Bulletin 52-53

INDUSTRIAL
CHEMICALS
DIVISION Soluble Silicates in
Geotechnical Grouting
Applications
INTRODUCTION
PQ® soluble silicates have been used successfully in chemical grouting and
other geotechnical applications for more than 50 years1. For soil stabilization
and water control during excavation and tunneling projects, silicate grouts
PQ CORPORATION
offer several advantages:
CORPORATE HEADQUARTERS
PO Box 840
● Reliable, proven performance
Valley Forge, PA 19482-0840 ● Safety and ease of use
Phone: 800-944-7411 ● Environmental acceptability
● Adaptability over a wide range of applications
IN CANADA
National Silicates
Soluble silicates are generally considered to be among the strongest and
Phone: 416-255-7771
least toxic of the existing chemical grouts2. Soluble silicates are inorganic,
IN MEXICO amorphous glasses. Unlike ordinary glass, these silicates are soluble in
Silicates y Derivados, S.A. water, hence the generic name “water glass”. PQ soluble silicates are pro-
Phone: 52-555-227-6801 duced by carefully fusing high-purity silica sand and either soda ash or
IN EUROPE potash in precisely controlled high-temperature furnaces. The silicates are
PQ Europe then processed into liquid and powdered products with a wide variety of
Phone: 31-33-450-9030 properties.
IN AUSTRALIA
Silicates are soluble because the alkaline sodium oxide (Na2O) or potassium
PQ Australia Pty. Ltd.
Phone: 61-3-9708-9200 oxide (K2O) maintains the pH at a level where silica (SiO2) can be dissolved.
If the pH is neutralized or lowered, the solubility of the silica is reduced and it
IN TAIWAN gels or polymerizes. Most silicate grouts depend on gel formation as the pre-
PQ Silicates Ltd. ferred chemical reaction.
Phone: 886-2-2383-0515

PQ Corporation is a privately held global
enterprise operating in 20 countries, with
annual revenues in excess of $500 million.
PQ is a leading producer of silicate, zeolite,
and other performance materials serving
the detergent, pulp and paper, chemical,
petroleum, catalyst, water treatment,
construction, and beverage markets.
Potters Industries, PQ’s wholly owned
subsidiary, is a leading producer of
engineered glass materials serving the
highway safety, polymer additive, fine
abrasive, and conductive product markets.
In addition to this gelling reaction, silicates can also react with soluble metals
to produce insoluble metal silicates or metal silicate gels. An example of this
would be the reaction of sodium silicate and calcium chloride which results in
the formation of hydrated calcium silicate3.
CHEMICAL GROUTING
Historically, chemical grouts have been used in sandy and gravelly soils
with less than 15 percent fines (<200 mesh) and permeabilities greater than
k=10-5(cm/s).4 Improved grouting techniques are proving to be successful in
clay/silt mixed soils once considered too impermeable to grout.5
PQ usually recommends N® sodium silicate for chemical grouting because it
is shipped ready to use and may be handled and stored easily. Of PQ’s
products, N® sodium silicate is the most readily-available and cost-effective
source of soluble SiO2.

® Registered trademarks of PQ Corporation

 Typical Properties of N® Sodium Silicate
INDUSTRIAL Wt. Ratio SiO2/Na2O 3.22
CHEMICALS % SiO2 28.7
DIVISION %Na2O 8.9
Density at 68o F, oBe 41.0
Density at 68o F, lb/gal 11.6
Density at 68o F, g/cm3 1.38
pH 11.3
Viscosity, cps 180
Characteristics syrupy liquid

N® silicate is typically diluted with water when used for chemical grouting.
Dilution reduces the product’s viscosity and increases its penetration into
soils. The dilution rate should be adjusted for soil permeability and the
desired strength of the grouted mass.

PQ CORPORATION Diluted silicate grouts are sometimes referred to as “percent silicate grouts.”
For example, a “50 percent silicate” grout contains 50 parts by volume N®
CORPORATE HEADQUARTERS
PO Box 840 silicate and 50 parts by volume water. The table below lists standard dilu-
Valley Forge, PA 19482-0840 tions and properties.
Phone: 800-944-7411
Volume Density Viscosity
IN CANADA
o
National Silicates N® Water Lb/gal Lb/ft3 Baume cps
Phone: 416-255-7771
100
100 0 11.6 86.8 40.8 180
IN MEXICO 70 30 10.6 79.6 31.5 11.0
Silicates y Derivados, S.A. 60 40 10.3 77.2 27.9 5.5
Phone: 52-555-227-6801
50 50 10.0 74.7 24.1 2.5
IN EUROPE 40 60 9.6 72.3 20.0 2.1
PQ Europe 30 70 9.3 69.8 15.6 2.0
Phone: 31-33-450-9030

IN AUSTRALIA STRENGTH AND PERMANENCE OF SILICATE-GROUTED SOILS

PQ Australia Pty. Ltd. The strength of a sodium silicate-grouted soil is determined by several factors:
Phone: 61-3-9708-9200

IN TAIWAN ● Concentration of silicate in the grout formulation

PQ Silicates Ltd. ● Composition and particle size distribution of the soil
Phone: 886-2-2383-0515 ● Selection and amount of hardening agents
● Chemistry of the surrounding waters

Soils consolidated with 50% silicate grouts generally achieve a minimum

compressive strength of 50 psi. Much higher compressive strengths are
attainable and have been reported.

Most silicate formulations (with the exception of bicarbonate gelled) are con-
sidered permanent materials6. Geotechnical grouting projects have been
examined after 10 years, and the grouted soils were still intact.

Since silicate grouts typically contain large amounts of water, they may
exhibit shrinkage or syneresis. While this is most commonly found in labora-
tory gelling studies where the grout is not incorporated in the soil matrix,
hardening systems which exhibit greater than 30% shrinkage should be
avoided.
 HARDENERS FOR SILICATE-BASED GROUT
INDUSTRIAL Many hardening or setting agents used with silicates are proprietary in their
CHEMICALS chemical compositions or application techniques. Any discussion of harden-
DIVISION ers and their gelling processes must therefore be general.

The gelling response of a silicate grout is usually temperature dependent.

Though the strength and environmental aspects of a chemical grout are
important, the gel time or pot life of the grout formulation needs to be flexible
enough for practical application in the field. An ideal gelling response is
shown in the figure below7.

.
VICOSITY GEL CURVE AND KIPP NUMBER
(MPa s
or cp)
100

80

60

PQ CORPORATION 40 Kipp
Number
20
CORPORATE HEADQUARTERS 15
PO Box 840 10 20 30 40 50 60 70
Valley Forge, PA 19482-0840 Setting Time (min)
Phone: 800-944-7411
Formulated grout should have an initial viscosity of less than 15 mPa-s (cp)
IN CANADA to insure optimal soil penetration. Viscosity should remain flat until within 2 to
National Silicates
Phone: 416-255-7771 3 minutes of the targeted gel time (40-60 min). The Kipp number is the time
at which the viscosity reaches 100 mPa-s. Setting agents may be organic,
IN MEXICO inorganic or a combination of the two.
Silicates y Derivados, S.A.
Phone: 52-555-227-6801
INORGANIC SETTING AGENTS
IN EUROPE Inorganic setting agents have many advantages. They generally produce the
PQ Europe highest strength grouts, have the least environmental impact and are low in
Phone: 31-33-450-9030 cost. The gel times for these systems are somewhat limited and more
IN AUSTRALIA
expertise is needed in formulating and placing them. Inorganic setting
PQ Australia Pty. Ltd. agents include:
Phone: 61-3-9708-9200
Calcium Chloride Microfine Cements
IN TAIWAN Calcium Hydroxide Portland Cement
PQ Silicates Ltd. Bicarbonates Mineral Acids
Phone: 886-2-2383-0515 Carbon Dioxide Calcium Carbonate
Calcium Oxide Pozzolans
Phosphates Aluminates

Compounds that modify pH and are sources of divalent or multivalent metal

cations also function as setting agents. Many of these compounds also
serve as secondary catalysts or accelerators.

ORGANIC SETTING AGENTS

Organic setting agents react with silicate to form silica gels through pH modi-
fication. These systems are generally much more flexible in their gelling
responses but typically yield lower strengths and tend to be more expensive
than the inorganic setting agents. Frequently used organic materials include:

Ethyl Acetate Terraset®8

Dibasic Ester
.
Propylene Carbonate
Monoacetin Diacetin
Triacetin
 Some of these organic hardening agents may be patented hardener/catalyst
INDUSTRIAL systems. We suggest that you contact the manufacturers of these com-
CHEMICALS pounds for information on intellectual property and health, safety and envi-
DIVISION ronmental issues.

CEMENT-BASED GROUTS
Sodium silicates function as rapid-setting additives for cement and cement-
clay grouts9. Unlike many accelerators, silicates are not corrosive. When
they are added to ordinary cement grouts in small quantities, silicates quick-
ly cause a gel. The gel time depends on the amount and type of silicate
used. In general, the more silicate added, the faster the set.

Cement grouts sometimes cause application problems. They may separate

or settle out due to excessive water bleed. Equipment and manpower may
be idled while waiting for curing to take place. In flooded environments, sur-
rounding water may dilute the grout and prevent it from setting. Sodium sili-
PQ CORPORATION cate can alleviate these problems.
CORPORATE HEADQUARTERS
PO Box 840 In some applications, liquid silicate products such as N® may react too
Valley Forge, PA 19482-0840 quickly with cements. The rate at which a silicate goes into solution in water
Phone: 800-944-7411 determines the set time of the cement grout. Liquid silicates obviously will
generate the fastest set times since they are already in solution. Through
IN CANADA
National Silicates
choice of the appropriate PQ dry silicate, this setting time can be controlled.
Phone: 416-255-7771
Rates of solution for selected PQ sodium silicates
IN MEXICO
Silicates y Derivados, S.A.
Phone: 52-555-227-6801
Product Description Solution Rate
N® liquid immediately
IN EUROPE
PQ Europe METSO® PENTABEAD 20 granules very fast
Phone: 31-33-450-9030 METSO BEADS® 2048 granules fast
GD® powder slow
IN AUSTRALIA
PQ Australia Pty. Ltd. G® powder slower
Phone: 61-3-9708-9200 SS® Powder powder slowest
IN TAIWAN
PQ Silicates Ltd.
Phone: 886-2-2383-0515 ALKALI-ACTIVATED CEMENTS
Alkali-activated cements have been used successfully in Europe for years
for geotechnical applications. They are derived primarily from metal process-
ing slags and are denser and less reactive than conventional Portland
cement.

Their setting method also differs from Portland cement. Less water is need-
ed and addition of an alkali is recommended. Researchers10,11 have found
that using disilicate (GD® sodium silicate) and METSO BEADS® 2048 sodi-
um metasilicate as the alkali source improves physical properties. Both slag
cements and Portland cements are available in a finely ground form, which
increases their penetration into soils and makes them more reactive12.

OSM TECHNOLOGY
Cement grouting in flooded environments has long been a tricky engineering
problem. In response to a request from the Office of Surface Mining (OSM),
PQ developed a technique that enables cement grouts to be placed under-
water. N® liquid silicate is the setting agent.

INDUSTRIAL
CHEMICALS
DIVISION
PQ CORPORATION
CORPORATE HEADQUARTERS
PO Box 840
Valley Forge, PA 19482-0840
Phone: 800-944-7411
IN CANADA
National Silicates
Phone: 416-255-7771
IN MEXICO
Silicates y Derivados, S.A.
Phone: 52-555-227-6801
IN EUROPE
PQ Europe
Phone: 31-33-450-9030
IN AUSTRALIA
PQ Australia Pty. Ltd.
Phone: 61-3-9708-9200
IN TAIWAN
PQ Silicates Ltd.
Phone: 886-2-2383-0515
The technology (U.S. Patent 4,804,297) utilizes a nozzle designed to deliver
silicate and cement grout in such a manner that the grout is not diluted and
dispersed in flooded environments.
Although this technique was originally
implemented for subsidence abatement
in flooded coal mines, it now has a wide
range of applications. It is especially
effective in stopping water. Projects
include the stemming of reservoir leaks,
the shoring of failing breakwaters, and
dam repairs where flows up to 600 gpm
were encountered.13 SILICATE
GROUT
Silicate-cement grout can be tailored to
meet a wide variety of geotechnical chal-
lenges by modifying mix ratios and pumping rates.
Modifications of grout set times
Grout:Silicate
Set Time Use
Ratio by Volume
.1:1 1-10 sec. High flow water blocking
10:1 1-10 min. High angle of repose
support columns or
cutoff walls
30:1 .10-20 min. Penetration into rubble
zones and formation
of column footings
50:1 30 min.-1 hr. Pressure grouting
applications
WASTE TREATMENT AND REMEDIATION
OF CONTAMINATED SOILS
The proliferation of sites where soils are found to be contaminated with haz-
ardous materials has generated public concern. Environmental engineers
have expressed interest in adapting existing geotechnical engineering tech-
niques for in situ soil stabilization and fixation. Silicate chemistry can play an
important role in these developing technologies.
For more information, please refer to Bulletin 52-52, PQ® Soluble Silicates in
Waste Treatment.
ENVIRONMENTAL CONSIDERATIONS
Sodium silicate solutions are generally considered to be non-toxic and non-
corrosive. They are considered to be free of health hazards and environ-
mental effects. However, sodium salts can leach from gelled silicate and
raise the pH of the surrounding environment.14
Some of the organic compounds used as setting agents and their reaction
by-products may have toxic, corrosive and/or environmental effects. Manufac-
turers’ recommendations for handling these products should be followed.
 PQ TECHNICAL SERVICE
INDUSTRIAL Contact your local PQ sales representative or the PQ Industrial Chemicals
CHEMICALS technical service team for further assistance.
DIVISION
NOTES
1. James G. Vail, Soluble Silicates, volume 2, Reinhold Publishing Corp., New York,
1952, pp. 484-488.

2. Reuben H. Karol, Chemical Grouting, 2d edition, Marcel Dekker, Inc., New York, 1990,
p. 143.

3. F.M. Lea, The Chemistry of Cement and Concrete, 1st American edition, Chemical
Publishing Company, New York, 1970, p. 252.

4. Reuben H. Karol, Chemical Grouting, p. 38.

5. Gularte et al., “Tunneling Performance of Chemically Grouted Alluvium and Fill, Los
Angeles Metro Rail, Contract A-130,” Proceedings of the 1991 Rapid Excavation and
PQ CORPORATION Tunneling Conference, AME-ASCE, Port City Press, Baltimore, 1991, p. 295.

CORPORATE HEADQUARTERS 6. Reuben H. Karol, “Chemical Grouts and Their Properties,” Proceedings of the
PO Box 840 Conference on Grouting in Geotechnical Engineering, American Society of Civil
Valley Forge, PA 19482-0840 Engineers, 1982, p. 366.
Phone: 800-944-7411
7. Akzo-PQ Silica, Internal documents, memo Mennings-Delaney, 4/19/92.
IN CANADA
National Silicates 8. Available from FOSROC INC., Celtite Division, Georgetown, K.Y.
Phone: 416-255-7771
9. A.C. Houlsby, Construction and Design of Cement Grouting, John Wiley & Sons, Inc.,
IN MEXICO New York, 1990, p. 65.
Silicates y Derivados, S.A.
Phone: 52-555-227-6801 10. B. Talling and J. Brandstetr, “Present State and Future of Alkali Activated Slag
Concretes,” American Contcrete Institute, SP, 114, (Flyash, Silica fume, Slag, Nat.
IN EUROPE Pozzolans, Concrete, volume II), 1989, pp. 1501-1517.
PQ Europe
Phone: 31-33-450-9030 11. J.S. Falcone, Internal PQ documents, 1989.

IN AUSTRALIA 12. William J. Clarke, “Performance Characteristics of Microfine Cement,” paper presented
PQ Australia Pty. Ltd. at the ASCE Meeting in Atlanta, GA, May 14-18, 1984.
Phone: 61-3-9708-9200
13. Engineering News Record, “Mix Stops Flowing Water in Seconds,” July 20, 1989, pp.
IN TAIWAN 26-27.
PQ Silicates Ltd.
Phone: 886-2-2383-0515 14. Karol, “Chemical Grouts and Their Properties,” p. 367.

PQ, N, GD, METSO, METSO BEADS, G, and SS are registered

trademarks of PQ Corporation.

Although the information and suggestions in this brochure

("information") are believed to be correct, PQ Corporation makes
no representations or warranties as to the completeness or accu-
racy of the information. The information is supplied upon the fol-
lowing conditions: The persons receiving the information will
determine its suitability for their purposes; PQ Corporation will not
be responsible for damages of any nature whatsoever resulting
from the use of, or reliance upon, the information or the materials,
devices or products to which the information refers; No
information is to be construed as a recommendation to use any
product, process, equipment or formulation in conflict with any
patent; PQ Corporation makes no representation or warranty,
express or implied, that the use thereof will not infringe any
patent; and NO REPRESENTATIONS OR WARRANTIES,
EITHER EXPRESS OR IMPLIED, OF MERCHANTABILITY, FIT-
NESS FOR A PARTICULAR PURPOSE OR OF ANY OTHER
NATURE ARE MADE HEREUNDER WITH RESPECT TO INFOR-
MATION OR THE MATERIALS, DEVICES OR PRODUCTS TO
WHICH THE INFORMATION REFERS.

Copyright © 2003 by PQ Corporation.

All rights reserved. No part of this publication may be reproduced,

stored in a retrieval system or transmitted in any form or by any
means electronic, mechanical, photocopying, recording or other-
wise, without the prior permission of the publisher and copyright
holder.

52-53/1203 Printed in U.S.A.