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The
chemical compound silicon dioxide, also known as silica (from the Latin
silex), is an oxide of silicon with a chemical formula of SiO2 and has
been known for its hardness since antiquity. Silica is most commonly
found in nature as sand or quartz, as well as in the cell walls of
diatoms. Silica is the most abundant mineral in the Earth's crust.[1][2]
Silica
is manufactured in several forms including glass, crystal, gel,
aerogel, fumed silica (or pyrogenic silica), and colloidal silica (e.g.
Aerosil). In addition, Silica Nanosprings are produced by the
vapor-liquid-solid method at temperatures as low as room temperature.[3]
Silica
is used primarily in the production of window glass, drinking glasses
and beverage bottles. The majority of optical fibers for
telecommunications are also made from silica. It is a primary raw
material for many whiteware ceramics such as earthenware, stoneware and
porcelain, as well as industrial Portland cement.
Silica is
common additive in the production of foods, where it is used primarily
as a flow agent in powdered foods, or to absorb water in hygroscopic
applications. It is the primary component of diatomaceous earth which
has many uses ranging from filtration to insect control. It is also the
primary component of rice husk ash which is used, for example, in
filtration and cement manufacturing.
Thin films of silica grown
on silicon wafers via thermal oxidation methods can be quite beneficial
in microelectronics, where they act as electric insulators with high
chemical stability. In electrical applications, it can protect the
silicon, store charge, block current, and even act as a controlled
pathway to limit current flow.
Silica is used as a raw material
for aerogel in the Stardust spacecraft. It is also used in the
extraction of DNA and RNA due to its ability to bind to the nucleic
acids under the presence of chaotropes. As hydrophobic silica it is used
as a defoamer component. In hydrated form, it is used in toothpaste as a
hard abrasive to remove tooth plaque.
In its capacity as a
refractory, it is useful in fiber form as a high-temperature thermal
protection fabric. In cosmetics, it is useful for its light-diffusing
properties and natural absorbency. Colloidal silica is used as a wine
and juice fining agent. In pharmaceutical products, silica aids powder
flow when tablets are formed. Finally, it is used as a thermal
enhancement compound in ground source heat pump industry.
Crystal
structure
Tetrahedral structural unit of silica (SiO2), the
basic building block of the most ideal glass former.
In the vast
majority of silicates, the Si atom shows tetrahedral coordination, with 4
oxygen atoms surrounding a central Si atom. The most common example is
seen in the quartz crystalline form of silica SiO2. In each of the most
thermodynamically stable crystalline forms of silica, on average, only 2
out of 4 of each the vertices (or oxygen atoms) of the SiO4 tetrahedra
are shared with others, yielding the net chemical formula: SiO2.[4]
The
amorphous structure of glassy silica (SiO2) in two-dimensions. No
long-range order is present, however there is local ordering with
respect to the tetrahedral arrangement of oxygen (O) atoms around the
silicon (Si) atoms. Note that a fourth oxygen atom is bonded to each
silicon atom, either behind the plane of the screen or in front of it;
these atoms are omitted for clarity.
For example, in the unit
cell of alpha-quartz, the central tetrahedron shares all 4 of its corner
O atoms, the 2 face-centered tetrahedra share 2 of their corner O
atoms, and the 4 edge-centered terahedra share just 1 of their O atoms
with other SiO4 tetrahedra. This leaves a net average of 12 out of 24
(or 1 out of 2) total vertices for that portion of the 7 SiO4 tetrahedra
which are considered to be a part of the unit cell for silica (see 3-D
Unit Cell).
SiO2 has a number of distinct crystalline forms in
addition to amorphous forms. With the exception of stishovite and
fibrous silica, all of the crystalline forms involve tetrahedral SiO4
units linked together by shared vertices in different arrangements.
Silicon-oxygen bond lengths vary between the different crystal forms,
for example in α-quartz the bond length is 161 pm, whereas in
α-tridymite it is in the range 154–171 pm. The Si-O-Si angle also varies
between a low value of 140° in α-tridymite, up to 180° in β-tridymite.
In α-quartz the Si-O-Si angle is 144°.[5]
Fibrous silica has a
structure similar to that of SiS2 with chains of edge-sharing SiO4
tetrahedra. Stishovite, the highest pressure form, in contrast has a
rutile like structure where silicon is 6 coordinate. The density of
stishovite is 4.287 g/cm3, which compares to α-quartz, the densest of
the low pressure forms, which has a density of 2.648 g/cm3.[6] The
difference in density can be ascribed to the increase in coordination as
the six shortest Si-O bond lengths in stishovite (four Si-O bond
lengths of 176 pm and two others of 181 pm) are greater than the Si-O
bond length (161 pm) in α-quartz. [7] The change in the coordination
increases the ionicity of the Si-O bond. [8] But more important is the
observation that any deviations from these standard parameters
constitute microstructural differences or variations which represent an
approach to an amorphous, vitreous or glassy solid.
Note that the
only stable form under normal conditions is α-quartz and this is the
form in which crystalline silicon dioxide is usually encountered. In
nature impurities in crystalline α-quartz can give rise to colours (see
list).
Note also that both high temperature minerals,
cristobalite and tridymite, have both a lower density and index of
refraction than quartz. Since the composition is identical, the reason
for the discrepancies must be in the increased spacing in the high
temperature minerals. As is common with many substances, the higher the
temperature the farther apart the atoms due to the increased vibration
energy.
The high pressure minerals, stishovite and coesite, on
the other hand, have a higher density and index of refraction when
compared to quartz. This is probably due to the intense compression of
the atoms that must occur during their formation, resulting in a more
condensed structure.
Faujasite silica is another form of
crystalline silica. It is obtained by dealumination of a low-sodium,
ultra-stable Y zeolite with a combined acid and thermal treatment. The
resulting product contains over 99% silica, has high crystallinity and
high surface area (over 800 m2/g). Faujasite-silica has very high
thermal and acid stability. For example, it maintains a high degree of
long-range molecular order (or crystallinity) even after boiling in
concentrated hydrochloric acid.[9]Crystalline forms of SiO2[5]
Form
Crystal symmetry
Pearson symbol, group, No
Notes
Structure
α-quartz
rhombohedral (trigonal)
hP9, P3121 No.152[10]
Helical chains making individual single crystals optically active;
α-quartz converts to β-quartz at 573 °C
β-quartz
hexagonal
hP18, P6222, No.180[11]
closely related to α-quartz
(with an Si-O-Si angle of 155°) and optically active; β-quartz converts
to β-tridymite at 870 °C
α-tridymite
orthorhombic
oS24,
C2221, No.20[12]
metastable form under normal pressure
β-tridymite
hexagonal
hP12, P63/mmc, No. 194[12]
closely related to
α-tridymite; β-tridymite converts to β-cristobalite at 1470 °C
α-cristobalite
tetragonal
tP12, P41212, No. 92[13]
metastable form under normal
pressure
β-cristobalite
cubic
cF104, Fd3m,
No.227[14]
closely related to α-cristobalite; melts at 1705 °C
keatite
tetragonal
tP36, P41212, No. 92[15]
Si5O10,
Si4O14, Si8O16 rings; synthesised from amorphous silica and alkali at
high pressure
coesite
monoclinic
mS48, C2/c,
No.15[16]
Si4O8 and Si8O16 rings; high pressure form (higher than
keatite)
stishovite
tetragonal
tP6, P42/mnm,
No.136[17]
rutile like with 6-fold coordinated Si; high pressure
form (higher than coesite) and the densest of the polymorphs
melanophlogite
cubic
cP*, P4232, No.208[18]
Si5O10, Si6O12 rings; mineral
always found with hydrocarbons in interstitial spaces-a clathrasil[19]
fibrous
orthorhombic
oI12, Ibam, No.72[20]
like SiS2
consisting of edge sharing chains
faujasite
cubic
cF576,
Fd3m, No.227[21]
sodalite cages connected by hexagonal prisms;
12-membered ring pore opening; faujasite structure.[9]
Molten
silica exhibits several peculiar physical characteristics that are
similar to the ones observed in liquid water: negative temperature
expansion, density maximum and a heat capacity minimum.[22] When
molecular silicon monoxide, SiO, is condensed in an argon matrix cooled
with helium along with oxygen atoms generated by microwave discharge,
molecular SiO2 is produced which has a linear structure. Dimeric silicon
dioxide, (SiO2)2 has been prepared by reacting O2 with matrix isolated
dimeric silicon monoxide, (Si2O2). In dimeric silicon dioxide there are
two oxygen atoms bridging between the silicon atoms with an Si-O-Si
angle of 94° and bond length of 164.6 pm and the terminal Si-O bond
length is 150.2 pm. The Si-O bond length is 148.3 pm which compares with
the length of 161 pm in α-quartz. The bond energy is estimated at 621.7
kJ/mol.[23]
Quartz glass
Main article: Glass
When
silicon dioxide SiO2 is cooled rapidly enough, it does not crystallize
but solidifies as a glass. The glass transition temperature of pure SiO2
is about 1600 K.
Chemistry
Manufactured silica fume
at maximum surface area of 380 m2/g
Silicon dioxide is formed
when silicon is exposed to oxygen (or air). A very thin layer
(approximately 1 nm or 10 Å) of so-called 'native oxide' is formed on
the surface when silicon is exposed to air under ambient conditions.
Higher temperatures and alternative environments are used to grow
well-controlled layers of silicon dioxide on silicon, for example at
temperatures between 600 and 1200 °C, using the so-called "dry" or "wet"
oxidation with O2 or H2O, respectively.[24] The thickness of the layer
of silicon replaced by the dioxide is 44% of the thickness of the
silicon dioxide layer produced.[24]
Alternative methods used to
deposit a layer of SiO2 include[25]
Low temperature oxidation
(400–450 °C) of silane
SiH4 + 2 O2 → SiO2 + 2 H2O
Decomposition
of tetraethyl orthosilicate (TEOS) at 680–730 °C
Si(OC2H5)4 → SiO2 +
2 H2O + 4 C2H4
Plasma enhanced chemical vapor deposition using
TEOS at about 400 °C
Si(OC2H5)4 + 12 O2 → SiO2 + 10 H2O + 8 CO2
Polymerization
of tetraethyl orthosilicate (TEOS) at below 100 °C using amino acid as
catalyst.[26]
Pyrogenic silica (sometimes called fumed silica or
silica fume), which is a very fine particulate form of silicon dioxide,
is prepared by burning SiCl4 in an oxygen rich hydrocarbon flame to
produce a "smoke" of SiO2:[6]
SiCl4 + 2 H2 + O2 → SiO2 + 4 HCl
Amorphous
silica, silica gel, is produced by the acidification of solutions of
sodium silicate to produce a gelatinous precipitate that is then washed
and then dehydrated to produce colorless microporous silica.[6]
Quartz
exhibits a maximum solubility in water at temperatures about 340
°C.[27] This property is used to grow single crystals of quartz in a
hydrothermal process where natural quartz is dissolved in superheated
water in a pressure vessel which is cooler at the top. Crystals of 0.5–1
kg can be grown over a period of 1–2 months.[5] These crystals are a
source of very pure quartz for use in electronic applications.[6]
Fluorine
reacts with silicon dioxide to form SiF4 and O2 whereas the other
halogen gases (Cl2, Br2, I2) react much less readily.[6]
Silicon
dioxide is attacked by hydrofluoric acid (HF) to produce
"hexafluorosilicic acid":[5]
SiO2 + 6 HF → H2SiF6 + 2 H2O
HF
is used to remove or pattern silicon dioxide in the semiconductor
industry.
Silicon dioxide dissolves in hot concentrated alkali or
fused hydroxide:[6]
SiO2 + 2 NaOH → Na2SiO3 + H2O
Silicon
dioxide reacts with basic metal oxides (e.g. sodium oxide, potassium
oxide, lead(II) oxide, zinc oxide or mixtures of oxides forming
silicates and glasses as the Si-O-Si bonds in silica are broken
successively).[5] As an example the reaction of sodium oxide and SiO2
can produce sodium orthosilicate, sodium silicate and glasses, depending
on the proportions of reactants:[6]
2 Na2O + SiO2 → Na4SiO4
Na2O
+ SiO2 → Na2SiO3
(0.25–0.8)Na2O + SiO2 → glass
Examples
of such glasses have commercial significance e.g. soda lime glass,
borosilicate glass, lead glass. In these glasses, silica is termed the
network former or lattice former.[5]
Bundle of optical
fibers composed of high purity silica.
With silicon at high
temperatures gaseous SiO is produced:[5]
SiO2 + Si → 2 SiO (gas)
Sol-gel
The
sol-gel process is a wet chemical technique used for the fabrication of
both glassy and ceramic materials. In this process, the sol (or
solution) evolves gradually towards the formation of a gel-like network
containing both a liquid phase and a solid phase. The basic structure or
morphology of the solid phase can range anywhere from discrete
colloidal particles to continuous chain-like polymer networks.[28][29]
The
term “colloid” is specific to the size of the individual particles,
which are larger than atoms but small enough not to settle to the bottom
of a container immediately. If the particles are large enough, then
their dynamic behavior would be governed by forces of gravity and
sedimentation. But if they are small enough to be colloids, then they
may remain suspended in a liquid medium indefinitely. This critical size
range (or particle diameter) typically ranges from tens of angstroms to
a few microns.
1) In basic solutions (pH > 7), the particles
may grow to sufficient size to become colloids, which are affected both
by sedimentation and forces of gravity. Particles like these may become
highly ordered in a manner similar to those seen in precious opal.
2)
Under acidic conditions (pH < 7), a more open continuous network of
chain-like polymers is formed. Polymers like this can be useful due to
their viscosity, which allows them to be drawn or spun from solution
into fibers, or drawn as thin films into surface coatings. Such glass
fiber is useful for guided lightwave transmission, with ceramic fiber
providing excellent thermal insulation.
Silica fiber mesh
for thermal insulation.
In either case, the sol evolves towards
the formation of a 2-phase gel. In the case of the colloid, the number
of particles in an extremely dilute suspension may be so low that a
significant amount of solvent may need to be removed initially for the
gel-like properties to be recognized. This can be accomplished in any
number of ways. The simplest method is to allow time for sedimentation
to occur, and then pour off the remaining liquid. A variable speed
centrifuge can also be used to accelerate the process of liquid removal.
Removal
of the remaining liquid (solvent) phase requires a drying process,
which is typically accompanied by a significant amount of shrinkage and
densification. Since the remaining water will most likely reside within
microstructural pores, the rate at which the solvent can be removed is
ultimately determined by the distribution of pore space in the gel.
Subsequent thermal treatment (or low temperature sintering at 500 – 600
°C) may be performed in order to obtain a higher density product. With
regard to methods of application:
1) The sol can be deposited on a
substrate to form a film using dip-coating or spin-coating;
2)
It can be cast into a suitable container with the desired shape;
3)
It can be used to synthesize fine high-purity powders.[30][31]
The
sol-gel approach is a cheap and low-temperature technique that
maintains a high degree of chemical purity. Thus it allows for total
control of the product’s chemical composition. It can be used in
ceramics manufacturing processes, as an investment casting material, or
as a means of producing thin films or coatings.[32]
Sol-gel
derived components have diverse applications in optics, electronics,
energy, space, physical and chemical sensors, biosensors, controlled
drug release in medicine, and chemical separation on a cellular level.
Ceramic powders of a wide range of chemical composition can be formed by
such techniques. The generation of particles uniform in size and shape
was investigated extensively by Egon Matijevic and his co-workers. In
the case of chromium, aluminum and titanium salts, spherical particles
were formed whereas particles of crystallographic symmetry resulted from
solutions of copper and iron salts.[30][33][34][35][36][37][38][39]
In
1956, Kolbe described the formation of spherical silica particles in
basic solution. The mechanisms of precipitation—and the chemical
conditions that bias the structure toward linear or branched
structures—are the most critical issues faced in the chemistry
laboratory by sol-gel scientists. Again, these are the factors which
will ultimately determine the form of the microstructure over a range of
length scales in the green or unfired body. Factors, such as chemical
acidity which lead to the formation of linear polymers (as opposed to
particles), are ideal for the formation of spinnable solutions such as
those used for the formation of thin films and coatings as well as
optical quality fiber.
Sand from Pismo Beach, California
including quartz, shell and rock fragments.
Biomaterials
Silicification
is quite common in the biological world and occurs in bacteria,
single-celled organisms, plants, and animals (invertebrates and
vertebrates). Crystalline minerals formed in this environment often show
exceptional physical properties (e.g. strength, hardness, fracture
toughness) and tend to form hierarchical structures that exhibit
microstructural order over a range of length or spatial scales. The
minerals are crystallized from an environment that is undersaturated
with respect to silicon, and under conditions of neutral pH and low
temperature (0–40 °C). Formation of the mineral may occur either within
or outside of the cell wall of an organism, and specific biochemical
reactions for mineral deposition exist that include lipids, proteins and
carbohydrates.
Health effects
Quartz sand (silica) as
main raw material for commercial glass production
Inhaling
finely divided crystalline silica dust in very small quantities (OSHA
allows 0.1 mg/m3) over time can lead to silicosis, bronchitis or (much
more rarely) cancer, as the dust becomes lodged in the lungs and
continuously irritates them, reducing lung capacities (silica does not
dissolve over time). This effect can be an occupational hazard for
people working with sandblasting equipment, products that contain
powdered crystalline silica and so on. Children, asthmatics of any age,
allergy sufferers and the elderly (all of whom have reduced lung
capacity) can be affected in much shorter periods of time. Amorphous
silica, such as fumed silica is not associated with development of
silicosis.[40] Laws restricting silica exposure with respect to the
silicosis hazard specify that the silica is both crystalline and
dust-forming.
In respects other than inhalation, pure silicon
dioxide is inert and harmless. Because some silicas take on water,
extended exposure may cause local drying of the skin or other tissue.
Pure silicon dioxide produces no fumes and is insoluble in vivo. (in the
body) It is indigestible, with zero nutritional value and zero
toxicity.[citation needed] When silica is ingested orally, it passes
unchanged through the gastrointestinal (GI) tract, exiting in the feces,
leaving no trace behind.[citation needed] Small pieces of silicon
dioxide are equally harmless[citation needed], as long as they are not
large enough to mechanically obstruct the GI tract, or jagged enough to
lacerate its lining.
A study which followed subjects for 15 years
found that higher levels of silica in water appeared to decrease the
risk of dementia. The study found that for every 10 milligram-per-day
intake of silica in drinking water, the risk of dementia dropped by
11%.[
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The
chemical compound silicon dioxide, also known as silica (from the Latin
silex), is an oxide of silicon with a chemical formula of SiO2 and has
been known for its hardness since antiquity. Silica is most commonly
found in nature as sand or quartz, as well as in the cell walls of
diatoms. Silica is the most abundant mineral in the Earth's crust.[1][2]
Silica
is manufactured in several forms including glass, crystal, gel,
aerogel, fumed silica (or pyrogenic silica), and colloidal silica (e.g.
Aerosil). In addition, Silica Nanosprings are produced by the
vapor-liquid-solid method at temperatures as low as room temperature.[3]
Silica
is used primarily in the production of window glass, drinking glasses
and beverage bottles. The majority of optical fibers for
telecommunications are also made from silica. It is a primary raw
material for many whiteware ceramics such as earthenware, stoneware and
porcelain, as well as industrial Portland cement.
Silica is
common additive in the production of foods, where it is used primarily
as a flow agent in powdered foods, or to absorb water in hygroscopic
applications. It is the primary component of diatomaceous earth which
has many uses ranging from filtration to insect control. It is also the
primary component of rice husk ash which is used, for example, in
filtration and cement manufacturing.
Thin films of silica grown
on silicon wafers via thermal oxidation methods can be quite beneficial
in microelectronics, where they act as electric insulators with high
chemical stability. In electrical applications, it can protect the
silicon, store charge, block current, and even act as a controlled
pathway to limit current flow.
Silica is used as a raw material
for aerogel in the Stardust spacecraft. It is also used in the
extraction of DNA and RNA due to its ability to bind to the nucleic
acids under the presence of chaotropes. As hydrophobic silica it is used
as a defoamer component. In hydrated form, it is used in toothpaste as a
hard abrasive to remove tooth plaque.
In its capacity as a
refractory, it is useful in fiber form as a high-temperature thermal
protection fabric. In cosmetics, it is useful for its light-diffusing
properties and natural absorbency. Colloidal silica is used as a wine
and juice fining agent. In pharmaceutical products, silica aids powder
flow when tablets are formed. Finally, it is used as a thermal
enhancement compound in ground source heat pump industry.
Crystal
structure
Tetrahedral structural unit of silica (SiO2), the
basic building block of the most ideal glass former.
In the vast
majority of silicates, the Si atom shows tetrahedral coordination, with 4
oxygen atoms surrounding a central Si atom. The most common example is
seen in the quartz crystalline form of silica SiO2. In each of the most
thermodynamically stable crystalline forms of silica, on average, only 2
out of 4 of each the vertices (or oxygen atoms) of the SiO4 tetrahedra
are shared with others, yielding the net chemical formula: SiO2.[4]
The
amorphous structure of glassy silica (SiO2) in two-dimensions. No
long-range order is present, however there is local ordering with
respect to the tetrahedral arrangement of oxygen (O) atoms around the
silicon (Si) atoms. Note that a fourth oxygen atom is bonded to each
silicon atom, either behind the plane of the screen or in front of it;
these atoms are omitted for clarity.
For example, in the unit
cell of alpha-quartz, the central tetrahedron shares all 4 of its corner
O atoms, the 2 face-centered tetrahedra share 2 of their corner O
atoms, and the 4 edge-centered terahedra share just 1 of their O atoms
with other SiO4 tetrahedra. This leaves a net average of 12 out of 24
(or 1 out of 2) total vertices for that portion of the 7 SiO4 tetrahedra
which are considered to be a part of the unit cell for silica (see 3-D
Unit Cell).
SiO2 has a number of distinct crystalline forms in
addition to amorphous forms. With the exception of stishovite and
fibrous silica, all of the crystalline forms involve tetrahedral SiO4
units linked together by shared vertices in different arrangements.
Silicon-oxygen bond lengths vary between the different crystal forms,
for example in α-quartz the bond length is 161 pm, whereas in
α-tridymite it is in the range 154–171 pm. The Si-O-Si angle also varies
between a low value of 140° in α-tridymite, up to 180° in β-tridymite.
In α-quartz the Si-O-Si angle is 144°.[5]
Fibrous silica has a
structure similar to that of SiS2 with chains of edge-sharing SiO4
tetrahedra. Stishovite, the highest pressure form, in contrast has a
rutile like structure where silicon is 6 coordinate. The density of
stishovite is 4.287 g/cm3, which compares to α-quartz, the densest of
the low pressure forms, which has a density of 2.648 g/cm3.[6] The
difference in density can be ascribed to the increase in coordination as
the six shortest Si-O bond lengths in stishovite (four Si-O bond
lengths of 176 pm and two others of 181 pm) are greater than the Si-O
bond length (161 pm) in α-quartz. [7] The change in the coordination
increases the ionicity of the Si-O bond. [8] But more important is the
observation that any deviations from these standard parameters
constitute microstructural differences or variations which represent an
approach to an amorphous, vitreous or glassy solid.
Note that the
only stable form under normal conditions is α-quartz and this is the
form in which crystalline silicon dioxide is usually encountered. In
nature impurities in crystalline α-quartz can give rise to colours (see
list).
Note also that both high temperature minerals,
cristobalite and tridymite, have both a lower density and index of
refraction than quartz. Since the composition is identical, the reason
for the discrepancies must be in the increased spacing in the high
temperature minerals. As is common with many substances, the higher the
temperature the farther apart the atoms due to the increased vibration
energy.
The high pressure minerals, stishovite and coesite, on
the other hand, have a higher density and index of refraction when
compared to quartz. This is probably due to the intense compression of
the atoms that must occur during their formation, resulting in a more
condensed structure.
Faujasite silica is another form of
crystalline silica. It is obtained by dealumination of a low-sodium,
ultra-stable Y zeolite with a combined acid and thermal treatment. The
resulting product contains over 99% silica, has high crystallinity and
high surface area (over 800 m2/g). Faujasite-silica has very high
thermal and acid stability. For example, it maintains a high degree of
long-range molecular order (or crystallinity) even after boiling in
concentrated hydrochloric acid.[9]Crystalline forms of SiO2[5]
Form
Crystal symmetry
Pearson symbol, group, No
Notes
Structure
α-quartz
rhombohedral (trigonal)
hP9, P3121 No.152[10]
Helical chains making individual single crystals optically active;
α-quartz converts to β-quartz at 573 °C
β-quartz
hexagonal
hP18, P6222, No.180[11]
closely related to α-quartz
(with an Si-O-Si angle of 155°) and optically active; β-quartz converts
to β-tridymite at 870 °C
α-tridymite
orthorhombic
oS24,
C2221, No.20[12]
metastable form under normal pressure
β-tridymite
hexagonal
hP12, P63/mmc, No. 194[12]
closely related to
α-tridymite; β-tridymite converts to β-cristobalite at 1470 °C
α-cristobalite
tetragonal
tP12, P41212, No. 92[13]
metastable form under normal
pressure
β-cristobalite
cubic
cF104, Fd3m,
No.227[14]
closely related to α-cristobalite; melts at 1705 °C
keatite
tetragonal
tP36, P41212, No. 92[15]
Si5O10,
Si4O14, Si8O16 rings; synthesised from amorphous silica and alkali at
high pressure
coesite
monoclinic
mS48, C2/c,
No.15[16]
Si4O8 and Si8O16 rings; high pressure form (higher than
keatite)
stishovite
tetragonal
tP6, P42/mnm,
No.136[17]
rutile like with 6-fold coordinated Si; high pressure
form (higher than coesite) and the densest of the polymorphs
melanophlogite
cubic
cP*, P4232, No.208[18]
Si5O10, Si6O12 rings; mineral
always found with hydrocarbons in interstitial spaces-a clathrasil[19]
fibrous
orthorhombic
oI12, Ibam, No.72[20]
like SiS2
consisting of edge sharing chains
faujasite
cubic
cF576,
Fd3m, No.227[21]
sodalite cages connected by hexagonal prisms;
12-membered ring pore opening; faujasite structure.[9]
Molten
silica exhibits several peculiar physical characteristics that are
similar to the ones observed in liquid water: negative temperature
expansion, density maximum and a heat capacity minimum.[22] When
molecular silicon monoxide, SiO, is condensed in an argon matrix cooled
with helium along with oxygen atoms generated by microwave discharge,
molecular SiO2 is produced which has a linear structure. Dimeric silicon
dioxide, (SiO2)2 has been prepared by reacting O2 with matrix isolated
dimeric silicon monoxide, (Si2O2). In dimeric silicon dioxide there are
two oxygen atoms bridging between the silicon atoms with an Si-O-Si
angle of 94° and bond length of 164.6 pm and the terminal Si-O bond
length is 150.2 pm. The Si-O bond length is 148.3 pm which compares with
the length of 161 pm in α-quartz. The bond energy is estimated at 621.7
kJ/mol.[23]
Quartz glass
Main article: Glass
When
silicon dioxide SiO2 is cooled rapidly enough, it does not crystallize
but solidifies as a glass. The glass transition temperature of pure SiO2
is about 1600 K.
Chemistry
Manufactured silica fume
at maximum surface area of 380 m2/g
Silicon dioxide is formed
when silicon is exposed to oxygen (or air). A very thin layer
(approximately 1 nm or 10 Å) of so-called 'native oxide' is formed on
the surface when silicon is exposed to air under ambient conditions.
Higher temperatures and alternative environments are used to grow
well-controlled layers of silicon dioxide on silicon, for example at
temperatures between 600 and 1200 °C, using the so-called "dry" or "wet"
oxidation with O2 or H2O, respectively.[24] The thickness of the layer
of silicon replaced by the dioxide is 44% of the thickness of the
silicon dioxide layer produced.[24]
Alternative methods used to
deposit a layer of SiO2 include[25]
Low temperature oxidation
(400–450 °C) of silane
SiH4 + 2 O2 → SiO2 + 2 H2O
Decomposition
of tetraethyl orthosilicate (TEOS) at 680–730 °C
Si(OC2H5)4 → SiO2 +
2 H2O + 4 C2H4
Plasma enhanced chemical vapor deposition using
TEOS at about 400 °C
Si(OC2H5)4 + 12 O2 → SiO2 + 10 H2O + 8 CO2
Polymerization
of tetraethyl orthosilicate (TEOS) at below 100 °C using amino acid as
catalyst.[26]
Pyrogenic silica (sometimes called fumed silica or
silica fume), which is a very fine particulate form of silicon dioxide,
is prepared by burning SiCl4 in an oxygen rich hydrocarbon flame to
produce a "smoke" of SiO2:[6]
SiCl4 + 2 H2 + O2 → SiO2 + 4 HCl
Amorphous
silica, silica gel, is produced by the acidification of solutions of
sodium silicate to produce a gelatinous precipitate that is then washed
and then dehydrated to produce colorless microporous silica.[6]
Quartz
exhibits a maximum solubility in water at temperatures about 340
°C.[27] This property is used to grow single crystals of quartz in a
hydrothermal process where natural quartz is dissolved in superheated
water in a pressure vessel which is cooler at the top. Crystals of 0.5–1
kg can be grown over a period of 1–2 months.[5] These crystals are a
source of very pure quartz for use in electronic applications.[6]
Fluorine
reacts with silicon dioxide to form SiF4 and O2 whereas the other
halogen gases (Cl2, Br2, I2) react much less readily.[6]
Silicon
dioxide is attacked by hydrofluoric acid (HF) to produce
"hexafluorosilicic acid":[5]
SiO2 + 6 HF → H2SiF6 + 2 H2O
HF
is used to remove or pattern silicon dioxide in the semiconductor
industry.
Silicon dioxide dissolves in hot concentrated alkali or
fused hydroxide:[6]
SiO2 + 2 NaOH → Na2SiO3 + H2O
Silicon
dioxide reacts with basic metal oxides (e.g. sodium oxide, potassium
oxide, lead(II) oxide, zinc oxide or mixtures of oxides forming
silicates and glasses as the Si-O-Si bonds in silica are broken
successively).[5] As an example the reaction of sodium oxide and SiO2
can produce sodium orthosilicate, sodium silicate and glasses, depending
on the proportions of reactants:[6]
2 Na2O + SiO2 → Na4SiO4
Na2O
+ SiO2 → Na2SiO3
(0.25–0.8)Na2O + SiO2 → glass
Examples
of such glasses have commercial significance e.g. soda lime glass,
borosilicate glass, lead glass. In these glasses, silica is termed the
network former or lattice former.[5]
Bundle of optical
fibers composed of high purity silica.
With silicon at high
temperatures gaseous SiO is produced:[5]
SiO2 + Si → 2 SiO (gas)
Sol-gel
The
sol-gel process is a wet chemical technique used for the fabrication of
both glassy and ceramic materials. In this process, the sol (or
solution) evolves gradually towards the formation of a gel-like network
containing both a liquid phase and a solid phase. The basic structure or
morphology of the solid phase can range anywhere from discrete
colloidal particles to continuous chain-like polymer networks.[28][29]
The
term “colloid” is specific to the size of the individual particles,
which are larger than atoms but small enough not to settle to the bottom
of a container immediately. If the particles are large enough, then
their dynamic behavior would be governed by forces of gravity and
sedimentation. But if they are small enough to be colloids, then they
may remain suspended in a liquid medium indefinitely. This critical size
range (or particle diameter) typically ranges from tens of angstroms to
a few microns.
1) In basic solutions (pH > 7), the particles
may grow to sufficient size to become colloids, which are affected both
by sedimentation and forces of gravity. Particles like these may become
highly ordered in a manner similar to those seen in precious opal.
2)
Under acidic conditions (pH < 7), a more open continuous network of
chain-like polymers is formed. Polymers like this can be useful due to
their viscosity, which allows them to be drawn or spun from solution
into fibers, or drawn as thin films into surface coatings. Such glass
fiber is useful for guided lightwave transmission, with ceramic fiber
providing excellent thermal insulation.
Silica fiber mesh
for thermal insulation.
In either case, the sol evolves towards
the formation of a 2-phase gel. In the case of the colloid, the number
of particles in an extremely dilute suspension may be so low that a
significant amount of solvent may need to be removed initially for the
gel-like properties to be recognized. This can be accomplished in any
number of ways. The simplest method is to allow time for sedimentation
to occur, and then pour off the remaining liquid. A variable speed
centrifuge can also be used to accelerate the process of liquid removal.
Removal
of the remaining liquid (solvent) phase requires a drying process,
which is typically accompanied by a significant amount of shrinkage and
densification. Since the remaining water will most likely reside within
microstructural pores, the rate at which the solvent can be removed is
ultimately determined by the distribution of pore space in the gel.
Subsequent thermal treatment (or low temperature sintering at 500 – 600
°C) may be performed in order to obtain a higher density product. With
regard to methods of application:
1) The sol can be deposited on a
substrate to form a film using dip-coating or spin-coating;
2)
It can be cast into a suitable container with the desired shape;
3)
It can be used to synthesize fine high-purity powders.[30][31]
The
sol-gel approach is a cheap and low-temperature technique that
maintains a high degree of chemical purity. Thus it allows for total
control of the product’s chemical composition. It can be used in
ceramics manufacturing processes, as an investment casting material, or
as a means of producing thin films or coatings.[32]
Sol-gel
derived components have diverse applications in optics, electronics,
energy, space, physical and chemical sensors, biosensors, controlled
drug release in medicine, and chemical separation on a cellular level.
Ceramic powders of a wide range of chemical composition can be formed by
such techniques. The generation of particles uniform in size and shape
was investigated extensively by Egon Matijevic and his co-workers. In
the case of chromium, aluminum and titanium salts, spherical particles
were formed whereas particles of crystallographic symmetry resulted from
solutions of copper and iron salts.[30][33][34][35][36][37][38][39]
In
1956, Kolbe described the formation of spherical silica particles in
basic solution. The mechanisms of precipitation—and the chemical
conditions that bias the structure toward linear or branched
structures—are the most critical issues faced in the chemistry
laboratory by sol-gel scientists. Again, these are the factors which
will ultimately determine the form of the microstructure over a range of
length scales in the green or unfired body. Factors, such as chemical
acidity which lead to the formation of linear polymers (as opposed to
particles), are ideal for the formation of spinnable solutions such as
those used for the formation of thin films and coatings as well as
optical quality fiber.
Sand from Pismo Beach, California
including quartz, shell and rock fragments.
Biomaterials
Silicification
is quite common in the biological world and occurs in bacteria,
single-celled organisms, plants, and animals (invertebrates and
vertebrates). Crystalline minerals formed in this environment often show
exceptional physical properties (e.g. strength, hardness, fracture
toughness) and tend to form hierarchical structures that exhibit
microstructural order over a range of length or spatial scales. The
minerals are crystallized from an environment that is undersaturated
with respect to silicon, and under conditions of neutral pH and low
temperature (0–40 °C). Formation of the mineral may occur either within
or outside of the cell wall of an organism, and specific biochemical
reactions for mineral deposition exist that include lipids, proteins and
carbohydrates.
Health effects
Quartz sand (silica) as
main raw material for commercial glass production
Inhaling
finely divided crystalline silica dust in very small quantities (OSHA
allows 0.1 mg/m3) over time can lead to silicosis, bronchitis or (much
more rarely) cancer, as the dust becomes lodged in the lungs and
continuously irritates them, reducing lung capacities (silica does not
dissolve over time). This effect can be an occupational hazard for
people working with sandblasting equipment, products that contain
powdered crystalline silica and so on. Children, asthmatics of any age,
allergy sufferers and the elderly (all of whom have reduced lung
capacity) can be affected in much shorter periods of time. Amorphous
silica, such as fumed silica is not associated with development of
silicosis.[40] Laws restricting silica exposure with respect to the
silicosis hazard specify that the silica is both crystalline and
dust-forming.
In respects other than inhalation, pure silicon
dioxide is inert and harmless. Because some silicas take on water,
extended exposure may cause local drying of the skin or other tissue.
Pure silicon dioxide produces no fumes and is insoluble in vivo. (in the
body) It is indigestible, with zero nutritional value and zero
toxicity.[citation needed] When silica is ingested orally, it passes
unchanged through the gastrointestinal (GI) tract, exiting in the feces,
leaving no trace behind.[citation needed] Small pieces of silicon
dioxide are equally harmless[citation needed], as long as they are not
large enough to mechanically obstruct the GI tract, or jagged enough to
lacerate its lining.
A study which followed subjects for 15 years
found that higher levels of silica in water appeared to decrease the
risk of dementia. The study found that for every 10 milligram-per-day
intake of silica in drinking water, the risk of dementia dropped by
11%.[
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freze takımlarından olan Parmak Freze imalatçısıdır. Çok geniş ürün
yelpazesine sahip olan firmanın başlıca ürünlerini Karbür Parmak
Frezeler, Kalıpçı Frezeleri, Kaba Talaş Frezeleri, Konik Alın Frezeler,
Köşe Radyüs Frezeler, İki Ağızlı Kısa ve Uzun Küresel Frezeler, İç Bükey
Frezeler vb. şeklinde sıralayabiliriz.
BW специализируется в
научных исследованиях и разработках, и снабжаем самым
высокотехнологичным карбидовым материалом для поставки режущих /
фрезеровочных инструментов для почвы, воздушного пространства и
электронной индустрии. В нашу основную продукцию входит твердый карбид /
быстрорежущая сталь, а также двигатели, микроэлектрические дрели, IC
картонорезальные машины, фрезы для гравирования, режущие пилы,
фрезеры-расширители, фрезеры-расширители с резцом, дрели, резаки форм
для шлицевого вала / звездочки роликовой цепи, и специальные нано
инструменты. Пожалуйста, посетите сайт www.tool-tool.com для получения
большей информации.
BW is specialized in R&D and sourcing
the most advanced carbide material with high-tech coating to supply
cutting / milling tool for mould & die, aero space and electronic
industry. Our main products include solid carbide / HSS end mills, micro
electronic drill, IC card cutter, engraving cutter, shell end mills,
cutting saw, reamer, thread reamer, leading drill, involute gear cutter
for spur wheel, rack and worm milling cutter, thread milling cutter,
form cutters for spline shaft/roller chain sprocket, and special tool,
with nano grade. Please visit our web www.tool-tool.com for more info
![clip_image002[1]](https://h59kma.bay.livefilestore.com/y1mF624_eahDipzgkNzZ0ZSPrTvH1EwVZkV_RJEI8QMkWgOrtmyZv2aMW5YAwdShe_4krKgh8dxt_kdy6lVZ-6BMG8-M9yZJnXYE_zKjekM-AJDjRhZbTJdN2AR1MgHjwniqS3mdFLEA-7nfUl_PDY0XA/clip_image002%5B1%5D%5B2%5D%20699B5E8D.jpg?download&psid=1 "clip_image002[1]")
Bewise Inc. 