Sodium silicate

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Sodium silicate is a generic name for chemical compounds with the formula Na
2x
Si
y
O
2y+x
or (Na
2
O)
x
·(SiO
2
)
y
, such as sodium metasilicate Na
2
SiO
3
, sodium orthosilicate Na
4
SiO
4
, and sodium pyrosilicate Na
6
Si
2
O
7
. The anions are often polymeric. These compounds are generally colorless transparent solids or white powders, and soluble in water in various amounts.

Contents

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, 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 2:1 and 3.75:1. [1] Grades with ratio below 2.85:1 are termed alkaline. Those with a higher SiO2:Na2O ratio are described as neutral.

History

Soluble silicates of alkali metals (sodium or potassium) were observed by European alchemists already in the 1500s. Giambattista della Porta observed in 1567 that tartari salis (cream of tartar, potassium hydrogen tartrate) caused powdered crystallum (quartz) to melt at a lower temperature. [2] Other possible early references to alkali silicates were made by Basil Valentine in 1520, [3] and by Agricola in 1550. Around 1640, Jean Baptist van Helmont reported the formation of alkali silicates as a soluble substance made by melting sand with excess alkali, and observed that the silica could be precipitated quantitatively by adding acid to the solution. [4]

In 1646, Glauber made potassium silicate, that he termed liquor silicum by melting potassium carbonate (obtained by calcinating cream of tartar) and sand in a crucible, and keeping it molten until it ceased to bubble (due to the release of carbon dioxide). The mixture was allowed to cool and then was ground to a fine powder. When the powder was exposed to moist air, it gradually formed a viscous liquid, which Glauber called "Oleum oder Liquor Silicum, Arenæ, vel Crystallorum" (i.e., oil or solution of silica, sand or quartz crystal). [5] [6]

However, it was later claimed that the substances prepared by those alchemists were not waterglass as it is understood today. [7] [8] [9] That would have been prepared in 1818 by Johann Nepomuk von Fuchs, by treating silicic acid with an alkali; the result being soluble in water, "but not affected by atmospheric changes". [10] [11]

The terms "water glass" and "soluble glass" were used by Leopold Wolff in 1846, [12] , by Émile Kopp in 1857, [13] and by Hermann Krätzer in 1887. [14]

In 1892, Rudolf Von Wagner distinguished soda, potash, double (soda and potash), and fixing (i.e., stabilizing) as types of water glass. The fixing type was "a mixture of silica well saturated with potash water glass and a sodium silicate" used to stabilize inorganic water color pigments on cement work for outdoor signs and murals. [15] [16] [17] [18]

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.

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 [19] 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 [20]

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 + SiO
2
(Na
2
O)
x
·SiO
2
+ xH
2
O

Sodium silicates can also be obtained by dissolving silica SiO
2
(whose melting point is 1713 °C) in molten sodium carbonate (that melts with decomposition at 851 °C): [21]

xNa
2
CO
3
+ SiO
2
(Na
2
O)
x
·SiO
2
+ CO
2

The material can be obtained also from sodium sulfate (melting point 884 °C) with carbon as a reducing agent:

2xNa
2
SO
4
+ C + 2 SiO
2
→ 2 (Na
2
O)
x
·SiO
2
+ 2 SO
2
+ CO
2

In 1990, 4 million tons of alkali metal silicates were produced. [1]

Uses

The main applications of sodium silicates are in detergents, paper, water treatment, and construction materials. [1]

Engineering

Adhesive

The largest application of sodium silicate solutions is a cement for producing cardboard. [1] When used as a paper cement, the tendency is for the sodium silicate joint eventually to crack within a few years, at which point it no longer holds the paper surfaces cemented together.

Drilling fluids

Sodium silicate is frequently used in drilling fluids to stabilize borehole walls and to avoid the collapse of bore walls. It is particularly useful when drill holes pass through argillaceous formations containing swelling clay minerals such as smectite or montmorillonite.

Concrete and general masonry treatment

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. [22] 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 (7 days or so depending on conditions). These coatings are known as silicate mineral paint.

Detergent auxiliaries

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. [1]

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. [1]

Refractory use

Water glass is a useful binder of solids, such as vermiculite and perlite. When blended with the aforementioned lightweight aggregates, water glass can be used to make hard, high-temperature insulation boards used for refractories, passive fire protection and high temperature insulations, such as 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.

Sand casting

It is used as a binder of the sand when doing sand casting of iron or steel. It allows the rapid production of a strong mold, by passing CO2 through the mixture of sand and sodium silicate in the mold box, which hardens it almost instantly.

Dye auxiliary

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. [23]

Passive fire protection

Expantrol proprietary sodium silicate suspended in about a 6.5-mm-thick layer of red rubber, type 3M FS195, inserted into a metal pipe, then heated, to demonstrate hard char intumescence, strong enough to shut a melting plastic pipe Fs195.jpg
Expantrol proprietary sodium silicate suspended in about a 6.5-mm-thick layer of red rubber, type 3M FS195, inserted into a metal pipe, then heated, to demonstrate hard char intumescence, strong enough to shut a melting plastic pipe
Palusol-based intumescent plastic pipe device used for commercial firestopping Palusolmanschette.jpg
Palusol-based intumescent plastic pipe device used for commercial firestopping

Sodium silicates are inherently intumescent. They come in prill (solid beads) form, as well as the liquid, water glass. The solid sheet form (Palusol) must be waterproofed to ensure long-term passive fire protection (PFP).

Standard, solid, bead-form sodium silicates have been used as aggregate within silicone rubber to manufacture plastic pipe firestop devices. The silicone rubber was insufficient waterproofing to preserve the intumescing function and the products had to be recalled, which is problematic for firestops concealed behind drywall in buildings.

Pastes for caulking purposes are similarly unstable. This, too, has resulted in recalls and even litigation. Only 3M's "Expantrol" version, which has an external heat treatment that helps to seal the outer surface, as part of its process standard, has achieved sufficient longevity to qualify for DIBt approvals in the US for use in firestopping.

Not unlike other intumescents, sodium silicate, both in bead form and in liquid form, are inherently endothermic, due to liquid water in the water glass and hydrates in the prill form. The absence in the US of mandatory aging tests, whereby PFP systems are made to undergo system performance tests after the aging and humidity exposures, are at the root of the continued availability, in North America, of PFP products that can become inoperable within weeks of installation. Indiscriminate use of sodium silicates without proper waterproofing measures are contributors to the problems and risk. When sodium silicates are adequately protected, they function extremely well and reliably for long periods. Evidence of this can be seen in the many DIBt approvals for plastic pipe firestop devices using Palusol (a product of BASF), which use waterproofed sodium silicate sheets.

Metal repair

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.

Automotive 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 within the head gasket. Commonly used on aluminum alloy cylinder heads, which are sensitive to thermally induced surface deflection. This can be caused by many things including head-bolt stretching, deficient coolant delivery, high cylinder head pressure, overheating, etc.

"Liquid glass" (sodium silicate) is added to the system through the radiator, and allowed to circulate. Sodium silicate is suspended in the coolant until it reaches the cylinder head. At 100–105°C (212-221°F), sodium silicate loses water molecules to form a glass seal with a remelt temperature above 810°C (1,490°F).

A sodium silicate repair can last two years or longer. The repair occurs rapidly, and symptoms disappear instantly. This repair works only when the sodium silicate reaches its "conversion" temperature at 100–105°C. Contamination of engine oil is a serious possibility in situations in which a coolant-to-oil leak is present. Sodium silicate (glass particulate) contamination of lubricants is detrimental to their function.

Sodium silicate solution is used to inexpensively, quickly, and permanently disable automobile engines. Running an engine with about 2 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. [24] In the United States, this procedure was used to comply with requirements of the Car Allowance Rebate System (CARS) program. [24] [25]

Safe 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.

Crystal gardens

When crystals of a number of metallic salts are dropped into a solution of water glass, simple or branching stalagmites of coloured 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. [26] Metal salts used included the sulfates and/or chlorides of copper, cobalt, iron, nickel, and manganese.

Pottery

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 5 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. [27]

Sealing of leaking water-containing structures

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. [28] 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 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. [29]

Firearm cartridges

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 during the period from 1851 until 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. [30] [31] 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

While not actually a medical use, 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 & under-eye bags. These creams, when applied as a thin film and allowed to dry for a few minutes, can present dramatic results. Unfortunately, it is not permanent, lasts few minutes or couple of hours. It works like water cement, once the muscle starts to move, it cracks and leaves white residues on the skin.

Food preservation

World War I poster suggesting the use of waterglass to preserve eggs (lower right). "Raise More Poultry...on Farms and Back Yards...More Eggs and Poultry Will save Beef and Pork." - NARA - 512571.tif
World War I poster suggesting the use of waterglass to preserve eggs (lower right).

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 were 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 so preserved, 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. [32]

Homebrewing

Sodium silicate 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 preserved in a bucket of waterglass gel, and their shells are sometimes also used (baked and crushed) to clear wine. [33]

Aquaculture

Sodium silicate gel is also used as a substrate for algal growth in aquaculture hatcheries. [34]

See also

Related Research Articles

Silicate class of chemical compounds, salts and esters of silicic acids

In chemistry, a silicate is any member of a family of anions consisting of silicon and oxygen, usually with the general formula [SiO(4−2x)−
4−x
]
n
, where 0 ≤ x < 2. The family includes orthosilicate SiO4−
4
, metasilicate SiO2−
3
, and pyrosilicate Si
2
O6−
7
. The name is also used for any salt of such anions, such as sodium metasilicate; or any ester containing the corresponding chemical group, such as tetramethyl orthosilicate.

Silicon dioxide chemical compound

Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula SiO2, most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and most abundant families of materials, existing as a compound of several minerals and as synthetic product. Notable examples include fused quartz, fumed silica, silica gel, and aerogels. It is used in structural materials, microelectronics (as an electrical insulator), and as components in the food and pharmaceutical industries.

Sodium hydroxide Chemical compound with formula NaOH

Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations Na+
and hydroxide anions OH
.

Base (chemistry) substance that can react with an acid, accepting hydrogen ions (protons) or more generally, donating a pair of valence electrons

In chemistry, bases are substances that, in aqueous solution, release hydroxide (OH) ions, are slippery to the touch, can taste bitter if an alkali, change the color of indicators (e.g., turn red litmus paper blue), react with acids to form salts, promote certain chemical reactions (base catalysis), accept protons from any proton donor or contain completely or partially displaceable OH ions. Examples of bases are the hydroxides of the alkali metals and the alkaline earth metals (NaOH, Ca(OH)2, etc.—see alkali hydroxide and alkaline earth hydroxide).

Sodium carbonate chemical compound

Sodium carbonate, Na2CO3, (also known as washing soda, soda ash and soda crystals) is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, water-soluble salts. All forms have a strongly alkaline taste and give moderately alkaline solutions in water. Historically it was extracted from the ashes of plants growing in sodium-rich soils. Because the ashes of these sodium-rich plants were noticeably different from ashes of wood (once used to produce potash), sodium carbonate became known as "soda ash". It is produced in large quantities from sodium chloride and limestone by the Solvay process.

The Bayer process is the principal industrial means of refining bauxite to produce alumina (aluminium oxide) and was developed by Carl Josef Bayer. Bauxite, the most important ore of aluminium, contains only 30–60% aluminium oxide (Al2O3), the rest being a mixture of silica, various iron oxides, and titanium dioxide. The aluminium oxide must be purified before it can be refined to aluminium metal.

Soda lime

Soda lime is a mixture of NaOH & CaO chemicals, used in granular form in closed breathing environments, such as general anaesthesia, submarines, rebreathers and recompression chambers, to remove carbon dioxide from breathing gases to prevent CO2 retention and carbon dioxide poisoning.

Sodium oxide is a chemical compound with the formula Na2O. It is used in ceramics and glasses. The compound is the base anhydride of sodium hydroxide; when water is added to sodium oxide, NaOH is produced.

Potassium silicate chemical compound

Potassium silicate is the name for a family of inorganic compounds. The most common potassium silicate has the formula K2SiO3, samples of which contain varying amounts of water. These are white solids or colorless solutions.

Sodium metasilicate chemical compound

Sodium metasilicate is the chemical substance with formula Na
2
SiO
3
, which is the main component of commercial sodium silicate solutions. It is an ionic compound consisting of sodium cations Na+
and the polymeric metasilicate anions [–SiO2−
3
–]n. It is a colorless crystalline hygroscopic and deliquescent solid, soluble in water, but not in alcohols.

Geopolymers are inorganic, typically ceramic, materials that form long-range, covalently bonded, non-crystalline (amorphous) networks. Obsidian fragments are a component of some geopolymer blends. Commercially produced geopolymers may be used for fire- and heat-resistant coatings and adhesives, medicinal applications, high-temperature ceramics, new binders for fire-resistant fiber composites, toxic and radioactive waste encapsulation and new cements for concrete. The properties and uses of geopolymers are being explored in many scientific and industrial disciplines: modern inorganic chemistry, physical chemistry, colloid chemistry, mineralogy, geology, and in other types of engineering process technologies. Geopolymers are part of polymer science, chemistry and technology that forms one of the major areas of materials science. Polymers are either organic material, i.e. carbon-based, or inorganic polymer, for example silicon-based. The organic polymers comprise the classes of natural polymers, synthetic organic polymers and natural biopolymers. Raw materials used in the synthesis of silicon-based polymers are mainly rock-forming minerals of geological origin, hence the name: geopolymer. Joseph Davidovits coined the term in 1978 and created the non profit French scientific institution Institut Géopolymère.

Alkali–silica reaction Expansive chemical reaction damaging concrete

The alkali–silica reaction (ASR), more commonly known as "concrete cancer", is a swelling reaction that occurs over time in concrete between the highly alkaline cement paste and the reactive non-crystalline (amorphous) silica found in many common aggregates, given sufficient moisture.

Dealkalization is a process of surface modification applicable to glasses containing alkali ions, wherein a thin surface layer is created that has a lower concentration of alkali ions than is present in the underlying, bulk glass. This change in surface composition commonly alters the observed properties of the surface, most notably enhancing corrosion resistance.

Compounds of oxygen any chemical compound having at least one oxygen atom

The oxidation state of oxygen is −2 in almost all known compounds of oxygen. The oxidation state −1 is found in a few compounds such as peroxides. Compounds containing oxygen in other oxidation states are very uncommon: −​12 (superoxides), −​13 (ozonides), 0, +​12 (dioxygenyl), +1, and +2.

Colloidal silicas are suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase.

Porous glass is glass that includes pores, usually in the nanometre- or micrometre-range, commonly prepared by one of the following processes: through metastable phase separation in borosilicate glasses (such as in their system SiO2-B2O3-Na2O), followed by liquid extraction of one of the formed phases; through the sol-gel process; or simply by sintering glass powder.

Geopolymer cement

Geopolymer cement is a binding system that hardens at room temperature.

Synthetic magnesium silicates are white, odorless, finely divided powders formed by the precipitation reaction of water-soluble sodium silicate and a water-soluble magnesium salt such as magnesium chloride, magnesium nitrate or magnesium sulfate. The composition of the precipitate depends on the ratio of the components in the reaction medium, the addition of the correcting substances, and the way in which they are precipitated.

The purpose of a mineralizer is to facilitate the transport of insoluble “nutrient” to a seed crystal by means of a reversible chemical reaction. Over time, the seed crystal accumulates the material that was once in the nutrient and grows. Mineralizers are additives that aid the solubilization of the nutrient solid. When used in small quantities, mineralizers function as catalysts. Typically, a more stable solid is crystallized from a solution that consists of a less stable solid and a solvent. The process is done by dissolution-precipitation or crystallization process.

The pozzolanic activity is a measure for the degree of reaction over time or the reaction rate between a pozzolan and Ca2+ or calcium hydroxide (Ca(OH)2) in the presence of water. The rate of the pozzolanic reaction is dependent on the intrinsic characteristics of the pozzolan such as the specific surface area, the chemical composition and the active phase content.

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Further reading