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Chemical Grouts
10.1
GENERAL
10.2
HISTORY
1967, this center published over 1000 pages of technical reports related to
chemical grouts and grouting) to develop grouting techniques and
technology.
At about the same time, chrome-lignin grouts (lignosulfonate
solutions catalyzed with chromate salts) were proposed and developed for
eld use.
In Europe, phenol and resorcinal formaldehydes, developed in the
latter 1940s, came into use. During the next several years, ureaformaldehyde-based grouts giving high strength such as Halliburtons Herculox and
Cyanamids Cyanaloc were developed and marketed (about 1956). In 1957,
Soletanche in France developed a single-shot silicate grout using ethyl
acetate as the reagent. Other esters came into use in the following years.
Around 1960, Diamond Alkali Company entered the market with a
single-shot silicate-based grout trade named SIROC, which offered high
strength or low viscosity, each coupled with gel time control. At about this
time Terra Firma, a dried precatalyzed lignosulfonate, also entered the
market.
Several years later Rayonier Incorporated marketed Terranier, a
single-shot grout comprised of low-molecular-weight polyphenolic polymers
(about 1963). Then, Borden Inc. marketed Geoseal, a resin prepolymer
(patent led in 1968).
Developments in chemical grouting were also taking place in Asia. In
Japan, an acrylamide grout was marketed in the early 1960s as Nitto SS, and
the TACSS system, a polyurethane which uses groundwater as the reactant,
was marketed several years later. In Europe, during the 1960s, renements
were made to the silicate systems, and in the late 1960s and early 1970s,
acrylamide-based grouts appeared. Rocagil AL (Rhone-Poulenc Inc.,
France) is a mixture of an acrylic monomer and an aqueous dispersion
resin, while Rocagil BT is primarily methylol acrylamide.
In the United States, the market was shared primarily by AM-9 and
SIROC until 1978, with SIROC getting the lions share. Proprietary
grouting materials had and still have a small part of the market. In Japan,
acrylamide grouts were banned in 1974 (ve reported cases of water
poisoning were linked to use of acrylamide on a sewer project), and several
months later the ban was extended to include all chemical grouting materials
except silicate-based grouts not containing toxic additives. These events
were to have strong effects on grouting practice in the United States.
Since the early 1970s concern over environmental polution had been
growing rapidly. In 1976 a federal agency (probably inuenced by events in
Japan) sponsored a study of acrylamide-based grouts used in the United
States. Acrylamide is a neurotoxic material, and the rst draft of the report
(which was never published) recommended that acrylamide grouts be
10.3
FIGURE 10.1
lens contained water, the grout would also have had to function as a seepage
barrier.
Different materials and procedures are used in the eld depending to a
large extent on the purpose of grouting. They are discussed more fully in
succeeding chapters.
10.4
GROUT PROPERTIES
For many years after the Joosten Process was proven in the eld, the term
chemical grout was synonymous with the Joosten Process and sodium
silicate. However, sodium silicate is the basis for many chemical grout
formulations in addition to the silicate-chloride two-shot injection. In a
similar manner to the way the techniques of cement grouting could not be
cost effectively applied to chemical grouting, the techniques of using high
viscosity silicates did not transfer well to the low viscosity materials coming
on the market.
The last half century since the introduction of the acrylamides has seen
a proliferation of materials totally unrelated to the silicates. These materials
cover a wide range of properties, and give the grouter the opportunity to
match a grout with specic job requirements, as well as treat problems that
could not be solved with high viscosity silicates.
The specic properties of commercial chemical grouts are well
documented by the various manufacturers and the technical literature. In
the sections that follow, a commercial chemical grout is considered to be
one which has been used on actual eld projects and which can be
purchased on the open market (or whose components can be purchased
on the open market). Proprietary materials, particularly those whose
components and properties are not publicly divulged, are not considered
commercial grouts and are not discussed by name in this book.
This does not imply that these materials are inferior in any way.
Some, in fact, are very similar and as effective as well-known products in
widespread use.
Practitioners often use additives to modify a grout for a specic use.
The change in properties is usually small. However, so many possible
additives are available that it is not feasible to catalog all the property
changes for all the grouts. Similarly, there are so many small differences in,
for example, the sodium-to-silicate ratio, that will give adequate grouts, that
it is not feasible to catalog all the possible variations. Thus, in the detailed
descriptions of grout properties which appear in subsequent sections, these
data should be viewed as average for minimally modied materials. By the
same token, reference to a specic property in, for example, an acrylamide
grout, can be taken as applicable to all similar acrylamides.
The mechanical properties of the various grouts that are important
factors in the selection of a grout for a specic job include permanence,
penetrability and strength. Similarly, the chemical properties include
permanence, gel time control, sensitivity, and toxicity, and the economic
factors include availability and cost. These properties are all discussed in
detail in the sections that follow, using data from specic materials
whenever such data will give a better understanding of chemical grouts.
Permanence
Permanence is a term which may have many denitions when applied to
chemical grouts, since it is related to specic applications. Specifying
permanent by a numerical time frame (such as 50 years), may unduly
eliminate the use of specic grouts for purposes in which they are totally
suitable. In many construction projects (for example, providing footing
support near a subsequent excavation, or seepage control during tunnel and
shaft construction), the grout need only function during the construction
period. In many other cases, it is more than likely that the grout need not
function beyond the life of the structure or project. Structural life is the most
universal and the most acceptable way to specify grout permanence. Since
many projects are designed for a 50-year life, specifying that grouts must
have a 50-year life is common practice. Records of performance on previous
works are used to satisfy the requirement. Such a specication obviously
precludes the use of new materials.
As eld data and job records accumulate, these may point to the
desirability of minor modications to grouts and catalysts. Also, of course,
new catalyst systems and additives may be developed that improve grout
properties or ease of application. These end products must be looked at
carefully to avoid the fallacy of arbitrary classication as new products, and
thus divorcing them from histories of performance and permanence which
may be totally applicable.
Over the past several decades, safe disposal of radioactive wastes has
become an increasingly serious problem. More serious is the treatment of
such wastes which have not been disposed of safely. Where hazardous
wastes have been buried underground, the options of isolating them from
contaminating the groundwater include chemical grout barriers. Thus, the
ability of grouts to withstand deterioration from radiation has become an
important grout property. Since the half-life of some of the radioactive
wastes may stretch into centuries, grouts used to contain such wastes must
have equivalent permanence. Except for the silicates which have been
around for a century or so, none of the other chemical grouts have been
around for more than a half century. Accelerated laboratory tests may be
used to attempt to extrapolate known performance.
There is still much interest in the chemical industry in developing new
grouts, particularly if these can be made from otherwise wasted byproducts.
At a recent seminar to discuss possible new materials, participants were
seriously talking about the need for products with 1000 year permanence,
for applications near radioactive wastes. Hopefully, technological progress
will evolve much better solutions to both ends of the problem long before
1000 years.
All grouts that contain water not chemically bound to the grout
molecules are subject to mechanical deterioration if subjected to
alternately freezethaw and/or wetdry cycles. The rate at which such
deterioration occurs varies with the amount of free water available in the
grout as well as with the degree of drying or freezing. Laboratory tests on
small sand samples grouted with a gel having a high free water content
indicated that signicant deterioration began only after the completion of
four to six complete cycles. The test conditions were probably more severe
than eld conditions would be, since total drying seldom occurs close
to the water table and freezing in temperate zones seldom extends
more than 5 to 10 ft below the ground surface. Nonetheless, it should be
* For example, complete wet-dry cycles may occur near a poorly insulated underground steam
pipe.
{ In the vicinity of a chemical plant, for example.
{ The effectiveness of pumping silicates into a formation to increase the take of the following
cement grout is more probably due to fracturing the formation or to preventing the smaller
voids from ltering the cement particles than to making the voids more slippery.
} Related terms are kinematic viscosity, the ratio of viscosity to density, and uidity, the
reciprocal of viscosity.
When a solid is subjected to a shearing force, the solid (simultaneously with the application of force) deforms, and internal stresses
develop until a condition of static equilibrium is reached. Within the elastic
limit of a substance, these internal stresses are proportional to the induced
shearing strains (deformation). The ability of a material to reach static
equilibrium, rather than deform continuously, is due to a property called
shear strength.
Fluids do not possess shear strength as such. Fluids do offer resistance
to deformation, due to internal molecular friction. However, under the
inuence of a shearing force, deformation will continue indenitely. The
property called viscosity is actually a measure of the internal friction
mobilized against shearing forces.
Viscosities of uids are generally not measured directly. Instead, a
parameter dependent on viscosity is measured and a predetermined
relationship used to arrive at an actual value. There are many different
commercial viscosimeters available, utilizing such principles as ow
through an orice or resistance offered to a known torque. In general,
viscosimeters cover only a limited range of values. Before using one for
measuring the viscosity of chemical grouts, it is necessary to determine
that the instrument functions properly in the required range. For
measuring a uid whose viscosity approaches that of water, a viscosimeter
that can measure accurately at 1 to 5 cP is required. Any instrument can
be readily checked in this range by using it to measure the viscosity of
water at room temperature. Unless the instrument gives repeated readings
of 1.0 within a few percent, it should not be relied upon. Methods for
determining grout viscosity have been studied and standardized. See
ASTM O-4016.
The viscosities of four different grouts, as measured by a Stormer
viscosimeter, are shown in Fig. 10.5. Viscosities, of course, vary with percent
(dissolved) solids, and the chart is presented in that fashion. The usable
viscosities of the various materials depend on the minimum desirable eld
concentration of solids. Thus, while it is obviously possible to work with a
20% sodium silicate solution in the Joosten process (a viscosity of between 3
and 4 cP), a gel would not form at that low a concentration, and it would be
misleading to claim a 4 cP viscosity. In a similar fashion, other silicate
formulations can be used to give either low viscosity of high strength, and it
is misleading to list those values simultaneously as if they were the
properties of the same uid.
The penetrability of various chemical grouts is shown in relation to
soil grain size in Figures 10.6a and b. In terms of permeability, a
conservative criterion is that grouts with viscosities less than 2 cP such as
acrylamide-based materials can usually be pumped without trouble into
FIGURE 10.5 Viscosities of several chemical grouts. Heavy lines indicate the
concentrations normally used for eld work.
soils with permeabilities as low as 104 cm/s. At 5 cP, grouts such as chromelignins and phenoplasts may be limited to soils with permeabilities higher
than 103 cm/s. At 10 cP, silicate-based formulations may not penetrate soils
below k 102 cm/s. All grouts may have trouble penetrating soils when the
silt fraction exceeds 20% of the total. (This is based on the assumption that
the soil is not fractured by the grouting pressure.) It is also important to
consider that permeability of a loosely compacted granular material may be
1 or more orders of magnitude greater than that of the same soil in the dense
state. These considerations have led to proposed new methods of
presentation of data on grout penetrability. Figure 10.6 (c, d, and e) show
three of these new approaches (Chapter 11, Refs. 1517).
FIGURE 10.6 (a) Penetrability of various grouts. (b) Effective range of ground
water control measures. (c) Indicative range of grout treatments. (From Ref.
11.15.) (d) Grout penetrability. (From Ref. 11.16.) (e) Groutability of soils by
various solution grouts. (From Ref. 11.17.)
Strength
Chemical grouts (except for epoxies and polyesters) have little strength
compared to cement, and the actual strength of a solid mass of chemical
grout is of academic interest only. However, the strength of soil formation
stabilized with chemical grout is of very practical interest.
Grouts that completely displace the uid in the soil pores form a
continuous but open and nonuniform latticework that binds the grains
FIGURE 10.6
Continued.
FIGURE 10.6
Continued.
water has been removed by air or oven drying. When water held by a grout
is lost through desiccation, the grout matrix shrinks. Shrinkage of the grout
between soil grains sets up forces analogous to capillary tensile forces but
often much stronger. This increases the resistance to relative motion
between grains and adds shear strength to the soil mass. Thus, desiccated
grouted soils will show strengths equal to or higher than wet strengths, often
higher by as much as 10 times. Dry values of strength are meaningless for
grouts that are placed and remain under the water table, and all references
to strength in this book, unless otherwise stated, refer to wet strength.
The strength of a fully permeated grouted soil depends on the specic
grout used but also on other factors. Chief among these are the density, the
average grain size, and the grain size distribution of the soil. In general,
strength increases with increasing density and with decreasing effective grain
size. Well-graded soils give higher strengths than narrowly graded soils with
the same effective grain size. Because of these variables, general discussion
of the anticipated strength of grouted soils should present ranges of values
rather than a specic number.
The shear strength of soils is composed of two components: (1) the
mechanical resistance of the individual soil particles to sliding and rolling
over each other (termed frictional resistance and measured by the angle of
internal friction) and (2) the resistance of individual particles to relative
motion because of the attraction between particles (termed cohesion). Pure
clays have virtually no frictional resistance and a friction angle of zero. Clay
particles, however, are very small, and the attraction between particles is
large compared to the particle size. Clays can develop appreciable cohesion.
On the other hand, the particles of granular soils are so large in comparison
to molecular attractive forces that for practical purposes such soils have zero
cohesion. However, the particles of granular soils interlock and develop
signicant frictional resistance, with friction angles of the order of 358.
Many natural soils are mixtures of ne and coarse particles and exhibit both
friction and cohesion.
Soils that have appreciable cohesion are generally too impermeable to
accept grout. Thus, grouting is done primarily in soils with zero cohesion,
and the effect of lling the voids with gel is equivalent to adding a cohesive
component to the soil shear strength. If the grout by its lubricity also makes
it easier for the soil grains to move past each other, there will also be a
reduction in the soil friction angle.
It is common practice to dene the shear strength of a soil on
coordinate axes, where y represents shear forces [2]. The strengths of
granular materials are dened by the straight sloping line passing through
the origin and making an angle f (the friction angle) with the x axis, as
shown in Figure 10.7a. This line is called the failure line, and all stresses
FIGURE 10.7 (a) Failure lines for grouted and ungrouted granular soils. (b)
Drained triaxial test results for silicate grouted coarse and medium sands.
(From Ref. 11.15.) (c) Typical stress-strain curve from unconned compression test on chemically grouted sand. (d) Compression versus time data for
creep test on chemically grouted sand, under constant load. (e) Failure time
versus percent of unconned compression failure load. () indicates
unconned compression tests, and (.) indicates triaxial tests with
S3 25% of S1 .
FIGURE 10.7
Continued.
which fall below this line do not cause shear failure. It can be seen from the
diagram that the shear strength of a soil increases as the normal stress
increases.
FIGURE 10.7
Continued.
FIGURE 10.7
Continued.
The dashed line in Figure 10.7a illustrates the change in strength due
to groutingthe addition of cohesive forces and a possible decrease in the
friction angle. If shear strengths are compared at points such as A and B, it
is seen that at small loads the effect of grouting is to give a signicant
increase in strength but that at large loads the increase due to grouting is
insignicant. (In fact, if grouting reduces the friction angle, it is possible that
at high normal stresses the shear strength of the soil will be reduced by
grouting.) Each specic job must be analyzed separately to determine if
grouting can indeed provide a signicant strength increase.
soils fail rather quickly due to creep. As the loading decreases, it takes
longer and longer for the samples to fail. At some value of the applied
loads, failure will not occur. Data to nd the nonfailing value take much
effort to accumulate and have been published only for acrylamide and
silicate grouts. Figure 10.7e shows these data for both unconned
compression and triaxial creep tests.
It is possible to delineate a creep endurance limit below which failure
will not occur regardless of the load duration. Limited data suggest that the
endurance limit is about 25% of the unconned compressive strength for the
materials tested when applied to eld conditions where stabilized soil masses
are unsupported on one face, as in open cuts, tunnels, and shafts. For eld
conditions where lateral support exists for the grouted mass, triaxial tests
are more suitable. Limited data indicates that, using at-rest lateral
pressures (see Chapter 11, Ref. 3) the triaxial creep endurance limit
approaches half of the unconned compressive strength. These data, while
approximate and in need of further study, indicate the values of the safety
factor to be used when grouted soil strength is a design consideration.
Gel Time Control
The ability to change and control the setting time of a grout can be an
important factor in the successful completion of eld projects. Excepting the
Joosten process, there is always a time lag from the mixing of the chemical
components to the formation of a gel. If all other factors are held constant,
this time lag (referred to as the gel time or induction period) is a function of
the concentration of activator, inhibitor, and catalyst in the formulation.*
With most grouts, the gel time can be changed by varying the concentration
of one or more of those three components. If a wide range of gel times can
be obtained and accurately repeated, gel time control is called good or
excellent. If only a narrow range of gel time is possible and repeatability is
difcult, gel time control is rated fair or poor.
Certain chemical grouts, after catalyzation, maintain a constant
viscosity and at the completion of the induction period turn from liquid to
solid almost instantaneously. Other grouts maintain constant viscosity for
much less than the total induction period. Still others increase in viscosity
from the moment of catalysis to gel formation, as shown in Figure 10.8. For
the last two categories, it may not be possible to pump grout into a
formation during the full induction period. It is also difcult to judge when
gelation occurs and to gage accurately the effects on gel time of external
variables.
* For most grouting materials, the gel time is relatively independent of grout concentration.
FIGURE 10.8
Ref. 11.15.)
Sensitivity
For any given grout formulation, the gel time is a function of temperature.
Chemical reactions slow down as the temperature drops, and for many
materials the effect is to approximately double the gel time for every 108 F
drop in temperature.* In addition to temperature effects, when a grout is
used in the eld, many other factors may affect the gel time. Primary among
these is dilution with groundwater which (in addition to changing the
solution temperature) will dilute the concentration of activator, inhibitor,
and catalyst. Of course excessive dilution may bring the grout itself below a
concentration where gel will form. Groundwater may also carry dissolved
salts which affect the gel time either by chemical activity or by change in pH.
Gel times may also be affected by contact with undissolved solids, such as
the materials used in pumps, valves, and piping. The degree to which a grout
is sensitive to such factors is termed its sensitivity. Materials which are
highly sensitive generally cause difculty in handling in the eld.
Toxicity
Health and occupational hazards have come under increasing scrutiny in the
last decade, resulting in several instances of banning of grout components by
federal agencies. Among the products used in the past, and still in use, are
ones classed as neurotoxic, cancer-causing, toxic, corrosive, highly irritating,
and so forth. While there have been a number of incidents of people
adversely affected by exposure to grouts, a study of each case involving eld
projects for which data have come to the authors attention indicates that
the problems could have been readily avoided by the use of common sense
and following the manufacturers recommendation for handling.
Almost all of the reported incidents of grout-related health problems
have involved persons handling the materials, not the general public. Efforts
to contain the toxicity problems have been made largely by the distributors
of the products, and largely aimed at the users. Manufacturers, on the other
hand, have responded by either withdrawing products from the market, or
developing less toxic replacements. Many of the manufacturing decisions are
dictated by real or anticipated liability concerns, which may bear little
relationship to actual hazards of properly handled materials.
Hazardous chemicals are normally tested by manufacturers in
accordance with standardized procedures, and are often described by a
value for LD50. This is the dosage expressed in milligrams per kilogram of
body weight per day at which 50% of the experimental animals die. United
States Federal agencies rate products as follows:
Very toxic LD50 5 to 50
Moderately toxic LD50 50 to 500
Very slightly toxic LD50 500 to 5000
When LD50 values are known, they will be listed in later sections as various
grouts are discussed.
All chemical grouts should be handled with care in the eld, with
safety and cleanliness equal to or better than the manufacturers
recommendations.
Economic Factors
Cost is of course a very important factor in selecting the construction
method best suited to solving a specic eld problem. When grouting is
compared with other methods such as well pointing or slurry trenching,
chances are that the cost comparisons will be realistic. When comparing two
different grouts, however, the mistake is often made of comparing raw
materials costs rather than in-place costs. Chemical grouts are available
commercially at prices ranging from 50 cents to $40 per gallon. However,
the ease of placing and the effectiveness of these materials vary, and the cost
of placement is almost always a major part of the in-place cost. Thus, while
raw material costs may vary over an 80-to-1 ratio, in-place costs generally
range from 5 to 1 to about equal. Selecting the most suitable material for a
specic job will generally overcome the possible lower material cost of other
products.
10.5
Permanent gel
Unaffected by chemicals normally found in groundwater
Nontoxic, noncorrosive, nonexplosive
High strength
10.6
SUMMARY
The modern era of chemical grouting began a half century ago, with the
introduction of many new materials, and the signicant modications to the
silicates. The earliest two products, silicates with gel time control and the
acrylics still dominate the domestic market, although many other products
are in regular use throughout the world.
Grout properties that play a role in the selection and use of the various
products are permanence, penetrability, strength, safety, ease of handling,
availability, and cost. Values differ widely among the available products. An
ideal chemical grout would combine the best properties of the commercial
products. In reality, there is a trade-off in properties for each grout (for
example, to get high strength silicates you sacrice low viscosity). Except for
the area of strength, acrylamides come close to being ideal grouts.
10.7
REFERENCES
10.8
PROBLEMS
10.1
10.2
10.3
Describe eld projects for which the grout need not be permanent.
What conditions affect the longevity of chemical grouts?
Cement grouting under a small concrete dam on a farm has failed to
shut off seepage channels. You have recommended chemical
grouting. The owner of the dam requires assurance that the grout
will not harm his livestock or plantings. What is your response?
List the domestic suppliers of
10.4
(c) acrylate
(d) urethane
10.5
10.6