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Recent Silicate Binder Developments
Recent Silicate Binder Developments
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 VOCs. 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
2.
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 1200C. 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 oxygencornered 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
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.
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.
0
76.7
0.05
46.6
0.1
39.9
0.2
34.7
0.4
35.3
Seconds to wet
(darken) fiber
>600
>420
<180
<30
<15
Drop shape
Beads
Beads,
some
spreading
Slightly
flat
Flat
Flat
250
sodium silicate
sodium silicate + 2% KOH
viscosity (cps)
200
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
Water
Sodium silicate
Sodium silicate + water
+ 3% glycol
+2% ester
+ 1% TMAH
3.2
CoF
0.36
0.05
0.40
0.29
0.18
0.30
900
800
700
600
500
400
300
200
100
0
3% of Mix
10% of Mix
3Days
3 Months
4
2S
O
H
4
aS
O
C
co
lic
G
ly
SA
PP
g
aL
i
C
et
ic
Ac
Cl
H
l2
C
aC
180
160
140
120
100
80
60
40
20
0
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
4.
POTASSIUM SILICATE
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
Wt % Alkali
Wt % SiO2
Weight ratio
Molar ratio
pH
Sp. Gr.
Viscosity (cp)
Cation radius of
hydration (nm)6
Lithisil 25
2.5% Li2O
20.5
8.2
4.1
10.8
1.2
20
34.0
Kasil 1
8.3% K2O
20.8
2.5
4.1
11.3
1.26
40
27.6
N
8.9% Na2O
28.7
3.2
3.2
11.2
1.38
180
23.2
Stability
7 Days
<10 min.
3 hours
Gel
40 min.
Gel
>7 days
>7 days
50 min.
15 min.
45 hrs
<10 min
>7 days
3 days
45 min.
Gel
3 days
* 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