Titanium dioxide is a naturally occurring oxide of titanium.

It has the highest refractive index of any material known to man,

even the diamond, and is one of the whitest materials on earth. When ground into a fine powder, it transforms into a pigment
that provides maximum whiteness and opacity. TiO2 pigments are used in paints and coatings, plastics, paper, building
materials, cosmetics, pharmaceuticals, foods and many other commercial products.
However, nature does not yield titanium dioxide in a usable form. It must be carefully mined in one of its pure forms, such as
rutile beach sand, and refined into a fine uniform particle size.
The map below shows the world’s most important deposits of the basic raw materials used in the manufacture of TiO2
pigments.
Production The production method depends on the feedstock. The most common method for the production of titanium
dioxide utilizes the mineral ilmenite. Ilmenite is mixed with sulfuric acid. This reacts to remove the iron oxide group in the
ilmenite. The by-product iron(II) sulfate is crystallized and filtered-off to yield only the titanium salt in the digestion
solution. This product is called synthetic rutile. This is further processed in a similar way to rutile to give the titanium dioxide
product. Synthetic rutile and titanium slags are made especially for titanium dioxide production.[18] The use of ilminite ore
usually only produces pigment grade titanium dioxide. Another method for the production of synthetic rutile from ilmenite
utilizes the Becher Process.
Rutile is the second most abundant mineral sand. Rutile found in primary rock cannot be extracted hence the deposits
containing rutile sand can be mined meaning a reduced availability to the high concentration ore. Crude titanium dioxide (in
the form of rutile or synthetic rutile) is purified via converting to titanium tetrachloride in the chloride process. In this
process, the crude ore (containing at least 70% TiO2) is reduced with carbon, oxidized with chlorine to give titanium
tetrachloride; i.e., carbothermal chlorination. This titanium tetrachloride is distilled, and re-oxidized in a pure oxygen flame
or plasma at 1500–2000 K to give pure titanium dioxide while also regenerating chlorine.[19] Aluminium chloride is often
added to the process as a rutile promotor; the product is mostly anatase in its absence. The preferred raw material for the
chloride process is natural rutile because of its high titanium dioxide content.[20]
One method for the production of titanium dioxide with relevance to nanotechnology is solvothermal Synthesis of titanium
dioxide.
Nanotubes Anatase can be converted by hydrothermal synthesis to delaminated anatase inorganic nanotubes[21] and titanate
nanoribbons which are of potential interest as catalytic supports and photocatalysts. In the synthesis, anatase is mixed with
10 M sodium hydroxide and heated at 130 °C for 72 hours. The reaction product is washed with dilute hydrochloric acid and
heated at 400 °C for another 15 hours. The yield of nanotubes is quantitative and the tubes have an outer diameter of 10 to 20
nm and an inner diameter of 5 to 8 nm and have a length of 1 μm. A higher reaction temperature (170 °C) and less reaction
volume gives the corresponding nanowires.[22]
Another process for synthesizing TiO2 nanotubes is through anodization in an electrolytic solution. When anodized in a 0.5
weight percent HF solution for 20 minutes, well-aligned titanium oxide nanotube arrays can be fabricated with an average
tube diameter of 60 nm and length of 250 nm. Based on X-ray Diffraction, nanotubes grown through anodization are
amorphous.[23]
Applications The most important application areas are paints and varnishes as well as paper and plastics, which account for
about 80% of the world's titanium dioxide consumption. Other pigment applications such as printing inks, fibers, rubber,
cosmetic products and foodstuffs account for another 8%. The rest is used in other applications, for instance the production
of technical pure titanium, glass and glass ceramics, electrical ceramics, catalysts, electric conductors and chemical
intermediates.[24] It also is in most red-coloured candy.
Pigment Titanium dioxide is the most widely used white pigment because of its brightness and very high refractive index, in
which it is surpassed only by a few other materials. Approximately 4.6 million tons of pigmentary TiO2 are used annually
worldwide, and this number is expected to increase as utilization continues to rise.[25] When deposited as a thin film, its
refractive index and colour make it an excellent reflective optical coating for dielectric mirrors and some gemstones like
"mystic fire topaz". TiO2 is also an effective opacifier in powder form, where it is employed as a pigment to provide
whiteness and opacity to products such as paints, coatings, plastics, papers, inks, foods, medicines (i.e. pills and tablets) as
well as most toothpastes. In paint, it is often referred to offhandedly as "the perfect white", "the whitest white", or other
similar terms. Opacity is improved by optimal sizing of the titanium dioxide particles. Some grades of titanium based
pigments as used in sparkly paints, plastics, finishes and pearlescent cosmetics are man-made pigments whose particles have
two or more layers of various oxides – often titanium dioxide, iron oxide or alumina – in order to have glittering, iridescent
and or pearlescent effects similar to crushed mica or guanine-based products. In addition to these effects a limited colour
change is possible in certain formulations depending on how and at which angle the finished product is illuminated and the
thickness of the oxide layer in the pigment particle; one or more colours appear by reflection while the other tones appear
due to interference of the transparent titanium dioxide layers.[26] In some products, the layer of titanium dioxide is grown in
conjunction with iron oxide by calcination of titanium salts (sulfates, chlorates) around 800 °C[27] or other industrial
deposition methods such as chemical vapour deposition on substrates such as mica platelets or even silicon dioxide crystal
platelets of no more than 50 µm in diameter.[28] The iridescent effect in these titanium oxide particles (which are only partly
natural) is unlike the opaque effect obtained with usual ground titanium oxide pigment obtained by mining, in which case
only a certain diameter of the particle is considered and the effect is due only to scattering.
In ceramic glazes titanium dioxide acts as an opacifier and seeds crystal formation.
Titanium dioxide has been shown statistically to increase skimmed milk's whiteness, increasing skimmed milk's sensory
acceptance score.[29]
Titanium dioxide is used to mark the white lines of some tennis courts.[30]
The exterior of the Saturn V rocket was painted with titanium dioxide; this later allowed astronomers to determine that
J002E3 was the S-IVB stage from Apollo 12 and not an asteroid.
Sunscreen and UV blocking pigments in the industry In cosmetic and skin care products, titanium dioxide is used as a
pigment, sunscreen and a thickener. It is also used as a tattoo pigment and in styptic pencils. Titanium dioxide is produced in
varying particle sizes, oil and water dispersible, and in certain grades for the cosmetic industry.
Titanium dioxide is found in the majority of physical sunscreens because of its high refractive index, its strong UV light
absorbing capabilities and its resistance to discolouration under ultraviolet light. This advantage enhances its stability and
ability to protect the skin from ultraviolet light. Nano-scaled titanium dioxide particles are primarily used in sun screen lotion
because they scatter visible light less than titanium dioxide pigments while still providing UV protection.[25] Sunscreens
designed for infants or people with sensitive skin are often based on titanium dioxide and/or zinc oxide, as these mineral UV
blockers are believed to cause less skin irritation than other UV absorbing chemicals.
This pigment is used extensively in plastics and other applications not only as a white pigment or an opacifier but also for its
UV resistant properties where the powder disperses the light – unlike organic UV absorbers – and reduces UV damage, due
mostly to the extremely high refractive index of the particles.[31] Certain polymers used in coatings for concrete[32] or those
used to impregnate concrete as a reinforcement are sometimes charged with titanium white pigment for UV shielding in the
construction industry, but it only delays the oxidative photodegradation of the polymer in question, which is said to "chalk"
as it flakes off due to lowered impact strength and may crumble after years of exposure in direct sunlight if UV stabilizers
have not been included .
Photocatalyst TiO2 fibers and spirals.
Titanium dioxide, particularly in the anatase form, is a photocatalyst under ultraviolet (UV) light. It has been reported that
titanium dioxide, when doped with nitrogen ions or doped with metal oxide like tungsten trioxide, is also a photocatalyst
under either visible or UV light.[33] The strong oxidative potential of the positive holes oxidizes water to create hydroxyl
radicals. It can also oxidize oxygen or organic materials directly. Hence, in addition to its use as a pigment, titanium dioxide
can be added to paints, cements, windows, tiles, or other products for its sterilizing, deodorizing and anti-fouling properties
and is used as a hydrolysis catalyst. It is also used in dye-sensitized solar cells, which are a type of chemical solar cell (also
known as a Graetzel cell).
The photocatalytic properties of titanium dioxide were discovered by Akira Fujishima in 1967[34] and published in 1972.
[35] The process on the surface of the titanium dioxide was called the Honda-Fujishima effect (ja:本多-藤嶋効果).[34] Titanium
dioxide, in thin film and nanoparticle form has potential for use in energy production: as a photocatalyst, it can carry out
hydrolysis; i.e., break water into hydrogen and oxygen. With the hydrogen collected, it could be used as a fuel. The
efficiency of this process can be greatly improved by doping the oxide with carbon.[36] Further efficiency and durability has
been obtained by introducing disorder to the lattice structure of the surface layer of titanium dioxide nanocrystals, permitting
infrared absorption.[37]
In 1995 Fujishima and his group discovered the superhydrophilicity phenomenon for titanium dioxide coated glass exposed
to sun light.[34] This resulted in the development of self-cleaning glass and anti-fogging coatings.
TiO2 incorporated into outdoor building materials, such as paving stones in noxer blocks[38] or paints, can substantially
reduce concentrations of airborne pollutants such as volatile organic compounds and nitrogen oxides.[39]
A photocatalytic cement that uses titanium dioxide as a primary component, produced by Italcementi Group, was included in
Time's Top 50 Inventions of 2008.[40]
Attempts have been made to photocatalytically mineralize pollutants (to convert into CO2 and H2O) in waste water.[41]
TiO2 offers great potential as an industrial technology for detoxification or remediation of wastewater due to several factors:
[42]
The process uses natural oxygen and sunlight and thus occurs under ambient conditions; it is wavelength selective and is
accelerated by UV light.
The photocatalyst is inexpensive, readily available, non-toxic, chemically and mechanically stable, and has a high
turnover.
The formation of photocyclized intermediate products, unlike direct photolysis techniques, is avoided.
Oxidation of the substrates to CO2 is complete.
TiO2 can be supported as thin films on suitable reactor substrates, which can be readily separated from treated water.[43]
Electronic data storage medium
In 2010, researchers at the University of Tokyo, Japan have created a crystal form of titanium oxide with particles 5 to 20
nanometers that can be switched between two states with light. Use of the 5 nm particles could theoretically lead to a 25 TB
storage disc.[44]
Other applications Synthetic single crystals of TiO2, ca. 2–3 mm in size, cut from a larger plate.
Titanium dioxide in solution or suspension can be used to cleave protein that contains the amino acid proline at the site
where proline is present.[45]
Titanium dioxide is also used as a material in the memristor, a new electronic circuit element. It can be employed for solar
energy conversion based on dye, polymer, or quantum dot sensitized nanocrystalline TiO2 solar cells using conjugated
polymers as solid electrolytes.[46]
Synthetic single crystals and films of TiO2 are used as a semiconductor,[47] and also in Bragg-stack style dielectric
mirrors due to the high refractive index of TiO2 (2.5–2.9).[48][49]
Health and safety Ambox scales.svg
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talk page. (March 2011)

Titanium dioxide is incompatible with strong reducing agents and strong acids.[50] Violent or incandescent reactions occur
with molten metals that are very electropositive, e.g. aluminium, calcium, magnesium, potassium, sodium, zinc and lithium.
[51]
Titanium dioxide accounts for 70% of the total production volume of pigments worldwide.[citation needed] It is widely used
to provide whiteness and opacity to products such as paints, plastics, papers, inks, foods, and toothpastes. It is also used in
cosmetic and skin care products, and it is present in almost every sunblock, where it helps protect the skin from ultraviolet
light.
Many sunscreens use nanoparticle titanium dioxide (along with nanoparticle zinc oxide) which, despite reports of potential
health risks,[52] is not actually absorbed through the skin.[53] Other effects of titanium dioxide nanoparticles on human
health are not well understood.[54] Nevertheless, allergy to topical application has been confirmed.[55]
Titanium dioxide dust, when inhaled, has been classified by the International Agency for Research on Cancer (IARC) as an
IARC Group 2B carcinogen, meaning it is possibly carcinogenic to humans.[56] The findings of the IARC are based on the
discovery that high concentrations of pigment-grade (powdered) and ultrafine titanium dioxide dust caused respiratory tract
cancer in rats exposed by inhalation and intratracheal instillation.[57] The series of biological events or steps that produce the
rat lung cancers (e.g. particle deposition, impaired lung clearance, cell injury, fibrosis, mutations and ultimately cancer) have
also been seen in people working in dusty environments. Therefore, the observations of cancer in animals were considered,
by IARC, as relevant to people doing jobs with exposures to titanium dioxide dust. For example, titanium dioxide production
workers may be exposed to high dust concentrations during packing, milling, site cleaning and maintenance, if there are
insufficient dust control measures in place. However, the human studies conducted so far do not suggest an association
between occupational exposure to titanium dioxide and an increased risk for cancer. The safety of the use of nano-particle
sized titanium dioxide, which can penetrate the body and reach internal organs, has been criticized.[58] Studies have also
found that titanium dioxide nanoparticles cause inflammatory response and genetic damage in mice.[59][60] The mechanism
by which TiO2 may cause cancer is unclear. Molecular research suggests that cell cytotoxicity due to TiO2 results from the
interaction between TiO2 nanoparticles and the lysosomal compartment, independently of the known apoptotic signalling
pathways.[61]
The body of research regarding the carcinogenicity of different particle sizes of titanium dioxide has led the US National
Institute for Occupational Safety and Health to recommend two separate exposure limits. NIOSH recommends that fine TiO2
particles be set at an exposure limit of 2.4 mg/m3, while ultrafine TiO2 be set at an exposure limit of 0.3 mg/m3, as time-
weighted average concentrations up to 10 hours a day for a 40 hour work week.[62] These recommendations reflect the
findings in the research literature that show smaller titanium dioxide particles are more likely to pose carcinogenic risk than
the larger titanium dioxide particles.
There is some evidence the rare disease yellow nail syndrome may be caused by titanium, either implanted for medical
reasons or through eating various foods containing titanium dioxide.[63]

Brookite is orthorhombic, and one of the four naturally occurring polymorphs (minerals with the same composition but
different structure) of titanium dioxide, TiO2, approved by the International Mineralogical Association (IMA). The others are
akaogiite (monoclinic), anatase (tetragonal) and rutile (tetragonal). Brookite is rare compared to anatase and rutile and, like
these forms, it exhibits photocatalytic activity.[5] Brookite has a larger cell volume than either anatase or rutile, with 8 TiO2
groups per unit cell, compared with 4 for anatase and 2 for rutile.[6] Iron Fe, tantalum Ta and niobium Nb are common
impurities.[3]
It was named in 1825[3] for Henry James Brooke (1771–1857), an English crystallographer, mineralogist and wool trader.[1]
Arkansite is a variety of brookite from Arkansas, USA, that is also found in the Murunskii Massif, in the Eastern Siberian
region of Russia, where many other unusual minerals occur.[3]
At temperatures above about 750 °C, brookite will revert to the rutile structure.[7]
Unit cell Brookite belongs to the orthorhombic dipyramidal crystal class 2/m 2/m 2/m (also designated mmm). The space
group is Pcab and the unit cell parameters are a = 5.4558 Å, b = 9.1819 Å and c = 5.1429 Å. The formula is TiO2, with 8
formula units per unit cell (Z = 8).
Structure Crystal structure of brookite
The brookite structure is built up of distorted octahedra with a titanium ion at the center and oxygen ions at each of the six
vertices. Each octahedron shares three edges with adjoining octahedra, forming an orthorhombic structure.[8]
Appearance Brookite from Pakistan
Crystals are typically tabular, elongated and striated parallel to their length. They may also be pyramidal, pseudo-hexagonal
or prismatic.[3] Brookite and rutile may grow together in an epitaxial relationship.[3]
Brookite is usually brown in color, or sometimes yellowish or reddish brown, or even black. Beautiful, deep red crystals
(seen above-right) similar to pyrope and almandite garnet are also known. Brookite displays a submetallic luster. It is opaque
to translucent, transparent in thin fragments and yellowish brown to dark brown in transmitted light.[1][3][4]
Optical properties Brookite is doubly refracting, as are all orthorhombic minerals, and it is biaxial (+). Refractive indices are
very high, above 2.5, which is even higher than diamond at 2.42. For comparison, ordinary window glass has a refractive
index of about 1.5.
Brookite exhibits very weak pleochroism, yellowish, reddish and orange to brown.[3][4] It is neither fluorescent nor
radioactive.[1]
Physical properties Brookite is a brittle mineral, with a subconchoidal to irregular fracture and poor cleavage in one
direction parallel to the c crystal axis and traces of cleavage in a direction perpendicular to both the a and the b crystal axes.
[1][3][4] Twinning is uncertain.[3][4] The mineral has a Mohs hardness of 5½ to 6, between apatite and feldspar. This is the
same hardness as anatase and a little less than that of rutile (6 to 6½). The specific gravity is 4.08 to 4.18, between that of
anatase at 3.9 and rutile at 4.2.[3][4]
Occurrence and associations Brookite is an accessory mineral in alpine veins in gneiss and schist; it is also a common
detrital mineral.[3][4] Associated minerals include its polymorphs anatase and rutile, and also titanite, orthoclase, quartz,
hematite, calcite, chlorite and muscovite.[4]
The type locality is Twll Maen Grisial, Fron Olau, Prenteg, Gwynedd, Wales, UK,[3] and in 2004 fine brookite crystals were
found at Kharan, in Balochistan, Pakistan, together with brookite and rutile inclusions in quartz.[3]
Anatase is one of the three mineral forms of titanium dioxide, the other two being brookite and rutile. It is always found as
small, isolated and sharply developed crystals, and like rutile, a more commonly occurring modification of titanium dioxide,
it crystallizes in the tetragonal system; but, although the degree of symmetry is the same for both, there is no relation
between the interfacial angles of the two minerals, except in the prism-zone of 45° and 90°. The common pyramid of anatase,
parallel to the faces of which there are perfect cleavages, has an angle over the polar edge of 82°9', the corresponding angle
of rutile being 56°52½'. It was on account of this steeper pyramid of anatase that the mineral was named, by René Just Haüy
in 1801, from the Greek anatasis, "extension", the vertical axis of the crystals being longer than in rutile. There are also
important differences between the physical characters of anatase and rutile: the former is less hard (5.5–6 vs. 6-6.5 Mohs)
and dense (specific gravity about 3.9 vs. 4.2). Also, anatase is optically negative whereas rutile is positive, and its luster is
even more strongly adamantine or metallic-adamantine than that of rutile.
Crystal habit
Crystal structure of anatase Two types or habits of anatase crystals may be distinguished. The more common occurs as
simple acute double pyramids with an indigo-blue to black color and steely luster. Crystals of this kind are abundant at Le
Bourg-d'Oisans in Dauphiné, where they are associated with rock-crystal, feldspar, and axinite in crevices in granite and
mica-schist. Similar crystals, but of microscopic size, are widely distributed in sedimentary rocks, such as sandstones, clays,
and slates, from which they may be separated by washing away the lighter constituents of the powdered rock.
Crystals of the second type have numerous pyramidal faces developed, and they are usually flatter or sometimes prismatic in
habit; the color is honey-yellow to brown. Such crystals closely resemble xenotime in appearance and, indeed, were for a
long time supposed to belong to this species, the special name wiserine being applied to them. They occur attached to the
walls of crevices in the gneisses of the Alps, the Binnenthal near Brig in canton Valais, Switzerland, being a well-known
locality. Naturally occurring pseudomorphs of rutile after anatase are also known.
While anatase is not an equilibrium phase of TiO2, it is kinetically stabilized. At temperatures between 550 and about 1000
°C, anatase transforms to the equilibrium rutile phase, increasing its specific gravity to 4.2. The temperature of this
transformation strongly depends on the impurities or dopants present in the material as well as on the morphology of the
sample.[4]
Synthetic anatase Crystals of anatase can be prepared in laboratories by chemical methods such as sol-gel method.
Examples include controlled hydrolysis of titanium tetrachloride (TiCl4) or titanium alkoxides. Such synthetic anatases are
of considerable interest for photocatalysis and for Grätzel-cell photovoltaics.
Alternate and obsolete names Another name commonly in use for this mineral is octahedrite, a name which, indeed, is
earlier than anatase, and given because of the common (acute) octahedral habit of the crystals. Other names, now obsolete,
are oisanite and dauphinite, from the well-known French locality.
Rutile is a mineral composed primarily of titanium dioxide, TiO2.
Rutile is the most common natural form of TiO2. Two rarer polymorphs of TiO2 are known:
Anatase (sometimes known by the obsolete name "octahedrite"), a tetragonal mineral of pseudo-octahedral habit
Brookite, an orthorhombic mineral
Rutile has among the highest refractive indices at visible wavelengths of any known crystal, and also exhibits a particularly
large birefringence and high dispersion. Owing to these properties, it is useful for the manufacture of certain optical
elements, especially polarization optics, for longer visible and infrared wavelengths up to about 4.5μm.
Natural rutile may contain up to 10% iron and significant amounts of niobium and tantalum. Rutile derives its name from the
Latin rutilus, red, in reference to the deep red color observed in some specimens when viewed by transmitted light.
Occurrence Rutile output in 2005
Rutile is a common accessory mineral in high-temperature and high-pressure metamorphic rocks and in igneous rocks.
Thermodynamically, rutile is the most stable polymorph of TiO2 at all temperatures, exhibiting lower total free energy than
metastable phases of anatase or brookite.[5] Consequently, the transformation of the metastable TiO2 polymorphs to rutile is
irreversible. As it has the lowest molecular volume of the three main polymorphs; it is generally the primary titanium bearing
phase in most high-pressure metamorphic rocks, chiefly eclogites.
Rutile in quartz Within the igneous environment, rutile is a common accessory mineral in plutonic igneous rocks, though it
is also found occasionally in extrusive igneous rocks, particularly those that have deep mantle sources such as kimberlites
and lamproites. Anatase and brookite are found in the igneous environment particularly as products of autogenic alteration
during the cooling of plutonic rocks; anatase is also found in placer deposits sourced from primary rutile.
The occurrence of large specimen crystals is most common in pegmatites, skarns, and granite greisens. Rutile is found as an
accessory mineral in some altered igneous rocks, and in certain gneisses and schists. In groups of acicular crystals it is
frequently seen penetrating quartz as in the fléches d'amour from Graubünden, Switzerland. In 2005 the Republic of Sierra
Leone in West Africa had a production capacity of 23% of the world's annual rutile supply, which rose to approximately 30%
in 2008. The reserves, lasting for about 19 years, are estimated at 259,000,000 metric tons (285,000,000 short tons).[6]
Crystal structure The unit cell of rutile. Ti atoms are gray; O atoms are red.
Rutile has a body-centred tetragonal unit cell, with unit cell parameters a=b=4.584 Å, and c=2.953 Å.[7] The titanium cations
have a coordination number of 6 meaning they are surrounded by an octahedron of 6 oxygen atoms. The oxygen anions have
a co-ordination number of 3 resulting in a trigonal planar co-ordination. Rutile also shows a screw axis when its octahedra
are viewed sequentially.[8]
Uses and economic importance Acicular crystals of rutile protruding from a quartz crystal
In large enough quantities in beach sands, rutile forms an important constituent of heavy minerals and ore deposits. Miners
extract and separate the valuable minerals—e.g., rutile, zircon, and ilmenite. The main uses for rutile are the manufacture of
refractory ceramic, as a pigment, and for the production of titanium metal.
Finely powdered rutile is a brilliant white pigment and is used in paints, plastics, paper, foods, and other applications that call
for a bright white color. Titanium dioxide pigment is the single greatest use of titanium worldwide. Nanoscale particles of
rutile are transparent to visible light but are highly effective in the absorption of ultraviolet radiation. The UV absorption of
nano-sized rutile particles is blue-shifted compared to bulk rutile, so that higher-energy UV light is absorbed by the
nanoparticles. Hence, they are used in sunscreens to protect against UV-induced skin damage.
Small rutile needles present in gems are responsible for an optical phenomenon known as asterism. Asteriated gems are
known as "star" gems. Star sapphires, star rubies, and other "star" gems are highly sought after and are generally more
valuable than their normal counterparts.
Rutile is widely used as a welding electrode covering. It is also used as a part of the ZTR index, which classifies highly
weathered sediments.
Synthetic rutile Synthetic rutile was first produced in 1948 and is sold under a variety of names. Very pure synthetic rutile is
transparent and almost colorless (slightly yellow) in large pieces. Synthetic rutile can be made in a variety of colors by
doping. The high refractive index gives an adamantine luster and strong refraction that leads to a diamond-like appearance.
The near-colorless diamond substitute is sold as "Titania", which is the old-fashioned chemical name for this oxide.
However, rutile is seldom used in jewellery because it is not very hard (scratch-resistant), measuring only about 6 on the
Mohs hardness scale