Recent Developments in

Soluble Silicate Based Binders and Coatings

Mike McDonald, Janice Hamilton, National Silicates, Toronto, ON, and Judy
Thompson, PQ Corporation, Valley Forge, PA

ABSTRACT

While soluble silicate binders have been used effectively for decades in various
end uses, recent developments and discoveries may improve and expand the
use of silicates. This paper reviews the traditional use and chemistry of sodium
silicate binders and also describes how surfactants, viscosity modifiers,
lubricants and non-traditional setting agents can provide new characteristics and
flexibility in the use of silicate binders. The discussion also includes specialty
uses for potassium and lithium silicates. These developments should further
broaden the range of materials that can be agglomerated using soluble silicate
based binders, thus providing more formulation options.

1. INTRODUCTION

Soluble silicates have been used as binders for many years and in many
applications1,2. In fact, a 1949 reference paper from the PQ library lists 28 ores or
fuels and 10 patents where sodium silicate was used as the binding agent. These
“classic” silicate-based binder formulations either utilize a high SiO2/Na2O sodium
silicate by itself or exploit the setting reaction of sodium silicate with a common
calcium salt or cementitious based material. Iron ore, silica, detergents and
roofing granules are a few examples of materials that have used silicate based
binders and coatings for decades.

Recent trends have tended to favor the traditional advantages of silicate based
binders. As inorganic binders, soluble silicates do not face the handling, safety
and environmental issues associated with NOX and VOC’s. Furthermore, the
pricing of soluble silicates is not subject to the same market fluctuations as
petroleum based or sugar based binders.

Another trend that has favored sodium silicate is the agglomeration of waste or
low value materials into value added products. Typically, these value added
products require a higher level of binder performance such as strength, durability
and water resistance vs. agglomerated material that is to be recycled. An
example of such application is the use of a modified sodium silicate to make
light-weight porous spheres out of recycled container glass3
Recent developments and ideas summarized in this paper address some
improvements that can be made to better utilize soluble silicates including
sodium, potassium and lithium silicates.

2. SILICATE CHEMISTRY REVIEW

Soluble silicates are manufactured by fusing high purity quartz sand (SiO2) with
sodium or potassium carbonate (Na2CO3 or K2CO3) in an open hearth furnace at
1100 – 1200°C. The resulting glass is then dissolved using high pressure steam
to form liquid silicate or “waterglass” which is clear and slightly viscous. The key
parameter that determines the properties of soluble silicate solutions is the
weight ratio of SiO2/Na2O. For example, a “3.2” ratio sodium silicate has 3.2 kg
of SiO2 for every 1kg of Na2O. The typical range of commercially available ratios
is 1.6 to 3.2.

At the molecular level, the fundamental building block of silicate species is the
silica tetrahedron consisting of the silicon atom at the center of an oxygen-
cornered pyramid. Each oxygen atom may be associated with a hydrogen atom
an alkali metal (Na, K, Li), or it may be linked to another silica tetrahedron. The
silica can link to form chains, cyclic and larger polymeric structures. (Figure 1)
The species typically carry an overall negative charge having the monovalent
alkali atoms in loose association.

Monomer Linear Trimer Cyclic Trimer

Figure 1. Monomer Silica Tetrahedron, Linear and Planar Cyclic Silica

Species

Soluble silicates then are inorganic, polymeric, alkaline materials. They are also
moderately strong buffers and can be involved in four basic types of chemical
reactions, each of which can play a role in binder applications. The chemical
reactions are:
 Gelation
 Metal Ion Reactions / Precipitation
 Hydration / Dehydration
 Surface Charge Modification
3. SODIUM SILICATE AS A BINDER

Agglomerated materials require a binder in order to achieve acceptable strength.

In general, binders can be divided into three groups: matrix, film and chemical.4
Sodium silicate is unique in that it can serve in all three of these capacities. For
example, as a matrix binder, sodium silicate would be used in conjunction with
Portland cement or pozzolan blended cement binders. Further discussion on film
forming and chemical binding attributes follows.

3.1 SODIUM SILICATE AS A FILM FORMER

Film forming binders are like glues and function by the evaporation of water or
other solvent. Commercially available sodium silicates contain 45-65% water by
weight. Loss of a small portion of this water, even under ambient conditions, will
result in a strong, rigid, glassy film. Rate of drying will depend on ratio,
concentration, viscosity, film thickness as well as temperature and relative
humidity. The silicate binder may be subject to dissolution depending on use
conditions; however some moisture resistance can be obtained by simply drying
the silicate more completely through the addition of heat.

3.1.1 Surface Tension

Sodium silicate has a naturally high surface tension that is close to that of water
i.e. ~ 76 dynes. The penetration and adhesive quality of soluble silicates can be
improved with surfactant/wetting aids. With reduced surface tension, sodium
silicate can penetrate through smaller openings and spread over a greater area.
Table 1 provides a summary of the physical properties with the addition of an
anionic surfactant. Wetting agents appear to strengthen the bond by increasing
the spread, although if the spread is too great, decrease in bond strength can
result.

Table 1. % Surfactant vs. Surface Tension, Wetting and Drop Shape

% Surfactant 0 0.05 0.1 0.2 0.4

Surface tension* 76.7 46.6 39.9 34.7 35.3

Seconds to wet >600 >420 <180 <30 <15

(darken) fiber
Drop shape Beads Beads, Slightly Flat Flat
some flat
spreading
*Du Noüy Ring method
3.1.2 Viscosity and Texture

An increase in the viscosity of the silicate will decrease the wetting coefficient,
the amount of water absorbed and rate of absorption. Aside from adding water,
the viscosity of sodium silicate can be decreased by the addition of a small
amount of potassium hydroxide or by gently warming the silicate. (Figure 2)

250
sodium silicate

sodium silicate + 2% KOH

200
viscosity (cps)

150

100

50

0
21 30 38 43 50
temperature C
Sodium silicate – 3.2 ratio
KOH ~45% solids

Figure 2. Addition of 45% KOH reduces the viscosity of 3.2 ratio sodium
silicate. Decrease in viscosity as a function of temperature is also shown.

The presence of clay in sodium silicate does not influence the total water loss but
does serve to give a tougher, more coherent film, free of bubbles and drying
cracks. Glycerin and other plasticizers such as sorbitol may also aid by retaining
moisture to produce a smooth film.

3.1.3 Lubrication

Good lubrication properties are important in briquetting because reducing the

particulate friction and improving the flow onto the rolls provide for better and
more efficient compaction. Almost all liquid binders will also act as lubricants;
however some chemicals are better at performing this dual task. High quality,
unadulterated silicate has a very low coefficient of friction (CoF). Regrettably, this
low CoF is lost with the addition of solids and/or water. Other industries using
silicate (the oilfield industry in particular) have expressed a need for soluble
silicate with a lower CoF. Consequently, research was conducted to try to lower
the CoF by either adding a lubricant to the silicate or by chemically modifying the
silicate with respect to how it interacts with metal surfaces.
In developing a lubricant for alkali silicate, the basic criteria included: effective,
compatible with silicate, environmentally friendly and relatively low cost. A wide
range of chemical lubricants was investigated using a block and ring lubricity
tester. These materials included: glycols, olefins, phosphates, surfactants,
glucosides, asphaltenes and esters. Of these, the most effective were ester
based, and to a lesser extent, glycols and certain glucosides. (Table 2) Also
investigated and found effective was the modification of sodium silicate by the
addition of tetralkylammonium compounds such as tetramethyl ammonium
hydroxide (TMAH). It is thought that TMAH reacts with sodium silicate to form
tetramethylammonium silicate with improved lubricity coming via the methyl
groups.

Table 2. Effect of Lubricants on Coefficient of Friction

CoF
Water 0.36
Sodium silicate 0.05
Sodium silicate + water 0.40
+ 3% glycol 0.29
+2% ester 0.18
+ 1% TMAH 0.30

3.2 SODIUM SILICATE AS A CHEMICAL BINDER

Chemical binders function by reacting with the material being agglomerated or by

formulating with multiple components that will react with each other. Sodium
silicate has a long history of being used as a chemical binder. The best example
is the use of sodium silicate with a soluble source of calcium (i.e. the Midrex
process). The reaction of calcium salts with silicate forms calcium silicate
hydrate. Other traditional setting aids used with sodium silicate are shown in
Table 3.

Table 3: Traditional Setting Agents

Category Example
Inorganic Salts CaCl2, Ca(OH)2, Mg(OH)2,
NaH2BO3, Na2CO3
Mineral Acids H2SO4, HCl
Organic Acids CO2, acetic acid, citric acid
Inorganic Oxides ZnO, CaO, MgO

A study was carried out to demonstrate the strength and durability of materials
bound with sodium silicate. Figure 3 shows the benefits of time in developing
strength properties at 3% and 10% of binder matrix.
 900

Compressive Strength kPa

800
700
600
500 3% of Mix
400 10% of Mix
300
200
100
0
3Days 3 Months

Figure 3. Compressive Strength of Sodium Silicate Binder in Limestone

Gravel Matrix

Recently, development efforts have focused on non-traditional setting agents

such as glycolic acid, sodium acid pyrophosphate (SAPP), and calcium
lignosulfonate. The goal was to achieve one or more of the following attributes:

Higher final strength

Better control of set
Longer set
Environmental benefits

Figure 4 provides a compressive strength comparison of the non-traditional

versus other setting agents with 30% concentration sodium silicate in a limestone
gravel matrix at 25°C.
 Compressive Strength kPa
180
160
140
120
100
80
60
40
20
0

lic
Cl

4
ic
l2

4
PP

O
i

O
et

co
aL
aC

2S
SA

aS
Ac

ly
C
C

H
G

C
Figure 4. Compressive Strength Comparison of Setting Agents at 25°C.

Lignin products are used in many applications that are similar to silicate end
uses5. Traditionally, the two technologies have been viewed as competitive.
For example, lignins and silicates are used as dispersants and can sequester
metals. However, recent work has shown that there may be some
complementary applications, particularly for calcium lignosulfonate. A laboratory
study was designed to investigate the interaction between calcium lignosulfonate
and silicates over a range of concentrations. The interactive effects were
observed with both sodium and potassium silicates. The results of this work
showed that the setting characteristics of these systems were not typical of the
rapid interaction seen with other calcium salts and allowed for much more
flexibility in the binding process. Table 5 shows the setting effects of mixing
calcium lignosulfonate with sodium silicate. Calcium lignosulfonate is available as
a solid or liquid (~50% solids) and either form can be used with silicates.

Table 5: Setting Times of Sodium Silicate with Calcium Lignosulfonate

Sodium Silicate N Calcium Lignosulfonate Setting Time
(3.2 ratio) %w/w %w/w
5 5 3hr
5 10 4-5 min
10 25 1-2 min

At present, sodium silicate remains the workhorse of silicates for binder

applications primarily because it is the least expensive of the alkali silicates. For
specialty applications, however, there may be justification to use potassium or
lithium silicate as highlighted below in the following paragraphs.
 4. POTASSIUM SILICATE

Potassium silicate is typically used when sodium is undesirable for a particular

end use. For example, potassium silicate is preferred for the clays and fluxing
materials used in welding rod applications. It is also used to bind vanadium
pentoxide catalysts for sulfuric acid manufacture and in acid-resistant cements.
More recently potassium silicate is being considered as a binder for fertilizer
applications. In this case, the more soluble potassium silicate can strengthen
prills or pellets but then dissolve in use to release the nutrients of the fertilizer
while providing additional potassium and silicon for plants. Potassium is a
primary plant nutrient, and silicon has gained significant recognition as a
beneficial plant nutrient that helps to physically strengthen plant tissue as well as
improve nutrient uptake and alleviate salt and drought stress.

5. LITHIUM SILICATE

Lithium silicate is a specialty silicate that is now being manufactured in the US.
The properties of lithium silicate are intermediate between those of sodium
silicate and organic ammonium silicates. The difference in properties between
lithium and sodium silicate can be ascribed to the fact that hydrated lithium ion is
larger than the hydrated sodium ion and therefore can stabilize more silica in the
colloidal state. Table 6 provides a comparison between high ratio lithium,
potassium and sodium silicate.

Table 6: Property Comparison of Various High Ratio Alkali Silicates

Lithisil 25 Kasil 1 N
Wt % Alkali 2.5% Li2O 8.3% K2O 8.9% Na2O
Wt % SiO2 20.5 20.8 28.7
Weight ratio 8.2 2.5 3.2
Molar ratio 4.1 4.1 3.2
pH 10.8 11.3 11.2
Sp. Gr. 1.2 1.26 1.38
Viscosity (cp) 20 40 180
Cation radius of 34.0 27.6 23.2
hydration (nm)6

Compared to sodium and potassium silicate binders, certain surfaces can

achieve better adhesion with lithium silicate. As a binder or coating, lithium
silicate can also impart high levels of strength and water resistance. While lithium
silicate is considerably more expensive than sodium silicate, improvements in
adhesion can also be seen when a small amount of lithium silicate is blended
with sodium or potassium silicate7.
Lithium silicates are somewhat compatible with water-miscible organic solvents
and slightly compatible with non-polar solvents (Table 7). This behavior is
different from that of sodium silicate solutions which are not compatible with
organic solvents to any extent at comparable SiO2 concentrations. Lithium
silicate would allow for better bonding of material covered with organic solvents.

Table 7. Compatibility of Lithium Silicate with Water-Miscible Organic

Solvents

Composition Final
Solvent Mixture Stability
% SiO2 % Solvent
5.06 Mole Ratio Lithium Silicate
Methanol 18.5 7.1 7 Days
17.9 10.0 <10 min.
13.7* 19.7 3 hours
Ethanol 19.0 4.4 Gel
Acetone 17.9 10.2 40 min.
Dioxane 19.9 ------ Gel
Tetrahydrofura 19.2 3.5 >7 days
n 19.0 4.2 >7 days
7.52 Mole Ratio Lithium Silicate
Methanol 20.3 11.3 50 min.
19.2 15.7 15 min.
13.4* 18.0 45 hrs
Ethanol 19.6 8.8 <10 min
15.5* 5.7 >7 days
Acetone 18.8 12.3 3 days
Acetone 13.3* 19.0 45 min.
Dioxane 19.9 7.4 Gel
Tetrahydrofura 20.0 6.7 3 days
n

* From stock lithium silicate solutions containing about 17% SiO2. All
others from stock solutions containing about 20% SiO2

ACKNOWLEDGEMENT
The authors would like to thank PQ Corporation and National Silicates for
permission to publish this paper.

BIBLIOGRAPHY

1. W.L. Schleyer, “Sodium Silicate As A Briquetting Binder”,

Proceedings of the 9th Biennial Briquetting Conference, 1965
2. R.E. Wright, “Smelter Dust Agglomeration with Sodium Silicate”,
Proceedings of the 15th Biennial Conference of IBA, 1977
3. United States Patent 4430107
4. “Selecting Binders and Lubricants for Agglomeration Processes” by
Karl R. Komarek (Chemical Engineering Magazine, December, 1967)
5. SRI Consulting, 2005 Chemical Economics Handbook
6. .“Synthetic Inorganic Silicates,” Encyclopedia of Chemical
Technology, Vol. 18, 2nd ed., 1969 by John Wiley & Sons, Inc., p150.
7. US Patent 4,347,890; Allyn-Pyzik & Falcone, PQ Corp