SODIUM SILICATE
Sodium silicate is a generic name
for chemical compounds with the formula sodium metasilicate (Na2SiO3), sodium orthosilicate (Na4SiO4),
and sodium pyrosilicate (Na6Si2O7).
The anions are often polymeric. These compounds are generally colorless
transparent solids or white powders, and soluble in water in various amounts.
Sodium silicate is also the technical and
common name for a mixture of such compounds, chiefly the metasilicate, also
called waterglass, water glass, or liquid glass. The product has
a wide variety of uses, including the formulation of cements, coatings, passive fire protection, textile and lumber processing, manufacture
of refractory ceramics, as adhesives, and in the production of silica gel. The commercial product, available in water solution or in solid form, is often greenish or
blue owing to the presence of iron-containing impurities.
In industry, the various grades of sodium silicate are
characterized by their SiO2:Na2O weight ratio (which can
be converted to molar ratio by multiplication with 1.032). The ratio can vary
between 1:2 and 3.75:1. Grades with ratio below 2.85:1 are termed
alkaline. Those with a higher SiO2:Na2O ratio are
described as neutral.
Properties
Sodium silicates are colorless glassy or
crystalline solids, or white powders. Except for the most silicon-rich ones,
they are readily soluble in water, producing alkaline solutions. When dried up it still
can be rehydrated in water. Sodium silicates are stable in neutral and alkaline solutions. In acidic solutions,
the silicate ions react with hydrogen ions to
form silicic acids, which tend to decompose into hydrated silicon dioxide gel. Heated
to drive off the water, the result is a hard translucent substance called silica gel, widely used as a desiccant. It can withstand temperatures up to
1100 °C.
Production
Solutions of sodium silicates can be produced
by treating a mixture of silica (usually
as quartz sand), caustic soda, and water, with hot steam in a reactor. The overall reaction is
2x NaOH+ SiO2 → (Na2O)x·SiO2 + x H2O
Sodium silicates can also be obtained by
dissolving silica SiO2 (whose melting point is 1713 °C) in molten sodium carbonate (that melts with decomposition at
851 °C):
x Na2CO3 + SiO2 → (Na2O)x·SiO2 + CO2
The material can be obtained also from sodium sulfate (melting point 884 °C) with carbon as
a reducing agent:
2x Na2SO4 +C+2 SiO2 →2 (Na2O)x·SiO2 +2 SO2 + CO2
In 1990, 4 million tons of
alkali metal silicates were produced.
Ferrosilicon
Sodium silicate may be produced as a part
of hydrogen production by dissolving ferrosilicon in an aqueous sodium hydroxide (NaOH·H2O) solution:
2NaOH + Si + H2O → 2Na2SiO3 +
2H2
Bayer process
Though unprofitable, Na2SiO3 is
a byproduct of Bayer process which is often converted to calcium silicate (Ca2SiO4).
Uses
The main applications of sodium silicates are
in detergents, paper industry (as a deinking agent), water treatment, and
construction materials.
Adhesives
The adhesive properties of sodium silicate
were noted as early as the 1850s and have been widely used at least since
the First World War. The largest application of sodium
silicate solutions is a cement for producing cardboard. When used as a paper cement, the sodium
silicate joint tends to crack within a few years, at which point it no longer
holds the paper surfaces cemented together. Sodium silicate solutions can also
be used as a spin-on adhesive layer to bond glass to glass or a silicon
dioxide–covered silicon wafer to one another. Sodium silicate glass-to-glass bonding
has the advantage that it is a low-temperature bonding technique, as opposed to
fusion bonding. It also requires less processing than glass-to-glass
anodic bonding, which requires an intermediate layer such as silicon nitride (SiN) to act as a diffusion barrier for
sodium ions. The deposition of such a layer requires a low-pressure
chemical vapor deposition step. A disadvantage of sodium silicate bonding,
however, is that it is very difficult to eliminate air bubbles. This is in
part because the technique does not require a vacuum and also does not use
field assistance as in anodic bonding. This lack of field assistance
can sometimes be beneficial, because field assistance can provide such high
attraction between wafers as to bend a thinner wafer and collapse onto
nanofluidic cavity or MEMS elements.
Coatings
Sodium silicate may be used for various paints
and coatings, such as those used on welding rods. Such coatings can be cured in two ways. One
method is to heat a thin layer of sodium silicate into a gel and then into a
hard film. To make the coating water-resistant, high temperatures of 100 °C
(212 °F; 373 K) are needed. The temperature is slowly raised to
150 °C (302 °F; 423 K) to dehydrate the film and avoid steaming
and blistering. The process must be relatively slow, but infrared lamps may be
used at first. In the other method, when high temperatures are not
practical, the water resistance may be achieved by chemicals (or esters),
such as boric acid, phosphoric acid, sodium fluorosilicate, and aluminium phosphate. Before application, an aqueous solution
of sodium silicate is mixed with a curing agent. It is used in detergent
auxiliaries such as complex sodium disilicate and modified sodium disilicate.
The detergent granules gain their ruggedness from a coating of silicates.
Water treatment
Sodium silicate is used as an alum coagulant
and an iron flocculant in wastewater treatment plants. Sodium silicate binds to colloidal molecules, creating larger aggregates that sink to the bottom of the water
column. The microscopic negatively charged particles suspended in water
interact with sodium silicate. Their electrical double layer collapses due to the increase of ionic strength caused by the addition of sodium silicate
(doubly negatively charged anion accompanied by two sodium cations) and they
subsequently aggregate. This process is called coagulation.
Foundries, refractories and pottery
It is used as a binder of the sand when
doing sand casting of all common metals. It allows for the
rapid production of a strong mold or core by three main methods.
· Method 1 requires passing carbon dioxide gas through the mixture of sand and sodium silicate in the sand molding box or core box. The carbon dioxide reacts with the sodium silicate to form solid silica gel and sodium carbonate. This provides adequate strength to remove the now hardened sand shape from the forming tool. Additional strength occurs as any unreacted sodium silicate in the sand shape dehydrates.
· Method 2 requires adding an ester (reaction product of an acid and an alcohol) to the mixture of sand and sodium silicate before it is placed into the molding box or core box. As the ester hydrolyzes from the water in the liquid sodium silicate, an acid is released which causes the liquid sodium silicate to gel. Once the gel has formed, it will dehydrate to a glassy phase as a result of syneresis. Commonly used esters include acetate esters of glycerol and ethylene glycol as well as carbonate esters of propylene and ethylene glycol. The higher the water solubility of the ester, the faster the hardening of the sand.
· Method 3 requires microwave energy to heat and dehydrate the mixture of sand and sodium silicate in the sand molding box or core box. The forming tools must pass through microwaves for this to work well. Because sodium silicate has a high dielectric constant, it absorbs microwave energy very rapidly. Fully dehydrated sand shapes can be produced within a minute of microwave exposure. This method produces the highest strength of sand shapes bonded with sodium silicate.
Since the sodium silicate does not burn during
casting (it can actually melt at pouring temperatures above 1800 °F), it
is common to add organic materials to provide for enhanced sand breakdown after
casting. The additives include sugar, starch, carbons, wood flour and phenolic
resins.
Water glass is a useful binder for solids,
such as vermiculite and perlite. When blended with the latter lightweight
fraction, water glass can be used to make hard, high-temperature insulation
boards used for refractories, passive fire protection, and high-temperature insulations, such as in
moulded pipe insulation applications. When mixed with finely divided mineral
powders, such as vermiculite dust (which is common scrap from the exfoliation
process), one can produce high temperature adhesives. The intumescence disappears
in the presence of finely divided mineral dust, whereby the waterglass becomes
a mere matrix. Waterglass is inexpensive and abundantly available, which makes
its use popular in many refractory applications.
Sodium silicate is used as a deflocculant in casting slips helping reduce viscosity and the need for large amounts of water
to liquidize the clay body. It is also used to create a crackle effect in
pottery, usually wheel-thrown. A vase or bottle is thrown on the wheel, fairly
narrow and with thick walls. Sodium silicate is brushed on a section of the
piece. After five minutes, the wall of the piece is stretched outward with a
rib or hand. The result is a wrinkled or cracked look.
It is also the main agent in "magic
water", which is used when joining clay pieces, especially if the moisture
level of the two differs.
Dyes
Sodium silicate solution is used as a fixative
for hand dyeing with reactive dyes that require a high pH to react with the
textile fiber. After the dye is applied to a cellulose-based fabric, such as
cotton or rayon, or onto silk, it is allowed to dry, after which the sodium
silicate is painted on to the dyed fabric, covered with plastic to retain
moisture, and left to react for an hour at room temperature.
Repair work
Sodium silicate is used, along with magnesium silicate, in muffler repair and fitting paste. When dissolved
in water, both sodium silicate and magnesium silicate form a thick paste that
is easy to apply. When the exhaust system of an internal combustion engine heats
up to its operating temperature, the heat drives out all of the excess water
from the paste. The silicate compounds that are left over have
glass-like properties, making a temporary, brittle repair.
Sodium silicate is also used currently as an
exhaust system joint and crack sealer for repairing mufflers, resonators,
tailpipes, and other exhaust components, with and without fiberglass
reinforcing tapes. In this application, the sodium silicate (60–70%) is
typically mixed with kaolin (40–30%),
an aluminium silicate mineral, to make the sodium silicate "glued"
joint opaque. The sodium silicate, however, is the high-temperature adhesive;
the kaolin serves simply as a compatible high-temperature coloring agent. Some
of these repair compounds also contain glass fibres to enhance their
gap-filling abilities and reduce brittleness.
Sodium silicate can be used to fill gaps in
the head gasket of an engine. This is especially useful
for aluminum alloy cylinder heads, which are sensitive to thermally induced
surface deflection. Sodium silicate is added to the cooling system through
the radiator and allowed to circulate. When the
sodium silicate reaches its "conversion" temperature of
100–105 °C (212–221 °F), it loses water molecules and forms a glass
seal with a re-melting temperature above 810 °C (1,490 °F). This
repair can last two years or longer, and symptoms disappear instantly. However,
this repair works only when the sodium silicate reaches its
"conversion" temperature. Also, sodium silicate (glass particulate)
contamination of lubricants is detrimental to their function, and contamination
of engine oil is a serious possibility in situations in which a coolant-to-oil
leak is present.
Sodium silicate solution is used to
inexpensively, quickly, and permanently disable automobile engines. Running an
engine with half a U.S. gallon (or about two liters) of a sodium silicate
solution instead of motor oil causes the solution to precipitate, catastrophically damaging the engine's
bearings and pistons within a few minutes. In the United States, this
procedure was used to comply with requirements of the Car Allowance Rebate System (CARS) program.
Construction
A mixture of sodium silicate and sawdust has been used in between the double skin
of certain safes. This not only makes them more fire resistant, but also makes cutting them open with
an oxyacetylene torch extremely difficult due to the smoke emitted.
Sodium silicate is frequently used in drilling fluids to stabilize and avoid the collapse
of borehole walls. It is particularly useful when
drill holes pass through argillaceous formations containing swelling clay minerals such as smectite or montmorillonite. Concrete treated with a sodium silicate solution
helps to reduce porosity in most masonry products such as concrete, stucco,
and plasters. This effect aids in reducing water
penetration, but has no known effect on reducing water vapor transmission and
emission. A chemical reaction occurs with the
excess Ca(OH)2 (portlandite) present in the concrete that permanently
binds the silicates with the surface, making them far more durable and water
repellent. This treatment generally is applied only after the initial cure has taken place (approximately seven
days depending on conditions). These coatings are known as silicate mineral paint. An example of the reaction of sodium
silicate with the calcium hydroxide found in concrete to form calcium silicate hydrate (CSH) gel, the main product in hydrated
Portland cement, follows.
Na2SiO3 + yH2O + xCa(OH)2 → xCaO.SiO2.yH2O + 2NaOH
Crystal gardens
When crystals of a number of metallic salts
are dropped into a solution of water glass, simple or branching stalagmites of colored metal silicates are formed. This
phenomenon has been used by manufacturers of toys and chemistry sets to provide
instructive enjoyment to many generations of children from the early 20th
century until the present. An early mention of crystals of metallic salts
forming a "chemical garden" in sodium silicate is found in the
1946 Modern Mechanix magazine. Metal salts used included
the sulfates and/or chlorides of copper, cobalt, iron, nickel, and manganese.
Sealants
Sodium silicate with additives was injected
into the ground to harden it and thereby to prevent further leakage of highly
radioactive water from the Fukushima Daiichi
nuclear power plant in
Japan in April, 2011. The residual heat carried by the water used for
cooling the damaged reactors accelerated the setting of the injected mixture.
On June 3, 1958, the USS Nautilus, the world's first nuclear submarine, visited
Everett and Seattle. In Seattle, crewmen dressed in civilian clothing were sent
in to secretly buy 140 quarts (160 liters) of an automotive product containing
sodium silicate (originally identified as Stop Leak) to repair a leaking
condenser system. The Nautilus was en route to the North Pole
on a top secret mission to cross the North Pole submerged.
Firearms
A historical use of the adhesive properties of
sodium silicates is the production of paper cartridges for black powder revolvers produced
by Colt's Manufacturing Company between 1851 and 1873, especially during
the American Civil War. Sodium silicate was used to seal combustible
nitrated paper together to form a conical paper cartridge to hold the black
powder, as well as to cement the lead ball or conical bullet into the open end
of the paper cartridge. Such sodium silicate cemented paper cartridges were
inserted into the cylinders of revolvers, thereby speeding the reloading of
cap-and-ball black powder revolvers. This use largely ended with the
introduction of Colt revolvers employing brass-cased cartridges starting in
1873. Similarly, sodium silicate was also used to cement the top wad into
brass shotgun shells, thereby eliminating any need for a crimp at
the top of the brass shotgun shell to hold a shotgun shell together. Reloading
brass shotgun shells was widely practiced by self-reliant American farmers
during the 1870s, using the same waterglass material that was also used to
preserve eggs. The cementing of the top wad on a shotgun shell consisted of
applying from three to five drops of waterglass on the top wad to secure it to
the brass hull. Brass hulls for shotgun shells were superseded by paper hulls
starting around 1877. The newer paper-hulled shotgun shells used a roll crimp
in place of a waterglass-cemented joint to hold the top wad in the shell.
However, whereas brass shotshells with top wads cemented with waterglass could
be reloaded nearly indefinitely (given powder, wad, and shot, of course), the
paper hulls that replaced the brass hulls could be reloaded only a few times.
Food and medicine
Sodium silicate and other silicates are the
primary components in "instant" wrinkle remover creams, which
temporarily tighten the skin to minimize the appearance of wrinkles and
under-eye bags. These creams, when applied as a thin film and allowed to dry
for a few minutes, can present dramatic results. This effect is not permanent,
lasting from a few minutes up to a couple of hours. It works like water cement,
once the muscle starts to move, it cracks and leaves white residues on the
skin.
Waterglass has been used as an egg
preservative with large success, primarily when refrigeration is not available.
Fresh-laid eggs are immersed in a solution of sodium silicate (waterglass).
After being immersed in the solution, they are removed and allowed to dry. A
permanent air tight coating remains on the eggs. If they are then stored in
appropriate environment, the majority of bacteria which would otherwise cause
them to spoil are kept out and their moisture is kept in. According to the
cited source, treated eggs can be kept fresh using this method for up to five
months. When boiling eggs preserved that way, the shell is no longer permeable
to air, and the egg will tend to crack unless a hole in the shell is made
(e.g., with a pin) in order to allow steam to escape.
Sodium silicate's flocculant properties are also used to clarify wine
and beer by precipitating colloidal particles. As a clearing agent, though,
sodium silicate is sometimes confused with isinglass which is prepared from collagen extracted from the dried swim bladders of sturgeon and other fishes. Eggs can be preserved
in a bucket of waterglass gel, and their shells are sometimes also used (baked
and crushed) to clear wine.
Sodium silicate gel is also used as a
substrate for algal growth in aquaculture hatcheries.