aliphatic or
aromatic), thus, the carbonyl group appears at one "end" of the compound.
Ketones, however have two organic groups (aliphatic or aromatic) attached to
59
-------
TABLE 7. EXAMPLES OF CHEMICALS WITHIN EACH
OF THE CHEMICAL GROUPS
ALDEHYDES AND KETONES
Examples of Aldehydes
"CH = CH CHO
Acrolein
Examples of Ketones
CHO
Furfural
COCH
COCH
Methyl Ethyl Ketone
Acetone
COCH0
60
-------
TABLE 7. (Continued)
ALCOHOLS AND GLYCOLS
Examples of Alcohols
OH
Ethanol
Examples of Glycols
OHCHOHCH
1 ,2-Propanediol
CH3 OH
Methanol
CH2 OHCH2 OH
Ethylene Glycol
ALIPHATIC/AROMATIC HYDROCARBONS
Examples of Aliphatic Hydrocarbons
Cyclohexane
CH2 = CH - CH = CH - CH3
1,3-Pentadiene
Examples of Aromatic Hydrocarbons
10)
Toluene
Cyclohexanol
n-Hexane
Benzene
61
-------
TABLE 7. (Continued)
AMINES AND AMIDES
Examples of Amines
Aniline
H
CH3 CH2 - N - CH2
Methylethyl amine
Examples of Amides
NHCOCH.,
«•" ^
O
Acetanilide
NIL
/r ^v
o
NH0
p-Phenylenediamine
CH,,
n - C,H7 - N - CH-
n - propyldimethylamine
NHCOCH.,
^ ^+,
O
CH,
Aceto-p-toluidide
62
-------
TABLE 7. (Continued)
ETHERS AND EPOXIDES
Examples of Ethers
Cl - 0 - CH2 -
Bis (Chloromethyl Ether)
- 0 -
Diethyl Ether
CH2
Cl CH2 CH2 - 0 - CH = CH2
2-Chloroethyl Vinyl Ether
Furan 1,4-Dioxane
Examples of Epoxides
0
CH - CH = CH.,
Isosafrole
CHn
CH,,
Ethylene Oxides
63
-------
TABLE 7. (Continued)
HETERCYCLICS
N-H
Pyrrole Thiophene Tetrahydrofuran Pyridine
Indole
CHLORINATED HYDROCARBONS
Cl
1 ,2-dichlorobenzene
Hexachlorobenzene
o
C-C1,
CH( ( ) >C1
DDT
ORGANIC ACIDS
Organic Acids - carboxylic
^ ^*
O
COOH
Benzoic Acid
H3C- 0 - CHCOOH
-------
TABLE 7. (Continued)
Organic Acids - sulfonic
^ "N
o
S03H
p-Toluenesulfonic Acid
S03H
©
m-Nitrobenzenesulfonic Acid
NITRILES
N
Acetonitrile
n-Valeronitrile
.Benzonitrile
o.
CH3< ( ) >C=N
p-Tolunitrile
ORGANOMETALLIC COMPOUNDS
CH0
-
CH2 CH3
Tetraethyl Lead
CH,
\j
-L-
OH
CH,
Cacodylic Acid
CH3-Hg-Cl
Methylmercuric Chloride
O
>-Hg- Cl
Phenyl Mercuric Chloride
65
-------
TABLE 7. (Continued)
PHENOLS
OH OH OH
(o) (oL3 ci(f
^^^ Cl ^\.
5)"
X^ Cl
Cl
Phenol m-Cresol Pentachlorophenol
INORGANIC ACIDS
Sulfuric Acid
Nitric Acid
Hydrochloric Acid
Phosphoric Acid
HEAVY METAL SALTS AND COMPLEXES
Chromium Hydroxide
Zinc Cyanide
Cadmium Chloride
Nickel Cyanide
INORGANIC BASES
Sodium Hydroxide
Potassium Hydroxide
Calcium Hydroxide
HNO-,
HC1
Cr(OH),
2
ZnCCN),
Cd C12
Ni(CN),
NaOH
KOH
Ca(OH),
66
-------
TABLE 7. (Continued)
INORGANIC SALTS
Sodium Chloride NaCl
Magnesium Sulfate MgSO,
Calcium Bisulfite Ca(HSO,)2
Potassium Nitrate KNO-
67
-------
the carbonyl group, thus, the carbonyl groups appear in the "middle" of the
compound.
Aldehydes and ketones are polar compounds. The lower ones are soluble
in water and in organic solvents such as ethanol and ether. Aldehydes and
ketones containing more than 5 carbon atoms are not soluble in water. In
general, aldehydes are more reactive with bases and more readily oxidized
than ketones.
Aliphatic/Aromatic Hydrocarbons—
Hydrocarbons are compounds that contain carbon and hydrogen as the basic
structural part of the molecule. Examples of hydrocarbons are methane,
ethane, acetylene, benzene, n-hexane, and toluene. Many hydrocarbons are
used as organic solvents, and have been found in leachate from landfills
(Shuckrow et al, 1980). In general, they can be volatile, especially the
lower molecular weight compounds, and have been low water solubilities. In
general, the liquid hydrocarbons are lighter than water and will form a layer
on the surface of water. This is especially true of the more prevalent
solvents. Hydrocarbons are not expected to be particularly reactive under
conditions in landfills, although hydrocarbons containing a carbon-carbon
double bond may be subject to addition at that bond under certain conditions.
For example, the double bond may hydrate under acidic conditions to form an
alcohol.
Amines and Amides—
Amines and amides are nitrogen-containing organic compounds. Amines
contain nitrogen that is attached to one, two, or three aliphatic and
aromatic groups, thus, they have the general formula RNH_, R-NH, and R.N,
where R represents an aliphatic or aromatic group. Examples of amines are
aniline, p-phenylene- diamine, and benzidine. Amines are polar compounds,
can form hydrogen bonds with water, and are basic. Higher molecular weight
amines (greater than six carbon atoms) are not soluble in water, but the
lower molecular weight compounds are soluble at least to some extent. Amines
are soluble in less polar solvents such as ether, alcohol, and benzene.
Amides contain nitrogen that is attached to a carbonyl group (C=0) .
They have the general formula of R-CONH-, R-CONH-R, and R-CON-R_, where R may
be an aliphatic or aromatic group. Amides, like amines, are polar compounds
and are capable of strong hydrogen bonding. Amides containing up to five or
six carbon atoms are soluble in water. Higher molecular weight amides are
generally not water soluble.
Ethers and Epoxides—
Ethers consist of two compounds (aromatic or aliphatic) that are
attached by an oxygen atom; thus, ethers have the general structure R-O-R,
where R is either an aromatic or aliphatic group. Ethers are somewhat
soluble in water (comparable to the solubility of alcohols) and are compar-
atively unreactive compounds. Ethers are stable toward bases, oxidizing
agents, and reducing agents.
68
-------
Epoxides contain a three-member ring consisting of two carbon atoms and
one oxygen atom. They are grouped with ethers because they have the R-O-R
linkage, but their ring structure makes them highly rea.ctive, particularly to
acids and bases.
Heterocyclics—
Heterocyclic compounds are single or multi-ring compounds with the
ring(s) containing more than one kind of atom. In addition to carbon,
heterocyclic rings often contain sulfur, nitrogen, or oxygen. These rings
can either be aliphatic or aromatic. Five-membered aromatic heterocyclics
are fairly reactive. Of the six-membered rings, pyridine is the most common;
pyridine is a weak base.
Halogenated Hydrocarbons—
Halogenated hydrocarbons are aliphatic or aromatic compounds that also
contain halogens, such as chloride or bromide. In general, the more halogen
atoms present, the less water soluble the compound is. These compounds, as a
class, are unable to form hydrogen bonds and are stable.
Organic Acids and Acid Chlorides—
The two major classes of organic acids are carboxylic and sulfonic
acids. Carboxylic acids contain a carboxyl group (COOH) attached to an
organic group (aliphatic or aromatic). The lower carboxylic acids are
soluble in water; the higher acids (containing 5 or more carbon atoms) are
insoluble. Carboxylic acids are soluble in less polar solvents such as
ether, alcohol, and benzene. These acids can form hydrogen bonds.
Carboxylic acids containing more than eight carbon atoms are solids.
Sulfonic acids contain sulfur and are more acidic than carboxylic acids. The
sulfur is bonded directly to a carbon atom, and the general formula is
R-SO»H. As a class, these compounds are more soluble in water than any other
organic compounds, but are insoluble in organic solvents such as diethyl
ether, benzene, and carbon disulfide. The SO-H group is often used to make
otherwise insoluble compounds soluble, especially in the dye industry. Both
types of acids form salts with cations.
Acid chlorides are functional derivatives of carboxylic acids; the
hydroxyl group (-OH) of the carboxylic acid has been replaced by chloride
(-C1). An example is acetyl chloride, CH.COC1. Acid chlorides may contain
an aliphatic or aromatic group. Acid chlorides are polar compounds and are
soluble in organic solvents. Only the simpler acid chlorides are soluble in
water.
Nitriles—
Nitriles are organic compounds that contain a cyanide group (C N). Upon
hydrolysis, nitriles form acids. Acetonitrile, a simple nitrile, is a widely
used non-aqueous solvent.
Organometallic Compounds—
Organometallic compounds consist of organic compounds (aliphatic or
aromatic) and a metal such as chromium, cadmium, lithium, iron, cobalt,
nickel, or copper. These compounds play an important role as catalysts in
69
-------
many chemical reactions. Some of the complex organometallic substances such
as hemoglobin or chlorophyll are important biological materials. Organo-
metallics containing arsenic and cadmium are used as.pesticides. Tetraethyl
lead is used as an antiknock agent in gasoline. In general, organometallics
are resistant to degradation under ambient conditions, although arsenicals
are degraded rather quickly to arsine by biological action. Organometallics
such as tetraethyl lead are insoluble in water, but soluble in non-polar
organic solvents.
Phenols—
Phenols are aromatic compounds that have a hydroxyl (-OH) group attached
directly to the aromatic ring. The ring may have other groups attached;
cresols, for example, have an -OH and a -CH3 group attached to the ring.
Most of the phenols are insoluble in water although phenol itself is somewhat
soluble. These compounds are capable of hydrogen bonding, easily oxidized,
and fairly acidic. The lower molecular weight phenols are liquids or low
melting solids. Boiling points tend to be high because of hydrogen bonding.
Organic Esters—
Esters are the products of the reaction of acids with alcohols or
phenols. This reaction may be seen as comparable to the reaction of an
inorganic acid and inorganic base to form a salt. Low molecular weight
esters generally have a pleasant odor and are relatively unreactive. They
are not particularly soluble in water, but some, such as ethyl acetate are
good solvents. Esters occur naturally in animal and vegetable fats and
ordinary soap is made from fatty acid esters and sodium hydroxide.
Inorganic Acids—
Inorganic acids are compounds which produce H+ groups when they
dissociate. These compounds are readily soluble in water and will react with
bases to form salts.
Heavy Metal Salts and Complexes—
Heavy metals encompass a wide range of elements, with the environ-
mentally important ones being cadmium, chromium, copper, lead, mercury,
nickel, silver, and zinc. Under the conditions normally found in groundwater
systems, these, metals can form complexes with a number of inorganic and
organic compounds including SO ~2 CN~, OH~, and EDTA. The pH of the system
will control the solubility and the chemical form of the complexes.
Inorganic Bases—
Inorganic bases are compounds which produce an OH~ group when they
dissociate. These compounds are soluble in water and will react with
inorganic acids to form salts.
Inorganic Salts—
Salts are compounds consisting of metals (such as sodium, calcium, and
potassium) combined with various non-metals (such as chloride, sulfate, and
nitrate). The solubility of these compounds will vary with the constituent
compounds. For example, most salts of Group I elements (lithium, sodium,
potassium, rubidium, and cesium) are quite soluble in water.
70
-------
Compatibility Index
From the literature and our analysis, there are two general aspects of
grouts that may be affected by chemicals: set time of the grout and its
durability once it is set. The numerical codes developed for the chemical
compatibility matrices define the effect of the chemical classes on grout set
time:
1. No significant effect
2. Increase set time (lengthen or prevent from setting)
3. Decrease set time.
The alphabetic codes relate to the durability of the grout (after setting) in
the presence of chemicals:
a. No significant effect
b. Increase durability
c. Decrease durability (destructive action begins within a short time
period)
d. Decrease durability (destructive action occurs over a long time
period).
A question mark on the matrices indicates where information is not available
for one or the other of the codes, or both.
It should be noted that the matrix codes only address changes in set
time or durability as a result of exposure to chemicals. The codes do not
address the specific mechanisms that lead to changes in set time or
durability nor do they address mechanisms other than chemical action. For
example, bacterial action can destroy some grouts, thus, the bacteria affect
the durability of these grouts; this form of grout destruction is not
included in the matrix.
Compatibility Matrices
Figure 5 presents a matrix defining the interactions between grouts and
six general chemical classes: acids, bases, polar solvents, nonpolar
solvents, heavy metals, and salts. The chemical groups that are included
under each of these general classes are shown in Table 8. The data contained
in this matrix were derived from both specific chemical information and
general information regarding classes of chemicals. Much of the available
data refer to the effect of general classes, such as salts or solvents, and
not specific chemicals. These data were derived from available literature
and conversations with industry and persons knowledgeable about grouts.
Predictions or estimations of grout/chemical interactions are not included in
this matrix.
71
-------
Figure 5. Interactions Between Grouts and Generic Chemical Classes
Grout Type
Chemical Group
3
a
Portland Cement
•o
e
a
£
>
0
o
u
Polymers
i
I
o
J
i
|
O
<••
I
X
o
a
UJ
I
"5
a.
Acid
?a§
1d
1a
?c
3a
2c
2c
1d
?a§
?a§
?a
1a
?d
2c
3d
?d
?d
2c
?a
?d
Heavy Metals
?d
2c
2a
?d
2c
3?
2?
?a
Non-Polar Solvent
?d
2d
2d
?d
?a
?d
?a
2a
?d
?d
Polar Solvent
?d
2c
2?
?d
?a
3a
3a
2?
?d
Inorganic Salts
?d
2c
2a
2d
?d*
3?
3d'
3a
?d
?a
?a
?a
KEY: Compatibility Index
Effect on Set Time
1 No significant effect
2 Increase in set time (lengthen or prevent from setting)
3 Decrease in set time
Effect on Durability
a No significant effect
b Increase durability
c Decrease durability (destructive action begins within
a short time period)
d Decrease durability (destructive action occurs over a
long time period)
* Except sulfates, which are ?c
t Except KOH and NaOH, which are 1d
^ Except heavy metal salts which are 2
§ Non-oxidizing
* Modified bentonite is d
? Data Unavailable -,„
-------
Table 8. Constituents of the General Chemical Classes
• Acids
- Inorganic Acids
- Organic Acids and Acid Chlorides
• Bases
- Inorganic Bases
- Amides and Amines
• Heavy Metals
- Organometallics
- Heavy Metal Salts and Complexes
• Polar Solvents
- Alcohols and Glycols
- Aldehydes and Ketones
- Ethers and Epoxides
- Nitriles
- Hetrocyclics
• Non-Polar Solvents
- Aliphatic and Aromatic Hydrocarbons
- Chlorinated Hydrocarbons
• Inorganic Salts
73
-------
Figure 6 presents a more detailed matrix, where the chemical groups are
more specific. Sixteen chemical classes are represented and have been
divided into two categories: organic and inorganic. This matrix provides a
more detailed understanding of the types of chemicals that may have a
detrimental effect on grouts. The chemical classes presented in this matrix
were defined in the previous section on chemical groups. Like the general
matrix, Figure 6 does not contain any predictions or estimations of chemical/
grout interactions. Only direct compatibility data are presented.
PREDICTED COMPATIBILITY OF GROUT WITH CLASSES OF CHEMICALS
In order to fill the information gaps, a matrix was developed that
contains predictions or estimates of grout/chemical interactions. These
predictions are based on the chemical structure, reaction theory, and
estimated behavior of grouts in the presence of the various chemical groups.
In order to make these estimations, a number of assumptions were made; these
assumptions are described in detail below.
For the purposes of this report, typical landfill leachate is defined as
having the following properties:
• High salt content
• Organic compounds will be approximately 1% in the leachate, although
some may be in the ppm range
• Metal ions individually will not exceed 1%
• The pH will range from moderately acidic (pH 3) to moderately basic
(pH 11).
The groundwater may be considered a multicomponent dilute solution. It
will be further assumed that interactions between the components do not
occur, but that interactions between the grout and each of the separate
components may occur. These reactions will be considered to be free of
interference from the other components. Because groundwater has no turbu-
lence and is slow moving, the groundwater can be thought of as essentially
static in nature. In such cases, it is possible that chemicals which are
insoluble in water may form a layer either on top or on the bottom of the
groundwater depending on their densities. Although these layers would be
expected to be thin due to the low concentration of contaminants, the point
of contact with the grout would be would be essentially "pure" contaminant,
rather than a very dilute solution. This point of contact may then represent
a special case and be a point at which an incompatibility may result in a
critical weakening of the grouted structure. For example, if a thin layer of
organic solvents formed on top of the groundwater and the grout was either
solubilized or reacted with these solvents, the structure would be breached
at that point. Once breached, the solvents could then penetrate more deeply
resulting in a general weakening or alteration of the grout matrix.
74
-------
Figure 6. interactions Between Grouts and Specific Chemical Groups
^v Grout Type
Chemical Group N.
Organic Compounds
Alcohols and Glycols
Aldehydes and Ketones
Aliphatic and Aromatic
Hydrocarbons
Amides and Amines
Chlorinated Hydrocarbons
Ethers and Epoxides
Heterocyclics
Nitriles
Organic Acids and Acid
Chlorides
Organometallics
Phenols
Organic Esters
Inorganic Compounds
Heavy Metal Salts and
Complexes
Inorganic Acids
Inorganic Bases
Inorganic Salts
Bitumen
?a
?d"
?d
?
?d
?
?
?
?a
?
?d
?
Portland Cement
I
?d
7
2a
?
2d
7
?
?
1d
?
1d
7
>
1
o
1
?d
?
2?
?
2d
7
?
?
1d
?
?
?
Clay (Bentonite)
?d
?d
?d
?
?
?
?d
?
?d
7
?d
?
Clay-Cement
?d
?
?
?
?
?
?
?
?d
?
?d
?
Silicate
?
?
?
?
?
?
?
?
?a
?
?
1a
Polymers
Acrylamide
?d
?a
?a
7
?a
?a
?a
?
2a
?
?
?
?d
?as^
?a
?d
2c
1d
la
2c
2a
1a
1at
2a
?d
?c"
?c»-
2d
2c
?c
?d
?d*
3?
3a
2c
3?
2?
2c
3d
3d
Phenolic
?
3a
W*
?
?d
?
?
?
?a
?
2a
•?
?
?a§
?d
3a#
Urethane
3a
?d
?a
3?
?a
?a
?
?
2a
?
?c
?
?
2c
?d
?d
Urea-formaldehyde
?
?
2a
?
2a
?d
?
7
1a
?
?
?
?a
1d
2c
?a
§
a
1U
?a
?
?d
?
?d
?
?
7
?d
?
?
?
?
?aS
?a
?a
Polyester
?a
?
?d
?
?d
?
?
?
?d
?
?
?
?
?a*
?d
?a
KEY: Compatibility Index
Effect on Set Time
1 No significant effect
2 Increase in set time (lengthen or prevent from setting)
3 Decrease in set time
Effect on Durability
a No significant effect
b Increase durability
c Decrease durability (destructive action begins within
a short time period)
d Decrease durability (destructive action occurs over a
long time period)
* Except sulfates, which are ?c
t Except KoH and NaOH, which are 1d
t Low molecular weight polymers only
§ Non-oxidizing
v Non-oxidizing, except HF
G Except concentrated acids
• Except aldehydes which are 1a
# Except bleaches which are 3d
* For modified bentonites, ?d
? Data Unavailable
75
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One further assumption is made with respect to organic polymer grouts.
The reaction of the organic polymer grout and its curing agent is not
complete and a quantity of the unreacted polymer will remain. This
assumption reflects the fact that even under highly controlled conditions,
the stoichiometry of such reactions is ill-defined, and in a field situation,
the conditions are not only uncontrolled, but many times are undefined. The
unreacted resins will be assumed to be trapped in the polymer matrix with the
reactive sites randomly oriented. These resins will appear on the surface as
well as the interior of the grouting wall and will be available for reaction
with chemicals brought into contact with the surface. A certain amount of
migration from the interior to the exterior of the matrix is also expected to
take place. Migration is thought to occur slowly, so the possibility of
reactions between the grouted structure and the surroundings may continue for
an extended period of time. The predicted compatibilities, though, are made
for the totally reacted grout and do not take into account exposure of
unreacted resins to the various chemicals.
Based on these assumptions, a number of estimates of grout/chemical
compatibilities were made for the silicate and organic polymer grouts. The
other grout types were not evaluated due to the lack of knowledge of their
actual solidification chemistry. Predictions were made only where no data
currently exists. The predictions are only indicative based on reaction
chemistry. These are the effects a chemical might have on a grout and not
the true field effect. These predictions are presented in Figure 7 and are
discussed in the following sections.
Silicate Grouts
As discussed in Section 3, silicate grouts are composed of polymetric
chains of silicon-oxygen linkages with cations of alkali metals dispersed
along the chain and bonded to the oxygen. The alkali metals can be replaced
by divalent ions such as calcium and magnesium. The divalent ion permits
bonding with two oxygens, thus, a cross-linked polymeric structure is formed
(Hurley and Thornburn 1971). Because silica gel is a fairly efficient ion
exchanger, a landfill containing a high concentration of soluble salts may
cause either one of two effects:
1. Decrease durability by exchanging monovalent ions for divalent
ones, thus decreasing the cross-linking
2. Increase durability by exchanging divalent ions for monovalent ones,
thus increasing the cross-linking.
Ferric iron is reported to be an inhibitor for silicate grout, stopping
or slowing down gelation time. The resultant gel is weak (Office of the
Chief of Engineers 1973). The mechanism for the inhibiting effect may be due
in part to the tendency of aqueous ferric iron to hydrolyze and/or form
complexes (Cotton and Wilkinson 1972) thereby removing or bonding with the
water molecules from the grouting mixture.
76
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Figure 7. Predicted Grout Compatibilities
Organic Compounds
Alcohols and Glycols
Aldehydes and Ketones
Aliphatic and Aromatic
Hydrocarbons
Amides and Amines
Chlorinated Hydrocarbons
Ethers and Epoxides
Heterocyclics
Nitrites
Organic Acids and Acid
Chlorides
Organometallics
Phenols
Organic Esters
Inorganic Compounds
Heavy Metal Salts and
Complexes
Inorganic Acids
Inorganic Bases
Inorganic Salts
Silicate
la
la
1d
3a
1d
la
1d
1a
1-
1a
la
-
—a
-
—
-d
Polymers
Acrylamide
1-
7
1-
3d
1
1-
1-
3?
-
3a
la
?
-?
-
—
-
Phenolic
3b
-
?-
3b
?-
1a
la
la
3-
?
-
?
?
2-
3-
-
«
e
a
e
D
-
1-
1-
_a
1-
1-
1a
1a
2-
—
2-
?
3"?
-
•>—
•>-
Urea-formaldehyde
1?
?
-
1a
—
?_
1a
1a
-
1a
la
?
?-
-
—
?_
>
X
o
a
tu
1-
1a
1-
1a
1-
1a
1a
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?_
la
la
?
•
3?
1-
?-
?-
Polyester
1-
1a
1-
3a
1-
1a
la
la
1-
3»?
1?
1d
3?
1-
1-
3'-
KEY: Compatibility Index
Effect on Set Time
1 No significant effect
2 Increase in set time (lengthen or prevent from setting)
3 Decrease in set time
Effect on Durability
a No significant effect
b Increase durability
c Decrease durability (destructive action begins within
a short time period)
d Decrease durability (destructive action occurs over a
long time period)
* If metal salts that are accelerators
^ If metal is capable of acting as an accelerator
-? "Determination of compatibility could not be made
based on available information
77
-------
The presence of organic contaminants has been reported to have the
potential for completely preventing the settings of some gels (Hurley and
Thornburn 1971). No further details were given. Because each individual
organic chemical is present at a concentration of 1% or less, it is assumed
that the effect on the set time or durability will be negligible. However,
the total concentration of organics may be significant and if the presence
of known organic inhibitors such as hydroquinone or accelerators such as
alcohols or glycols is sufficiently large, set times and durability may be
adversely affected. Catalysts in general are present in mixtures at a 0.1 to
2 percent concentration.
Acrylamide Grouts
Acrylamide grouts, formed by reacting a mixture of two organic monomers
with a cross-linking agent are expected to be resistant to the deleterious
effects of most organic chemicals. However, other chemicals present during
the reaction period that alter the monomer cross-linking agent ratio may
result in a weaker, softer grout. The presence of metal ions in the landfill
may inhibit setting of acrylamide grout. The activator, triethanolamine, is
reported to be metal sensitive (Clarke 1982). Because the gel time is
dependent on the concentration of the catalyst, activator-inhibitor any
interference with these chemicals will result in a change in the process
(Clarke 1982).
The accelerators are reported to be organic compounds such as
nitrilotrispropionamide, dimethylaminopropionitrile and triethanolamine. It
is expected, therefore, that similar compounds, e.g., nitriles, amides, and
amines, present in the landfill at concentrations of 1% will have an
accelerating effect on the gel time of the grout. Unreacted monomer trapped
in the gel matrix may be expected to react with components in the landfill
and these reactions would be characteristic of the reactive site on the
molecule, in this case, the amide and the double bond. Amides in general
will undergo hydrolysis under either acidic or basic conditions.
Addition to the double bond in the amide is a common reaction and under
acidic conditions double bonds undergo hydration to form alcohols. Chlorine
and bromine will react with double bonds to form the halogenated compounds in
solvents such as carbon tetrachloride. Thus, an organic solvent layer
containing halogens in contact with the grout could result in halogenation of
the unreacted monomer at the surface. If these reactions result in soluble
compounds in either the aqueous or organic layers, the durability of the
grout wall may be decreased. This type of reaction would be expected to
occur slowly. These reactions may also alter the permeability of the grouted
mass in the short term by providing "holes" caused by the solubilization of
the reaction products.
Phenolic Grouts
The most common grout in this class results from the polymerization of
resorcinol and formaldehyde. In this reaction, the function of the catalyst
is to control the pH (Clarke 1982). A pH of slightly above 9 produces the
78
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shortest setting time. The most commonly used catalyst is sodium hydroxide
but many other materials may function as catalysts (Clarke 1982). In this
case, any class of compound that is acidic will contribute to the lengthening
of the set time and thus weaken the gel; basic compounds will contribute to a
shorter gel time and a stronger gel.
Unreacted monomer contains reactive hydroxyl groups (resorcinol) and an
aldehyde group (formaldehyde). Under basic conditions, formaldehyde may
react to form methanol and a formate salt. This reaction would result in
water soluble products. The solubility of these compounds would be expected
to produce a gradual weakening of the grout wall. Contact with organic
solvents where carbon tetrachloride is present could result in solubilization
of the residual resorcinol, because of its great solubility in that medium.
Resorcinol is also soluble in water, alcohol, ether, and acetone (Weast
1972). Formaldehyde is extremely soluble in either an aqueous layer con-
taining acetone or an organic layer containing ether and/or benzene. Thus,
prolonged contact with either an aqueous layer containing acetone or an
organic layer containing ether and/or benzene could also result in a
weakening of the grout by solubilization of the trapped monomers.
Aqueous hydroxides will convert phenols into their respective water
soluble phenolic salts. Phenols also form complexes with ferric chloride
(Morrison and Boyd 1969).
Urethane Grouts
Urethane grouts are formed from the reaction of isocyanates and polyols
where the monomer cross-links with itself. Catalysts are tertiary amines and
tin salts. Isocyanate groups will also react with carboxylic groups, hydrogen
and nitrogen ions, and water (Clarke 1982). Toluene diisocyanate (TDl) the
monomer, will polymerize in the presence of water. Unreacted isocyanate
groups trapped in the grout matrix are expected to be available for chemical
reaction.
The isocyanate moiety is highly reactive and will react with a host of
organic compounds. The aromatic isocyanates in general are more reactive
than their aliphatic counterparts (Saunders and Frisch 1962). Because of
this reactivity, unreacted isocyanate that is trapped at the surface of the
grouted mass may be expected to react with the majority of the substances
present in the landfill. If these reaction products are water soluble, a
weakening in the grouted structure may occur. For example, the reaction of
alcohols with isocyanates produces a class of compounds called carbonates
(these are also urethanes) (Saunders and Frisch 1962). The water solubility
of these compounds varies from insoluble to very soluble with many being only
slightly soluble in water. While it is not possible to generalize an effect
of this reaction, the potential exists for extremely soluble reaction
products. Additionally, if enough of the isocyanate reacts with the ground-
water contaminants, the grout may not set.
Many metallic compounds have been found to be catalysts for the
isocyanate-hydroxyl reaction. Examples include: bismith, lead, tin, strong
79
-------
bases, titanium, iron, antimony, uranium, cadmium, aluminum, mercury, zinc,
and nickel (Saunders and Frisch 1962). Since many of these metals are
commonly found in leachate from landfills, their potential catalytic effect
cannot be ignored.
Once the grout has set, the fully reacted species are expected to be
resistant to the effects of a great majority of the chemicals found in
landfills.
Urea-Formaldehyde Grouts
Urea-formaldehyde grouts will set up only under acidic conditions
(Clarke 1982). Once properly formed, the urea- formaldehyde grouts are
impervious to most chemicals. However, free formaldelyde is usually present
to some degree in the grout matrix and surface contact may result in a
leaching of the free formaldehyde by the aqueous media, since formaldehyde is
quite soluble in water. The presence of methanol enhances the solubility of
formaldehyde in water (Meyer 1979). The leaching of formaldehyde from the
matrix surface may result in a migration of free formaldehyde from the
interior matrix to the surface and a gradual weakening of the grout.
Epoxy Resin Grouts
The most important raw materials for epoxy resins are epichlorohydrin
and bisphenol-A. These chemicals are reacted in the presence of a caustic
soda solution, generally with a large excess of epichlorohydrin. This excess
produces epoxide-terminated resin molecules (Scheldknecht and Skeist 1977).
Prior to injection, the resin is then cross-linked with either reactive
curing agents, such as tertiary amines combined with reactive primary and
secondary amines, or through homopolymerization by use of catalysts
(Scheldknecht and Sheist 1977). The epoxy resins are soluble in ketones,
esters, and glycol ethers which are used as diluents. Aromatic hydrocarbons
and alcohols are sufficiently compatible to also function as diluents.
Reactive diluents such as butyl glycidyl ether, cresyl glycidyl ether, phenyl
glycidyl ether, and styrene oxide decrease viscosity but also reduce the
cross-linking. Thus, the water resistance of the polymer is lowered somewhat
(Scheldknecht and Sheist 1977).
The chemical resistance of epoxy grouts is, with the exception of
oxidizing acids, reported to be excellent (Scheldknecht and Sheist 1977). It
would appear, therefore, that uncured resin trapped in the cross-linked
matrix would be subject to the solubilization effects of ketones, esters,
ethers, aromatic hydrocarbons, and alcohols.
The curing of epoxy resins is reported to be accelerated by metallic
driers such as cobalt naphthenate (Scheldknecht and Sheist 1977). Therefore,
any metallic driers or similar compounds present in the landfill have the
potential to accelerate the curing process.
80
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Polyester Resin and Grouts
Polyester resins are condensation products of unsaturated diacids and
dialcohols. Because these products are quite viscous, they are often mixed
with a diluent such as styrene. The polymerization process is catalyzed by a
peroxide which generates free radicals in the presence of an accelerator such
as cobalt, manganese, and vanadium salts; tertiary amines; mercaptans; or
quaternary ammonium salts (Tallard and Caron 1977a). Once polymerized, the
grout would be expected to be relatively impervious to most components of a
landfill.
However, during the polymerization process, the presence of excess
accelerator as components of landfill leachates may have an adverse effect on
the grout by decreasing the set time. The polymerization process normally
gives off considerable amounts of heat and if this process were speeded up,
more heat would be generated (Tallard and Caron 1977a). In such cases, the
heat would be transferred to the immediate surrounding area. Since many
chemical reactions are enhanced in the presence of heat, the unreacted
components of the grouting mixture may undergo reactions with chemicals in
the leachate rather than continue the polymerization process. For example,
depending upon the temperatures generated, halogen additions to the double
bond of any of the components of the grouting mixture may occur. Water may
also add to the double bonds, forming alcohols. The diluent, styrene, may
dimerize instead of co-polymerizing with the reactants. In such cases, the
formation of the simple ester may not be inhibited, but the polyester
formation may be inhibited by competitive reactions, or the final polymer may
be altered in structure because other parts of the molecule (i.e., the double
bonds) may have reacted with components of the leachate. In such cases, the
durability of the grout is unpredictable, and thus it may be inadvisable to
use.
81
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SECTION 7
GROUT COMPATIBILITY TESTING PROCEDURES
In order to establish the compatibility of compounds contained in
groundwater with the materials used in the grouting, a series of laboratory
tests must be performed. The two grout properties that must be investigated
are the permeability of the grouted mass, and the set time of grout in the
contaminated environment. There are as yet no established procedures for
determining the effect that various chemicals would have on these character-
istics. An evaluation of currently utilized grout and soil test methods,
however, has identified several potential procedures.
The following sections outline the testing procedures that are
applicable to determining grout/chemical compatibility.
PERMEABILITY OF GROUTED SAND
The effect that leachate will have on the ability of a grouted mass to
contain leachate can be measured in the laboratory. By bringing chemicals at
representative concentration levels into contact with a sample of the grouted
material within a permeameter, their rate of movement through the grouted
sample can be measured. By comparing this rate with that obtained with
water, the change in permeability can be determined.
Laboratory determinations of permeability are based on Darcy1s Law.
This expression relates the flow of a liquid through a porous medium with the
hydraulic gradient, permeability, and cross-sectional area of the flow, as
follows (Spangler and Handy 1973):
Q = kiA
where:
o
Q = flow rate (units: [length] /time)
i = hydraulic gradient
A = cross-sectional area of the flow
k = coefficient of permeability (units: length/time)
In order to calculate the coefficient of permeability (k) in the labora-
tory, Q, i, and A are measured. The coefficient of permeability (often
termed permeability) will depend on the size and shape of the soil grains,
83
Receding page blank
-------
the void ratio of the sample, the shape and arrangement of the voids, and the
sample saturation (Office of the Chief of Engineers 1970).
Permeability computed on the basis of Darcy's Law is limited to condi-
tions of laminar flow and complete saturation of the voids. Under turbulent
flow conditions, the flow is no longer proportional to the first power of the
hydraulic gradient. Under conditions of incomplete saturation, the flow is
in a transient state and is time dependent (Office of the Chief of Engineers
1970). Thus, all permeability testing procedures must be carried out under
the Darcy conditions of flow.
There are a number of permeability test methods that have been developed
for use in low permeability soils and/or grouted samples. These methods
have been used to determined the effect of leachate on soil or soil bentonite
mixtures. These methods, and the sample preparation procedures used, are
discussed in the following subsections.
Permeameters
To measure permeability in the laboratory while observing the limits
established by Darcy's Law, two types of tests have been developed:
constant-head and variable head. These tests can be performed by a variety
of testing equipment, depending on the samples characteristics. The three
basic categories of test equipment are as follows:
• Fixed wall permeameter cells
• Triaxial permeameter cells
• Consolidation permeameter cells (Office of the Chief of Engineers
1970).
Permeability tests on samples with low permeability, such as grouted
formations, must be performed carefully if they are to be accurate. Leaks,
losses of volatiles, or channelized flow between the permeameter and the
sample can greatly effect permeability values (Anderson and Brown 1981). The
following sections outline test procedures and equipment that have been
developed to overcome these potential problems as well as the limitations of
each procedure.
Permeability Tests: Constant Head and Variable Head—
The difference between these types of permeability tests, constant head
and variable head, is the way in which the amount of liquid that flows
through the sample is measured; thus the procedures used for calculating
permeability are different. For example, in the constant head test, the
hydraulic gradient "i" is held constant throughout the test. Figure 8
illustrates a simple constant head permeameter.
84
-------
Screen
Graduate (q)
Source: Office of the Chief of Engineers, 1970
Figure 8. Constant Head Permeameter
85
-------
By utilizing a variation of Darcy's Law, permeability can be calculated
as follows:
hAt
where :
k = coefficient
q = quantity of flow
L = length of sample
h = head of liquid
A = cross-sectional area of sample
t = time interval of test (Office of the Chief of Engineers 1970) .
This type of test is usually used for determining permeability in only
coarse grained soils with a k value of greater than 10~ cm/ sec because of
the small heads that can be applied (unless excess pressure is applied
through the use of compressed gases) (Office of the Chief of Engineers 1970,
Olson and Daniel 1981). The major advantages of this type of test are the
simplicity of data interpretation, and the fact that the use of a constant
head minimizes confusion due to the changing volume of air filled voids when
the soil is not saturated (Olson and Daniel 1981).
For samples with a lower permeability, a variable head test is usually
used (Spangler and Handy 1973). In this procedure, the head is allowed to
decrease over the course of test as liquid moves through the sample. Figure
9 illustrates a simple variable head test apparatus. The permeability of the
sample is calculated from the following variation of Darcy's Law:
T h
where :
L = length of sample
t = time interval of test
hQ = height of liquid in the standpipe at the beginning of the test
he = height of liquid in the standpipe at the end of the test.
This test procedure is usually used on fine grained samples with k
values less than 10~ cm/sec (Office of the Chief of Engineers 1970). The
advantage of this test is that small flows can be measured more easily
(Spangler and Handy 1973).
To reduce the time necessary to run these tests, the flow rates can be
increased by superimposing a gas pressure (such as air) on top of the liquid
86
-------
\' r
• Liquid
•Sample
Screen
Source: Office of the Chief of Engineers, 1970
Figure 9. Variable Head Permeameter
87
-------
A pressure of 4-5 pounds per square inch (psi) is commonly utilized for soil
permeability testing while up to 40 psi can be used for grouted soils.* °
While this can significantly reduce the time that these tests take, it can
also present several potential problems. At elevated pressures, the liquid
can become saturated with the gas in accordance with Henry's Law (Olson and
Daniel 1981). Thus, as the liquid flows through the sample and the pressure
drops, there may be a tendency for gas bubbles to develop in the sample.
This can have a significant effect on the sample's permeability. Also, when
using gas pressure in the variable head test, a point is reached where the
gas pressure will be significantly higher than the pressure due to the
liquid, and the test becomes just a constant head test.
Fixed Wall Permeameter Cells—
Fixed-wall permeameter cells are the simplest type of permeameters that
can be utilized. In this type of permeameter, the sample is contained in a
fixed wall cylinder supported by a porous disk or screen. To prevent
swelling of the sample, a plate can be clamped against the sample's upper
surface (Office of the Chief of Engineers 1970, Olson and Daniel 1981). This
apparatus can be either a constant head or variable head system as illus-
trated in Figure 10. The advantage of this technique is that the apparatus
is readily available and easy to use. The disadvantage is that improper
placement of the sample in the permeameter can cause leakage between the
sample and the permeameter wall. This will invalidate any measurements made
with the sample (Zimmie 1981). General procedures for performing this test
can be found in Appendix VII of Laboratory Soils Testing (Office of the Chief
of Engineers 1970). This type of permeameter has been used by Northwestern
University to measure permeability of grouted sand samples. In these tests,
the permeameter cell was the mold in which the sand sample was grouted. This
approach eliminates problems that could result from mishandling of the sample
during its removal from the mold and insertion into a permeameter.
The American Petroleum Institute (API) also recommends the use of a
fixed wall perraeameter to test the permeability of cement (API 1982). In
this test, the sample is first saturated by drawing water through it with a
vacuum. A pressure of 200 psi is then applied to the feed solution and a
backpressure of 20 psi is applied to the solution that has permeated the
sample. This results in an effective pressure of 180 psi being utilized to
force the feed solution through the sample.
Consolidation Permeameter Cells—
Consolidation permeameter cells are similar to fixed wall cells except a
load can be placed onto the top of the sample (see Figure 11). The load
*Hale, G. USAE Waterways Experimental Station, Vicksburg, MS. Personal
communication with G. Hunt, August 30, 1982.
Ayers, J. GZA Corp, Newton Upper Falls, MA. Personal communication with G.
Hunt, September 3, 1982.
Krizek, R. Northwestern University, Chicago, IL. Personal communication
with G. Hunt, October 11, 1982.
88
-------
Overhead Deaired Distilled Water Supply
I I
. Manometer Board
Screen
Over
Openings
Perforated Disk
Covered with Screen
i
SWiSSft
Sfjji&i&S:
"'""V
f
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I
*
>nstBnt«— *
aad Tank
neter
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.
h
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Valve A .
*)L
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ir _ Umm^ »*!—*—.-
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a
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*
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flow 1
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J_L
-
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-
-
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Valve
—
•^
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—
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-•
••
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-
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Screen
-Valve
H A ^ B
II
•"•*•*•*•'•
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-------
NOTE: Valve Between Deaired Distilled Water
Jug and Consolidation Apparatus Should
Be Closed During the Permeability Test.
Dial Indicator
Thermometer
n
Source: Office of the Chief of Engineers, 1970
Figure 11. Variable Head Consolidation Permeameter
90
-------
placed upon the sample will cause an effective seal to be formed between the
sample and the walls of the permeameter. This test is best used for undis-
turbed soil samples. With this type of apparatus, permeabilities as low as
10 cm/sec have been measured (Olson and Daniel 1981).
Procedures for performing this test can be found in Appendix VII of
Laboratory Soils Testing (Office of the Chief of Engineers 1970).
Triaxial Permeameter Cells—
In a triaxial permeameter cell, a cylindrical sample is confined in a
rubber membrane and subjected to an external hydrostatic pressure during the
permeability test. This prevents leaks and sideflow along the sides of the
specimen (Zimmie 1981, Office of the Chief of Engineers 1970). An example of
this type of permeameter is shown in Figure 12.
Another advantage of this system is that through an increase in pressure
on the sample, gas bubbles contained within the sample can be dissolved in
the pore fluid, thus leaving the sample totally saturated. This is accom-
plished by simultaneously increasing the chamber pressure and the pressure on
the pore fluid, while maintaining the same effective stress on the sample
(Zimmie 1981). The pressure applied to the pore fluid is known as the back-
pressure and is typically about 40 psi* for soil samples.
The advantages of using this type of permeameter are that it greatly
reduces the chance of liquid flow around the sample, and allows for complete
saturation of the sample. The disadvantage is that it is a relatively
complex procedure requiring expensive equipment. Several laboratories
recommended the use of triaxial peraeameters because of their ability to
reduce short circuiting of the leachate* .
It should be noted that backpressure does not have to be utilized in
performing triaxial permeability tests. Tallard and Caron (1977b) utilized a
modified triaxial permeameter to deterime the permeability of grouted sand
(see Figure 13). In this system, the grouted sand sample is covered with a
latex membrane and placed in the permeameter. Water, under a pressure of
14 psi, is then drawn through the sample by a vacuum. When the water has
saturated the sample, the vacuum is released and the test is run with a
confining pressure of 21.8 psi on the membrane. This system has been
utilized to study a wide range of grouts including silicates, lignochromes,
polyacrylamides, phenoplasts, and bentonite.
*Schwartz, G. ECI, Pittsburgh, PA. Personal communication with G. Hunt,
August 20, 1982.
Hentz, D. Federal Bentonite Belle Fourche, SD. Personal communication with
G. Hunt, August 19, 1982.
91
-------
Differential Pressure Gage (Optional)
Dial Indicator
Back Pressure Gage
Vacuum Line (Optional)
for Deairing Lines
Valve J
Valve M
Back
Pressure
Regulator
Vacuum Line (Optional)
for Deairing Lines
, Valve L
Differentia! Pressure
Gage (Optional)
Valve K
Electrical Pressure Transducer or
Acceptable No-Flow Pore Pressure
Measuring System
Source: Office of the Chief of Engineers, 1970
Figure 12. Triaxial Permeameter with Back Pressure
-------
\
^Constant Level Tank
Membranes
Sample Cell
— Graduate
Source: Tallard and Caron, 1977b
Figure 13. Constant Head Triaxial Permeameter
93
-------
Potential Problems Presented by Permeability Tests—
There are several sources of error associated with laboratory perme-
ability tests that can affect the accuracy of the results. These include:
• Incomplete initial saturation of the test sample, or accumulation of
gas bubbles with the sample. This can greatly reduce the measured
permeability.
• Leakage around the sides of the sample can significantly affect the
measured permeability.
• Changes in the temperature of low permeability samples in long term
tests can affect the measured permeability (Office of the Chief of
Engineers 1970, Olson and Daniel 1981).
While all permeability tests can be affected by a number of problems,
the evaluation of a particular permeameter test hinges not so much on the
types of equipment utilized, but the test and quality control procedures
followed during the study. The preliminary results of an on-going study show
that the use of fixed wall or triaxial devices will not affect the results of
the permeability tests of a soil/bentonite mixture.* Thus, more attention
should be paid to the test procedures than to the type of equipment used.
Grout Sample Preparation
The grout to be tested must be first mixed with a material that
resembles soil. Since an inert, well defined material that is easy to mix
with grout is needed, sand is usually used. Tallard and Caron (1977b)
recommend sand with a gradation from 0.1 to 0.3 mm. Other studies have used
sands with well-defined size ranges including Ottawa 20-30 sand (Borden,
Krizek, and Baker 1982), Number 20 Monterey sand (Vinson and Mitchell 1972) ,
and Number 20 and 16 Monterey sand (clough, et al. 1977).
While the sand can be mixed with the grout in a beaker, the best results
are obtained when the grout is injected into the sand contained within a mold
or column (Tallard and Caron 1977b). Although there is no current method
established for preparing the grouted sand sample, an ASTM procedure has been
proposed which outlines the packing and injection procedures for preparing a
chemically grouted sand specimen. This procedure basically consists of
placing the sand in a split mold at the desired density and injecting the
sand with grout (Baker 1982).
Various studies have developed procedures for packing the sand into the
container and injecting the grout into the sand. The apparatus in which the
sand is contained can be a column, fixed-wall permeameter cell, or mold such
*Ay.ers, I. GZA Corp., Newton Upper Falls, MA. Personal communication with G.
Hunt, September 2, 1982.
94
-------
as a California Bearing Ration (GBR) mold* (Vinson and Mitchell 1972, Tallard
and Caron 1977b, Clough et al. 1977, Johnson 1979). Tallard and Caron
(I977b) give detailed directions as to what size column should be used, how
the sand should be packed into the column, under what pressure the grout
should be injected, and how long the grout should be cured. Another study
(Clough et al. 1977) utilized an apparatus which allowed water to first be
injected into the columns, followed by the grout (see Figure 14).
The container of sand into which the grout is injected should contain
the fluid, either water or leachate, that the grout must withstand. Once
injected, the grout should be allowed to cure for a specific period of time
before it is used in a permeability test. The cure should be under wet
conditions in order to simulate those found in the field.
EFFECT OF LEACHATE ON GROUT SET TIME
The moment at which a grout sets can be expressed as a specific point in
the evaluations of a property characteristic of the grout. Some of these
could be:
• Rheological - viscosity, rigidity, shear limit
• Mechanical - compression strength, shear strength
• Thermal - critical temperature
• Optical - nephelometry
• Physio-chemical - pH, conductivity, electrical potential for
reducing oxides
• Physical - solubility, surface tension (Tallard and Caron 1977b).
Unfortunately, there is no one property that can be used for all grouts
to indicate when they have set (Tallard and Caron 1977b). The simplest
method, applicable to most grouts (except bituminous emulsions), is the
interval of time after which the grout can no longer be transferred from one
container to another (Tallard and Caron 1977b). This method of observation,
while somewhat subjective, can give a fairly accurate measurement of the
setting time for most chemical grouts.*
Setting time in the field is usually determined when the required
injection pressure increases noticeably. This measurement is unfortunately
not applicable to laboratory scale tests. In small test containers the grout
will not set while injection pressure is still being applied. Thus, the set
*Krizek, R. Northwestern University, Chicago, IL. Personal communication
with G. Hunt, October 11, 1982.
95
-------
'ressure *^*»-
Grout — ^__
Mixing
Propeller ..
—•»,
=• =
M
F
F
JL
•« i
1 C
V F
JL
•'
0
•Ml
.t h
'•':
:•
m£
3 C
•« r
JL
.t _
•;
*i.
3 C
T p
±
&^»i
j ,_
^, tmuent
i
Sand, Placed at
-^- Controlled Density
i
\
Grout Flow
Source: Clough et al., 1977
Figure 14. Schematic of Grouting Test Apparatus
-------
time can be artificially extended to periods longer than would actually be
encountered in the field, or as indicated by other laboratory measurements.*
A number of devices have been utilized that will give quantitative
measurements of setting time by measuring changes in viscosity with time.
The viscosity of a grout will increase with time until some point is reached
at which it is deemed set. This relationship can vary depending on the type
of grout utilized. The viscosity of silicate grouts will slowly increase
with time until a rapid gelation takes place. Acrylamide grouts stay at
about the initial viscosity until a rapid change in viscosity takes place
indicating set (Clarke 1982). Clays, on the other hand, will show a steady
increase in viscosity with time, with no point of rapid viscosity change
(Tallard and Caron 1977b). The set time for clays, then, can be determined
when a pre-selected viscosity is reached.
For chemical grouts, a Brookfield Viscometer can be utilized to measure
the change in viscosity. This method is outlined in ASTM Standard D4016-81:
Standard Test Method for Viscosity of Chemical Grouts by Brookfield
Viscometer. The change in viscosity with time can also be determined for
most grout types by a direct indicating viscometer, known as a Fann
Viscometer (Tallard and Caron 1977b). In this device the slurry is sheared
between two cylinders. The shear stress is derived from the torque on one of
the cylinders, while the average rate of shear is estimated from the measured
rate of rotation and the diameters of the two cylinders, as illustrated in
Figure 15 (Xanthakos 1979). The procedures for performing this test and the
required calculations are outlined in Standard Procedures for Testing
Drilling Fluids, API RP13B. API has also established procedures for
measuring the thickening time of cement using a consistometer. This device
relates the torsion of a paddle rotating in a slurry to degrees of firmness.
The procedures for performing this test can be found in API Specification 10:
API Specification for Materials and Testing for Well Cements.
All of the methods discussed so far relate only to measuring the setting
time of the pure grout. The setting time in a sand/grout mixture is also
important. The gelation can be determined through variations in the
mechanical strength properties, such as compression or tension and shear of
the sand/grout mixture. The problem in measuring these properties is that
the gelation that occurs in the early stages is very weak and difficult to
distinguish from the natural cohesion of sand saturated with a viscous liquid
(Tallard and Caron 1977b). Also, the sand/grout mixture must be removed from
its container in order for the tests to be run. This could prove to be
difficult in the early stages of gelation.
In all cases where the setting time is being measured, the chemicals in
question should be mixed with the grout to determine their effects. In the
case of pure grouts, they can be mixed into the grout. Where grout is
injected into sand, the sand can be saturated with the chemical. By
+Ayers, J. GZA Corp., Upper Newton Falls, MA. Personal communication with G.
Hunt, September 3, 1982.
97
-------
Scale
\
Slurry Level
Pointer
Helical Torsion Spring
Splash Guard
Rotor Sleeve
Cup
Source: Adapted from Xanthakos, 1979
Figure 15. Rotational Viscometer
98
-------
comparing the effect of mixing the grout with pure water or the chemical,
their effect on set time can be determined.
OVERVIEW OF COMPATIBILITY TESTS
Unfortunately, there are no established procedures identified in the
literature for determining grout/chemical compatabilities. However, there
has been a lot of current research done on the effects of chemicals on the
permeability of clays and bentonite-soil mixtures (Anderson, Brown, and Green
1982, D'Appolonia and Ryan 1979, D'Appolonia 1980a). The procedures utilized
in these studies are applicable to the types of compatibility tests that must
be performed on grouts. Though the type of permeability apparatus utilized
is not critical, strict quality control procedures must be utilized in
running the studies.
For determining the effect of chemicals on set time, there are no
procedures that could be readily utilized on all types of grouts. While
visual observation of the grout is the easiest way of determining set time,
it is not applicable to all grouts and is somewhat subjective. This is an
area where more research must be done in order to develop a quantitative
method for determining set time.
99
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SECTION 8
GROUT SELECTION
The success of a grouting operation will depend on the selection of the
proper grouting materials for the specific area to be treated. Thus the
properties of the grout must be matched with the hydrogeological and geo-
logical properties of the area to be grouted. This can be accomplished by a
step-wise analysis of three basic grout properties:
• Injectability
• Strength
• Durability.
In addition to these properties, other factors such as cost and toxicity, not
directly related to the geological setting, should also be considered. In
some cases these may be the controlling factors.
By comparing each property to the conditions present in the geological
structure, the proper type of grout can be selected. The steps in this se-
lection process are illustrated in Figure 16. The selection of a specific
formulation for field application though, requires the assistance of experts
in the grouting field. (Tiedemann and Graver 1982).
These properties as they apply to the selection of a proper grout type
are discussed in the following subsections. A more detailed discussion of
relevant grout properties can be found in Section 5.
INJECTABILITY
The injectability of a grout is controlled either by its viscosity or
particle size. This property will dictate the grout's ability to penetrate a
soil/rock structure. The lower the viscosity, the finer the voids that can
be penetrated. Also, the smaller the particle size in suspension grouts, the
smaller the voids that can be penetrated.
For all grouts, the closer the viscosity is to that of water (1.0 cP),
the greater the penetration power. (Tiedemann and Graver 1982). Grouts with
a viscosity less than 2 cP, such as many of the chemical grouts, can
penetrate strata with permeabilities less than 10 cm/sec. Higher viscosity
grouts, like particulate and some chemical grouts with a viscosity greater
than 10 cP, can only penetrate coarse strata having permeabilities greater
than 10~ cm/sec (Sommerer and Kitchens 1980).
101
Preceding page blank
-------
o
Ki
All
Grout • »»
Types
Injectability
^-
Strength
Durability
^ Candidate
Grouts
111
Rejected Rejected Rejected
Grouts Grouts Grouts '
Figure 16. Grout Selection Process
-------
For suspension grouts, the particle size will also influence the ability
to penetrate voids. A general rule of thumb for determining grout penetra-
bility is sometimes used, which equates grain size of the particles within
the grout to soil particles within the stratum. This relationship is:
D85
where: 15 = diameter of grains in the stratum where 15% of the soil mass is
finer
85 = diameter of particles within the grout where 85% of the
particles is finer
This ratio should be at least 19 and preferably greater than 24 to insure
adequate penetration of grout into soil voids (Guertin and McTigue 1982) .
Based on these factors, Figure 17 illustrates the type of grout that can
be utilized based on the grain size of the stratum. By utilizing this table,
grouts that can be injected at a specific site can be identified.
STRENGTH
Once a grout has set in the voids in the ground, it must be able to
resist hydrostatic forces in the pores that would tend to displace it
(Tallard and Caron 1977b) . This ability will depend on the mechanical
strength of the grout and can be estimated by the grout's shear strength
(Tallard and Caron 1977b) .
The shear strength of a grout will depend not only on its class, but
also on its formulation. Thus, a class of grouts, such as silicates, can
possess a wide range of mechanical strengths depending on the concentration
and type of chemicals used in its formulation. The strength of the gel,
then, can be adjusted, within limits, to the specific situation. Examples of
the ranges of shear strengths for several classes of grouts are shown in
Table 9.
DURABILITY
For permanent control of groundwater or leachate movement, the grout
must not deteriorate with the influence of the soil or groundwater chemistry.
Therefore, in the selection process the short and long term durability of the
grout must be evaluated.
Deterioration of a grouted area over time can occur through several
physical/chemical mechanisms. The grout can be dissolved or structurally
changed by water or chemical action. Also, removal of water from the grout
through dessication or syneresis can lead to shrinkage of the grout. These
factors can weaken a grout, leading to increased permeability (Tallard and
Caron 1977b, Sommerer and Kitchens 1980).
103
-------
U.S. Standard Sieve Size
2 in. tin. 3/4 in. 1/2 in. No.4 No. 10 No.20 No.40 No.60 No. 100 No.200
(Ill
1 1 1 1
Grouting
Synerisis
Possible "
•
i 1 I i
Acrylamides
Resins
Chrome-Lignin
Silicates
Clay-Bentonite
Cement
1 Emulsions
Cement & Fillers
1
1 1 1
1
1
|
II Hi
!•*— 1 Ben
r
\
....]
J
rn
onitt
I
LJ
L.
1
"""* 1
1 * 'V
i —
i
1 ^ !
Bry
Join
Di
tic
Utl
ns
i
O
100
10
1.0
Grain Size in Millimeters
0.1
Dashed Lines Represent Extreme Limits of Application as Reported
in the Literature; Solid Lines Apply to More Typical Applications
0.01
0.001
Cobbles
Gravel
Coarse j Fine
Sand
Coarse J Medium 1 Fine
Silt or Clay
Source: Guertin and McTigue 1982
Figure 17. Applicability of Different Classes of Grouts Based on Soil Grain Size
-------
TABLE 9. RANGES OF VALUES OF VARIOUS PROPERTIES
OF SELECTED GROUT TYPES
GROUT TYPE
Bentonite
Silicate
Acrylamide
Phenolic
Ur ethane
Urea-Formaldehyde
Epoxy
Polyester
VISCOSITY
(cP)
10-20
1.5-50
1.2-1.6
1.2-10
20-200
10-13
20-100
10-200
SETTING TIME
(minutes)
—
0.1-3000
0.1-1000
1.5-2880
0.08-120
1-60
variable -
15
SHEAR STRENGTH
(gm/cm )
NA
1-150
20-200
10-1200
NA
NA
NA
NA
NA: Not available
Sources : Sommerer
and Kitchens 1980
Tallard and Caron 1977a
Tallard and Caron 1977b
Karol 1982a
Bowen 1981
Avanti International 1982
105
-------
Short term deterioration of the grout can be caused by rapid chemical
degradation or by an incorrect setting time. The effect on setting time can
be caused by a miscalculation of the grout formulation, dilution of the grout
by groundwater, or changes caused by chemicals contained within the grouted
strata. The effect that chemicals in the groundwater have on grout perfor-
mance is addressed in Section 6, which provides information on the effect
that different classes of chemicals will have on the set time and durability
of each grout type.
The effect that groundwater will have on the stability of grout depends
on the grout class and formulation. For areas that have large groundwater
flow rates, the grout must be able to quickly set before it is diluted or
washed away. The set time is, in many cases, a controlable parameter.
Ranges of set times for the different classes of grouts are illustrated in
Table 9. Water can also redissolve some of the grout constituents due to the
reversibility of many of the polymerization or gellation reactions (Tallard
and Caron 1977b).
The actual durability of a grout in a specific geological setting should
be determined by laboratory testing. The selection of grout could also be
based on the results of actual field applications- in similar geologic
settings.
OTHER FACTORS
Another grout selection factor that might be considered is the toxicity
of the grout's components and the solidified grout. This factor will be
important if the aquifer with which the grout comes in contact is a potential
drinking water source. The oral toxicity of most of the compounds used in
grouts has been determined as have many of the values for the set grout.
Table 10 shows LDcn values f°r some of the commonly used grout materials.
These values provide only an indication of the potential risk that a grout
poses to the groundwater. The specific grout application and the amount of
unreacted material must also be considered.
The cost of the grouting operation is also a factor that must be
considered. This should include the costs of the materials as well as the
injection costs. Current costs for grouted soils range from $100/yd to
$500/yd of grouted soil, depending on the type of grout used and the
characteristics of the soil. For chemical grouts, their expense is offset to
some degree by the fact that particulate grouts may be three to five times
more costly to pump into the ground (Guertin and McTigue 1982). Table 11
gives some costs of selected grouting materials.
OVERVIEW
By going through this process in a step-wise fashion, a number of
candidate grouts can be selected. Unfortunately, there is not enough infor-
mation available to create a series of tables listing all relevant selection
factors. Much of this information must be collected for each specific site
due to the wide variation of environmental and geological considerations.
106
-------
TABLE 10. TOXICITY OF SELECTED GROUTS ORAL
(mg/kg) FOR RATS
GROUT TYPE
COMPONENTS
ORAL LD..Q (mg/kg)
COMPONENTS SET GROUT
Silicate
Acrylamide
Phenolic
Urethane
Urea-Formaldehyde
Sodium Silicate 1100
Calcium Chloride 1000
Magnesium Chloride 2800
Dimethylformamide 1500
Acrylamide Monomer 200
Mechylenebiracrylamide 390
Resorcin 301
Phenol 414
Formaldehyde 800
Toluene Diisocyanate 5800
Acetone 9750
>15,000
5,000
>15,000
5,000
NA
Formaldehyde
800
Sources: Tallard and Caron 1977b
Berry 1982
Geochemical Corporation 1982
107
-------
TABLE 11. APPROXIMATE COST OF GROUT1
APPROXIMATE COST
GROUT TYPE $/GALLON OF SOLUTION
Portland cement 0.95
Bentonite 1.25
Silicate - 20% 1.75
- 30% ' 2.10
- 40% 2.75
Lignochrome 1.55
Acrylamide 6.65
Urea-formaldehyde 5.70
^980 Dollars
Source: JRB Associates 1982
108
-------
SECTION 9
RESEARCH NEEDS
During the course of this study several areas were identified that
lacked available information but are important in determining the usefulness
of grouts at hazardous waste disposal sites. These areas would be good
candidates for further research and include:
• Grout specifications and applications
• Compatibility of grouts with chemicals
• Long-term stability of grout
• Compatibility testing procedures.
The specific topics that are included in these general areas are discussed in
the following subsections.
GROUT SPECIFICATIONS AND APPLICATIONS
During the information search, very little data were found on the for-
mulation of currently or potentially utilized grouts and their specific areas
of application. Information on the chemical make-up and specific area of
application of each type of grout must be known in order to select the grouts
and testing procedures to be included in a laboratory evaluation program.
The specific areas that should be investigated.include:
• Areas of potential and actual grout application at waste disposal
sites
• Information on actual grout formulations currently utilized.
COMPATIBILITY OF GROUTS WITH CHEMICALS
As noted in the text, there is very limited information on the effect
chemicals would have on grouts utilized at disposal sites. Moreover, most
compatibility information deals with the effects of high concentrations of
simple chemicals. In order to evaluate the affect of leachates on grouts,
information on compatibility of grouts with low chemical concentrations and
chemical mixtures must be known. Thus, areas for further research including
a pilot scale program are:
• Effects of dilute chemicals on grouts
109
-------
• Effects of chemical mixtures 'on grouts
• Effects of actual leachates on grouts.
LONG-RANGE STABILITY OF GROUTS
Once in the ground, the ability of grout to withstand not only leachate
but water, hydrostatic pressure, and biodegradation, must be known. This
type of information is very limited in the literature and is very important
if a permanent seal is to be obtained. Thus, the environmental effects on
the structural integrity of grouts should be further researched in both a
laboratory and pilot scale program.
COMPATIBILITY TESTING PROCEDURES
There currently are no established compatibility testing procedure for
grouts. However, there is the potential to utilize the same types of testing
procedures developed for evaluating soils, bentonite slurries, and cement.
Permeability measurement techniques have been developed in all of these
areas, which are directly applicable to grout compatibility evaluations. Set
time measurements, on the other hand, are a little more difficult to apply
because of the greatly varying nature of the set grouts. For both types of
measurements, though, different laboratory techniques have to be used for
testing the different grout types due to variation in physical/chemical
properties. The areas that need further research include:
• Evaluation and selection of permeability testing procedures
• Evaluation and selection of set time testing procedures.
110
-------
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Conference on Grouting in Geotechnical Engineering, American Society of
Civil Engineers, NY. 1982.
126
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Lundberg, L.A., J.C. Schlegel, and J.E. Carpenter. Resinous Composition.
(To American Cyanamid Co.) U.S. Patent No. 3,091,936. June 4, 1963.
Malone, P.G., L.W. Jones, and R.J. Larson. Guide to the Disposal of
Chemically Stabilized and Solidified Wastes. SW-872. U.S. Army
Engineer Waterways Experiment Station. Prepared for: USEPA, Municipal
Environmental Research Laboratory, Cincinnati, OH. 1980.
Matrecon, Inc. Lining of Waste Impoundment and Disposal Facilities. SW-870.
USEPA, Municipal Environmental Research Laboratory, Cincinnati, OH.
1980.
McCabe, K.W. Polyurethane gives stabilty to mine roofs. Modern Plastics.
January 1982.
McLaughlin, H.C. Method of Stabilizing or Sealing Earth Formations. (To
Halliburton Co.) U.S. Patent No. 3,334,689. August 8, 1967.
McLaughlin, H.C. Preparation and Use of Sodium Silicate Gels. (To
Halliburton Co.) U.S. Patent No. 3,202,214. August 24, 1965.
Meyer, B. Urea-Formaldehyde Resins. Addison-Wesley. Publishing Company,
Inc., London. 1979.
Miles, M.M. amd R.G.H. Boyes. Slurry trenching developments. Civil
Engineering, pp. 51-52. April 1982.
Millet, R.A. and J.Y. Perez. Current USA Practice: Slurry Wall
Specifications. Journal of the Geotechnical Engineering Division.
Vol. 107, No. 8. pp. 1041-1056. 1981.
Mobay Chemical Corporation. Roklok Binder. Technical Information. 1982.
Modern Plastics Encyclopedia. Vol. 58, No. 10A. McGraw-Hill, Inc., NY.
1981.
Moller, K. Control of groundwater and unstable soils. Water Services.
Vol. 80, No. 969. pp. 684-686. 1976.
Morrison, R.T. amd R. N. Boyd. Organic Chemistry. 2nd ed. Allyn and Bacon,
Inc., Boston, MA. 1969.
Nasiatka, D.M., T.A. Shepherd, and J.D. Nelson. Clay Liner Permeability in
Low pH Environments. In: Symposium on Uranium Mill Tailings
Management, Fort Collins, CO. October 26-27, 1981.
Neelands, R.J, and A-.N. James. Formulation and Selection of Chemical Grouts
with Typical Examples of their Field Use. In: Grouts and Drilling Muds
in Engineering Practice. Butterworths, London, pp. 150-155. 1963.
127
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Neville, A.M. Properties of Concrete. 2nd ed. John Wiley and Sons, New
York, NY. 1973.
Office of the Chief of Engineers. Engineering Design. Chemical Grouting.
EM 1110-2-3504. Department of the Army, Washington, DC. May 1973.
Office of the Chief of Engineers. Engineering and Design. Laboratory Soils
Testing. EM 110-2-1906. Department of the Army, Washington, DC. 1970.
Olson, R.E. and D.E. Daniels. Measurement of the Hydraulic Conductivity of
Fine-grained Soils, in Zimmie, T.T. and C.O. Riggs (eds.): Permeability
of Groundwater Contaminant Transport, ASTM Special Technical Publication
746. American Society for Testing and Materials, Philadelphia, PA. pp.
18-64. 1981.
Peeler, C.E. Chemical Composition and Process for Soil Stabilization. (To
Diamond Alkali Co.) U.S. Patent No. 2,968,572. January 17, 1961.
Perrott, W.E. British Practice for Grouting Soils. Journal of the Soil
Mechanics and Foundations Division, Proceedings of the ASCE. Vol. 91,
No. SM 6. pp. 57-79. 1965.
Pusch, R. Rock Sealing with Bentonite by Means of Electrophoresis. Bulletin
of the International Association of Engineering Geology. No. 18. pp.
187-190. 1978.
Rensvold, R.F. Epoxy Resin Grouting Fluid and Method for Stabilizing Earth
Formations. (To Halliburton Co.) U.S. Patent No. 3,416,604. December
17, 1968.
Rhoderick, J.E. and A.D. Buck. Borehole Plugging Program (Waste Disposal).
Report 2. Petrographic Examination of Several Four-Year Old Laboratory
Developed Grout Mixtures. Miscellaneous Paper of C-78-1. U.S. Army
Waterways Experiment Station, Vicksburg, MS. 1981.
Riedel, C.M. Chemical Soil Solidification—Theory and Applications in
Construction Work. Transaction of the New York Academy of Sciences.
Ser. II, Vol. 27, No. 2. pp. 189-202. 1964.
Rogoshewski, P., H. Bryson, P. Lee, K. Wagner, P. Spooner, and S. Paige.
Manual for Remedial Actions at Waste Disposal Sites. JRB Associates.
Prepared for: USEPA, Region II, Office of Research and Development, New
York, NY. 1980.
Rollinger, G. Operations and Maintenance Manual. In-Situ Containment/
Treatment Equipment. Rexnord, Inc. Prepared for: USEPA, Office of
Research and -Development, Industrial Environmental Research Laboratory,
Edison, NJ.
Rushing, H.B. Evaluation of Masonry Coatings. Research Project No.
68-3C(B). Louisiana Department of Highways, Materials Division. 1969.
128
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Saunders, J.H. and K.C. Frisch. Polyurethanes. Chemistry and Technology.
part I. Chemistry. Wiley-Interscience Publishers, NY. 1962.
Scheldknecht, C.E. and Skeist, I. (eds.) Polymerization Processes.
Wiley-Interscience Publishers, New York, NY. 1977.
Schupack, F. Grouting of post-tensioning tendons. Civil Engineering, pp.
72-73. March 1978.
Scott, R.L. and R.M. Hays. Inactive and Abandoned Underground Mines—Water
Pollution Prevention and Control. EPA 440/9-75-007. Michael Baker,
Jr., Inc. Prepared for: USEPA, Office of Water Planning and Standards,
Washington, DC. 1975.
Slurry Systems. General Information on ASPEMIX Slurry Test on Various
Leachates. Slurry Systems, Gary, IN. March 25, 1982.
Soletanche. Soils Grouting. Technical Bulletin. Paris. No Date.
Soletanche. Consolidation of Fissured Rocks by High Pressure Grouting.
gyf-pc.mm No. 10.271. Paris. 1962.
Sommerer, S. and J.F. Kitchens. Engineering and Development Support of
General Decon Technology for the DARCOM Installation Restoration
Program. Task 1 Literature Review on Groundwater Containment and
Diversion Barriers. Draft. Atlantic Research Corporation. Prepared
for: U.S. Army Hazardous Materials Agency, Aberdeen Proving Ground, MD.
October 1980.
Spangler, M.G. and R.L. Handy. Soil Engineering. In Text. Harper and Rowe
Publishers, New York. 1973.
Stewart, W.S. State-of-the-Art Study of Land Impoundment Techniques. EPA
600/2-78-196. Exxon Research and Engineering Company. Prepared for:
USEPA, Municipal Environmental Research Laboratory, Cincinnati, OH.
1978.
Tallard, G.R. and C. Caron. Chemical Grouts for Soils. Vol. I Available
Materials. FHWA-RD-77-50. Soletanche and Rodio, Inc. Prepared for:
United States Department of Transportation, Federal Highway
Administration, Offices of Research and Development, Washington, DC.
June 1977a.
Tallard, G.R. and C. Caron. Chemical Grouts for Soils. Vol. II Engineering
Evaluation of Available Materials. FHWA-RD-77-51. Soletanche and
Rodio, Inc. Prepared for: United States Department of Transportation,
Federal Highway Administration, Offices of Research and Development,
Washington, DC. June 1977b.
129
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Technical Information Center and Concrete Laboratory. Miscellaneous Paper
C-78-8. Bibliography on Grouting. U.S. Army Engineer Waterways
Experiment Station, Vicksburg, MS. June 1978.
Thompson, D.W., P.G. Malone, and L.W. Jones. Survey of Available
Stabilization Technology. In: Toxic and Hazardous Waste Disposal.
Volume I. Processes for Stabilization/Solidification. Ann Arbor Science
Publishers, Inc., Ann Arbor, MI. 1980.
Urethane Grouts. Technical Information. 3M, St. Paul, MN. 1981-1982.
Sealing Gel System Field Manual. 3M, St. Paul, MN. August 1980.
Tiedemann, H.R. and J. Graver. Groundwater Control in Tunneling.
Vol. 2—Preventing Groundwater Intrusion into Completed Transportation
Tunnels. FHWA/RD-81/074. Jacobs Associates. Prepared for: USDOT,
Federal Highway Administration, Washington, DC. 1982.
Tolman, A.L., A.P. Ballestero, Jr., W.W. Beck, Jr., and G.H. Emrich.
Guidance Manual for Minimizing Pollution from Waste Disposal Sites. EPA
600/2-78-142. A.W. Martin Associates, Inc. Prepared for: USEPA,
Municipal Environmental Research Laboratory, Cincinnati, OH. 1978
Tomlinson, M.J. Foundation Design and Construction. 4th ed. Pitman
Advanced Publishing Program, Boston, MA. 1980.
U.S. Grout Corporation. Five Star Grout Technical Bulletins. Riverside, CT.
1980.
U.S. Grout Corporation. Grouting Handbook. A Professional1s Guide to
Non-Shrink Grouting for: Owners, Architects, Engineers, Contractors,
and Specifiers. Fairfield, CT. 1981.
Vinson, T.S. and J.K. Mitchell. Poly-urethane Foamed Plastics in Soil
Grouting. Journal of the Soil Mechanics and Foundations Division.
Proceedings of the ASCE. Vol. 98, No. SM 6, pp. 579-602. 1972.
Walley, D.M. Investigation of the Resistance of Freshly Injected Grout to
Erosion and Dilution by Flowing Water. Miscellaneous Paper C-76-4.
U.S. Army Engineer Waterways Experiment Station, Vicksburg, MS. 1976.
Warner, J. Epoxies—"Miracle" materials don't always give miracle results.
Civil Engineering, pp. 48-55. February 1978.
Watertight diaphragm walls. (Technical Bulletin.) Soletanche, Paris.
Weast, R.C. (ed.) Handbook of Chemistry and Physics. 52nd ed. CRC Press.
Cleveland, OH. 1972.
Williams, D.R. Silicate Grout. (To The Cementation Co., Ltd., London.)
U.S. Patent No. 3,294,563. December 27, 1966.
130
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Xanthakos, P.P. Slurry Walls. McGraw-Hill Book Company, New York. 1979.
Zimmie, T.F. Geotechnical Testing Considerations in the Determination of
Laboratory Permeability for Hazardous Waste Disposal Siting. In Conway,
R.C. and B.C. Malloy (eds.): Hazardous Solid Waste Testing, ASTM
Special Technical Publication 760. American Society for Testing and
Materials, Philadelphia, PA. pp. 209-304. 1981.
131
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APPENDIX A
ANNOTATED BIBLIOGRAPHY
Anderson, D., K. Brown, and J. Green. Effect of Organic Fluids on the
Permeability of Clay Soil Liners. In: Land Disposal of Hazardous Waste.
Proceedings of the Eighth Annual Research Symposium. EPA-600/9-P2-002.
USEPA, Municipal Environmenal Research Laboratory, Cincinnati, OH. 1982.
Report evaluates the permeability of four compacted clay soils when
exposed to chemicals representative of four classes of organic fluids found
in hazardous waste. Since permeability remains the primary criterion for
evaluating the suitability of clay lines for the lining of hazardous waste
disposal facilities, results indicate the need to test the permeability of
prospective clay liners using the leachate to which they will be exposed.
Laboratory investigations of the influence of organic chemicals on the
properties of clay indicate tha organic fluids can substantially increase the
permeability of compacted clay soils.
API. American Petroleum Institute. API Specification for Materials and
Testing for Well Cements. API Spec 10. American Petroleum Institute,
Washington, DC. 1982.
The purpose of this specification is to provide standards for well
cements, well cement additives, and well cement testing procedures.
Specification requirements are detailed for sampling and preparation of
slurry. Specification tests address: soundness and fineness, determination
of free water content of slurry, strength, thickening time, and atmospheric
pressure consistometer. Individual sections are devoted to bentonite,
barite, fly ash, marking, packaging, and storage, and inspection and
rejection. Includes appendices.
Baker, W.H. (ed.) Proceedings of the Conference on Grouting in Geotechnical
Engineering. American Society of Civil Engineers, New York, NY. 1982.
This is a publication of proceedings from the 1982 Conference in
Geotechnical Engineering sponsored by the American Society of Civil
Engineers. The 63 papers included represent 12 countries and deal with the
pertinent advances in grouting materials and technology that have occurred
throughout the world over the past decades. The conference was comprised of
12 sessions addressing the following topics: materials for cement and mortar
grouts; dam grouting technology; applications; design and control; chemical
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grouts materials, technology, and applications; behavior of chemically
grouted soil; grouting for tunnels, shafts, and mines; and grouting testing,
control, applications, and alternatives.
Bowen, R. Grouting in Engineering Practice. 2nd ed. John Wiley and Sons, NY.
1981.
Text examines various grout types, paying particular attention to two
important categories: cement and clay-cements in water and chemical solu-
tions. The techniques for application as well as specifications for utiliza-
tion of different grouts is discussed. Book includes case histories as well
as several new topics which did not appear in first edition. Also contains
expanded glossary.
Herndon, J. and T. Lenahan. Grouting in Soils. Vol. One, A State-of-the-Art
Report. FHWA-RO-76-26. Halliburton Services. Prepared for: USDOT,
Federal Highway Administration, Washington, DC. 1976.
Report summarizes present grouting technology applicable to soils, from
theory to field practices. Particular applications are given for cut-and-
cover construction and soft ground tunneling. Includes: summary of patents
applicable to grouting; list of grouting specialists, material, and equipment
suppliers; bibliography of publications; and unpublished case histories of
grouting jobs. Notes distinct differences between grouting performed in the
United States and that performed in Europe. Contains summary and recommenda-
tions for improvements in the grouting field.
Herndon, J. and T. Lenahan. Grouting in Soils. Vol. II. Design and
Operations Manual. FHWA-RO-76-26. Halliburton Services. Prepared for:
USDOT5, Federal Highway Administration. Washington, DC. 1976.
Manual provides guidelines for design and conduct of soil grouting
operations, from the selection of the grout and the design of the injection
pattern to construction contol methods and evaluation of the completed
treatment. This report emphasizes grouting applications associated with
excavation and tunneling in an urban environment. Three general grouting
techniques (permeation, void filling, and compaction) are described. Details
are given on the following applications: groundwater control, sand stabil-
ization, soil strengthening, backpacking, tunnel liners, leak repairs, and
tieback anchorages.
Hurley, C. and T. Thornburn. Sodium Silicate Stabilization of Soils—A
Review of the Literature. UILU-ENG-71-2007. University of Illinois, Urbana,
IL. 1971.
This report consists of an annotated bibliography and summary review of
the important literature on the use of sodium silicates in soil stabilization
134
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processes. Annotations are given for approximately 90 articles published
between 1931 and 1965. On the basis of these articles the authors have sum-
marized pertinent information on stabilizer properties, reaction mechanisms,
injection methods of soil solidification, preparations of stabilizer-soil
mixtures, use of sodium silicates as dustproofers and waterproofers, and
their use as secondary additives with other stabilizers. Where warranted,
conclusions have been drawn regarding the conditions under which sodium
silicates appear to have potential value in the soil stabilization field.
Neville, A. Properties of Concrete. 2nd ed. John Wiley and Sons,
New York, NY. 1973
The text provides a complete overview of Portland cement from its
history to its manufacture. Addresses chemical composition and such physical
properties as: hydration, setting, fitness, structure, volume, and strength.
Includes detailed discussion on different types of cements. Incorporates
information on current research and development and deals with some topics
not included in first edition.
Office of the Chief of Engineers. Engineering and Design: Laboratory Soils
Testing. EM 1110-2-1906. Department of the Army, Washington, DC. 1970.
Manual presents recommended testing procedures for making determinations
of the soil properties to be used in the design of civil works'projects.
Appendices address physical characteristics of soils. Other chapters are
devoted to soils tests, including permeability, consolidation, swell and
swell pressure, and triaxial compression.
Tallard, G.R. and C. Caron. Chemical Grouts for Soils. Vol. I. Available
Materials. FHWA-RD-77-50. Soletanche and Rodio, Inc. Prepared for: United
States Department of Transportation, Federal Highway Administration, Offices
of Research and Development, Washington, DC. June 1977.
Research involves the search for more economical grouts not dependent on
petroleum. Based on the nature of the major component, a general classifi-
cation of chemical grouts has been proposed. Factors forming the basis of
evaluating grout materials include: permeability, strength, toxicity,
durability, and injectability. A selected number of grouts have been tested
for possible improvement, with lignochrome gels and furan resin deriviatives
showing the most promise. This volume addresses the classification and
evaluation of grouts, aqueous and colloidal solutions, non-aqueous grouts,
emulsions, and products reacting with the ground.
135
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Tallard, G.R. and C. Caron. Chemical Grouts for Soils. Vol. II.
Engineering Evaluation of Available Materials. FHWA-RD-77-51. Soletanche
and Rodio, Inc. Prepared for: United States Department of Transportation,
Federal Highway Administration, Offices of Research and Development,
Washington, DC. June 1977.
Examines more economical grouts not directly dependent on petroleum.
Based on the nature of the major component, a general classification of
chemical grouts has been proposed. Factors of evaluation include: inject-
ability, permeability, setting time, strength of pure grout, strength of
grouted soil, durability, and toxicity. Of a selected number of grouts which
were tested for possible improvement, lignochrome gels and furan resin
derivatives are particularly promising. This volume discusses testing
requirements, proposed standard testing procedures, properties of promising
grout materials, and evaluation of those materials.
Office of the Chief of Engineers. Engineering and Design: Chemical
Grouting. EM 1110-2-3504. Department of the Army, Washington, DC. 1973.
Manual provides guidance and information regarding the use of chemical
grouts, and for planning, executing, analyzing, and evaluating chemical
grouting operations. Chemical grout materials and grouting equipment are
described and methods of injection are presented. Provisions of this manual
are applicable to Corps of Engineers concerned with civil works design and
construction. Addresses the planning procedures of a chemical grouting
program.
136
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APPENDIX B
GROUT MANUFACTURERS/SUPPLIERS INFORMATION
TABLE B-l
PRODUCT MANUFACTURERS AND SUPPLIERS
Type of Grout
Product Name
Manufacturer or Supplier
Acrylamide
Bentonite
Epoxy
Phenolic
AC-400
AV-100
®
Injectite -80
Rocagil
Q-Seal
Akwaseal
Imclay
Volelay
Ancamine, MCA
Epon
Epotuf
Five Star
Geoseal
Rogacil
Terraseal
Geochemical Corporation
Avanti International
Penetryn Restoration
Rhone Progil Company (France)
Cues, Inc.
Federal Bentonite
International Minerals and
Chemicals Corporation
American Colloid Co.
Pacific Anchor
Shell Chemical
Reichhold Chemicals, Inc.
U.S. Grout Corporation
Borden Chemical
(Great Britain)
Rhone Progil Company
(France)
Cellite, Inc.
137
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TABLE B-l (Continued)
Type of Grout
Product Name
Manufacturer or Supplier
Urea-Formaldehyde
Urethane
Silicate
Herculox
(formulated for
company use only)
CR-250 and CR-202
Rokloc
TACSS
Geloc
(formulated for
company use only)
SIROC
Terraset
(formulated for
company use only)
(formulated for
company use only)
(formulated for
company use only)
Halliburton
Services
3M
Mobay Chemical
Takameka
Komuten (Japan)
Hayward Baker
No longer manufactured under
this name
Celtite, Inc.
Halliburton Services
Raymond International
SOLING
138
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TABLE B-2
LOCATION OF U.S. MANUFACTURERS AND SUPPLIERS
Avanti International
1275 Space Park Drive
Houston, Texas 77058
713-333-5430
Contact: F. David Magill
American Colloid Company
Environmental Products Division
5100 Suffield Court
Skokie, Illinois 60077
312-966-5720
Celtite, Inc.
Cleveland, Ohio 44133
216-237-3232
Contact: Tony Plaisted
Cues, Inc.
3501 Vineland Road
Orlando, Florida 32805
305-849-0190
Federal Bentonite
1002 Greenfield Road
Montgomery, Illinois 60538
910-232-0759
Contact: Bruce Beattie
Geochemical Corporation
162 Spencer Place
Ridgewood, New Jersey 07450
201-447-5525
Halliburton Services
Duncan, Oklahoma 73533
405-251-3760
Hayward Baker Company
1875 MayfieId Road
Odenton, Maryland 21113
301-551-8200
Contact: Joseph Welsh
139
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TABLE B-2 (Continued)
International Minerals and Chemical Corporation
666 Garland Place
Des Plaines, Illinois 60016
312-296-0600
Mobay Chemical Corporation
Plastics and Coatings Division
Pittsburg, Pennsylvania 15205
412-788-1458
Contact: Kirk McCabe
Pacific Anchor Chemical Corporation
Richmond, California 94804
415-529-1020
Penetryn Restoration
Division of BPR Corporation
Knoxville, TN
Raymond International, Inc.
6825 Wertfield Avenue
Pennsauken, New Jersey 08110
609-667-3323
Contact: Dick Colle
Reichhold Chemicals, Inc.
RCI Building
White Plains, New York 10602
617-475-6600
SOLING
Soletanch and Rodio, Inc.
6849 Old Dominion Drive
McLean, Virginia 22101
703-821-6727
Contact: Edmond Cardoza
U.S. Grout Corporation
401 Stillson Road
Fairfield, Connecticut 06430
203-336-7900
140
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TABLE B-2 (Continued)
3M Center
Adhesives, Coatings and Sealers Division
St. Paul, Minnesota 55144
612-733-1110
Contact: Joe Gasper
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