DOI 10.

1007/s11148-019-00304-2
Refractories and Industrial Ceramics Vol. 60, No. 1, May, 2019

SCIENTIFIC RESEARCH AND DEVELOPMENT

ALUMINUM OXIDE AND ALUMINA CERAMICS (REVIEW).

PART 1. PROPERTIES OF Al2O3 AND COMMERCIAL PRODUCTION
OF DISPERSED Al2O3

A. M. Abyzov1,2

Translated from Novye Ogneupory, No. 1, January, pp. 16 – 23, 2019.

Original article submitted June 22, 2018.

This paper provides a review of aluminum oxide properties associated with its use, varieties of commercial
products, methods for producing aluminum oxide in a disperse state, in the form of polycrystalline ceramics
and single-crystal products, as well as chemical aspects of the related technological processes.
Keywords: aluminum oxide, alumina ceramics, abrasives, composites.

ALUMINIUM OXIDE AND ITS COMMERCIAL terials as a filler (Al2O3 fibers) or matrix (for example, rein-
PRODUCTION [1 – 5] forced with SiC fibers). In addition, Al2O3 demonstrates
biocompatibility and is used in medicine for implants, in-
Aluminum oxide3 possesses such useful properties, as cluding synthetic eye lens. Due to high mechanical charac-
high melting point, hardness and strength, wear resistance, teristics, low density and availability, Al2O3 is the most com-
and chemical stability. Sapphire and ruby represent a sin- mon material used in ceramic armor.
gle-crystal corundum with impurities (Ti, Fe and Cr), which The variety of uses is caused by various useful character-
provide coloring (blue and red colors), and are used in jew- istics of Al2O3. Some of its properties are provided in Table 1
elry-making. Synthetic colorless leucosapphires are used as along with the properties of other common oxides, which can
high-strength optical components for the cabin windows, ac- be present in alumina-based materials as impurities or specif-
tive laser components, etc. Polycrystalline Al2O3 is relatively ically introduced additives. The provided characteristic val-
inexpensive and is one of the most common types of ceram- ues refer to both, crystalline (and amorphous, in case of
ics used as refractory material, electrical insulators, wear-re- SiO2) materials and dense sintered ceramics; the latter is true
sistant mechanical components, abrasive material for ma- predominantly for the database provided in Ref. [6]. For ex-
chining, etc. In electronics, dielectric substrates made of ample, the range of density values (g) refers to a number of
both, polycrystalline and single-crystal Al2O3 are used. The technical products.
majority of produced a-Al2O3 is used as an intermediate Corundum distinctively surpasses all other oxides in
product to obtain aluminum by fusion electrolysis. The white terms of hardness (H) and also has a very high compressive
color of sintered Al2O3 (as opposed to transparent sapphire) strength (sc). Its ultimate flexural (sf) and tensile (st)
is caused by light scattering by pores and inclusions of impu- strength values, as well as crack resistance (K1c) are lower
rity phases. Aluminum oxide is used in some composite ma- than those of some oxides, such as ZrO2. The wear resistance
1
of polycrystalline Al2O3 (dense corundum ceramics) sur-
Federal State Budgetary Educational Institution “Saint Petersburg passes that of a single-crystal alumina (sapphire). Corundum
State Technological Institute (Technical University)”, Saint Pe-
ceramics and sapphire are the best insulators among the ex-
tersburg, Russia.
2
andabyz@mail.ru isting oxides, except for SiO2, which has a much higher elec-
3
A reference to aluminum oxide (Al2O3) in general often implies tric field (breakdown) strength (Ebr) and, according to certain
corundum (a-Al2O3), although in a stricter sense, Al2O3 includes data, higher specific electrical resistivity (r) (see Table 1).
all, even metastable modifications. The values of some properties provided in different sources

24
1083-4877/19/06001-0024 © 2019 Springer Science+Business Media, LLC
Aluminum Oxide and Alumina Ceramics (Review). Part 1 25

TABLE 1. Selected properties of alumina, silica, zirconia, titania, and magnesia.

Property a-Al2O3 SiO2 ZrO2 TiO2 MgO Reference
3
Density (g), g/cm3 3.99 2.20 – 2.65 (5.80 – 6.05)* 4.24 3.58 [1]
3 – 3.98 2.20*1, 2.65*2 5 – 6.15 4 3.54 – 3.58 [6]
Melting point (Tm), oC 2054 1710*4 2710 1855 2852 [1]
2004 – 2096 — 2550 – 2700 — 2807 – 2862 [6]
Ultimate strength, MPa:
flexure (sf) 282 310 430 – 720*3 340 441 [1]
152 – 800 110 – 200 177 – 1000 140 100 – 200 [6]
compression (sc) 2550 – 3100 680 – 1380 1850*3 800 – 940 1300 – 1380 [1]
690 – 5500 2070*1, (690 – 1380)*2 1200 – 5200 680 830 – 1670 [6]
Modulus of elasticity (E), GPa 365 – 393 73 200*3 248 – 282 303 [1]
215 – 413 66 – 75 100 – 250 230 270 – 330 [6]
Crack resistance (K1c), MPa·m0.5 — — (7 – 15)*3 — — [1]
3.3 – 5.0 0.62 – 0.67 1–8 3.2 2.7 – 2.8 [6]
Hardness:
Vickers (HV), GPa 20.6 – 29.4 8 14.4, 15.7 — 7.4 [1]
5.5 – 22.0 4.5 – 9.5 5.5 – 15.8 8.6 5–7 [6]
Mohs (HM) 9 7 6.5*5 7.0 – 7.5 5.5 – 6.0 [1]
9 7 8 6.5 — [7]
TCLE, ppm/K 7.1 – 8.3 0.55 10.1*3 7.1 11.5 [1]
4.5 – 10.9 0.4*1, 12.3*2 2.3 – 12.2 — 9 – 12 [6]
Thermal conductivity (l), W/(m(K) 36 – 39 1.4 (1 – 2)*3 7.4*6, 10.4*7 50 – 75 [1]
12.0 – 38.5 14*1 (6.2*6, 6*7)*2 1.7 – 2.7 11.7 30 – 60 [6]
Specific volumetric electrical 2 ´ 10 17
1014 — 1013 109 [1]
resistivity (r), Ohm·cm 1012 – 1018 (1012 – 1016)*1, (>1018)*2 107 – 1012 1012 1014 – 1015 [6]
Breakdown strength (Ebr), kV/mm 13 (470 – 670)*1 11 — — [8]
8 – 43 15 – 40 4–6 4 6 – 10 [6]
Relative specific permittivity (er) 9.3*8, 11.5*9 4.4*8, 4.6*9 12.5 86*8, 170*9 9.6 [8]
7.8 – 11.1 3.6 – 4.2 10 – 23 85 6.8 – 9.6 [6]

*1 Quartz glass.
*2 Quartz (a-SiO2).
*3 Cubic partially stabilized MgO (~3 wt.%).
*4 Cristobalite (formed as a result of quartz transition upon heating).
*5 Baddeleyite.
*6 Perpendicular to crystallographic c-axis (^c).
*7 Parallel to crystallographic c-axis (||c).
*8 Tensor components along main crystal axes (e11 = e22).
*9 Tensor component along main crystal axes (e33).

may vary. This primarily relates to such structure-sensitive tanate (~103), etc. Based on its value of er < 15, Al2O3 is
mechanical properties, as strength and crack resistance, and placed into a group of materials with low dielectric
specifically, Ebr. The value of Ebr depends on the type of permittivity [10]4. This limits somewhat the Al2O3 applica-
electrical voltage (ac versus dc), and to a certain extent, the tion in electric condensers and microwave resonators. How-
thickness of the dielectric layer [9]. Therefore, comparing ever, there are some types of condensers, which contain a di-
Ebr — related data from different sources is often compli- electric Al2O3 layer (thin-film, electrolytic). Besides,
cated or incorrect. Al2O3 poses interest for microwave equipment, since sap-
The dielectric permittivity (er) of Al2O3, which is about 4
There is an alternative classification, according to which materi-
10, although higher compared to the majority of dielectrics, als with er > 7 (silicon nitride), including Al2O3, are placed in the
but is still relatively low compared to TiO2 (~102), barium ti- high dielectric permittivity group.
26 A. M. Abyzov

phire has the lowest values of the dielectric loss tangent perature increases with Al2O3 purity in the raw material. For
(tand) among known substances [11]. This enables the use of high-purity corundum ceramics (>99.7%), the sintering tem-
nonporous fine-grained Al2O3 of high purity in quality reso- perature can reach 1900 – 2000°C. Frequently, in order to re-
nators used in low-noise oscillators. Some additives (i.e., move the binder, as well as traces of water and other volatile
TiO2 in the amount of 0.25 wt.%) improve dielectric proper- impurities, a slow heating or soaking at an intermediate tem-
ties of Al2O3 by reducing dielectric losses. perature (calcination) is used. In general, the methods of pro-
The thermal conductivity (l) of Al2O3 at the room tem- ducing Al2O3 ceramics may vary quite significantly and in-
perature is much higher compared to the majority of other clude the following: extrusion, dry pressing, pressure cast-
nonmetals. The only oxides having higher thermal conduc- ing, slip casting, isostatic pressing (dry or wet), and hot iso-
tivity than Al2O3 are MgO (~60 W/(m·K)) and BeO static pressing. A single-crystal Al2O3 (sapphire) is produced
(230 – 370 W/(m·K)) [12]. When dielectric substrates are re- by growing crystals from the melt at a high temperature
quired to remove the increased amounts of heat, Al2O3 is re- (above the melting point of 2054°C) using the raw materials
of higher purity compared to those used for producing corun-
placed with AlN (l ranges from 140 – 200 W/(m·K) for
dum ceramics, which has a polycrystalline structure.
polycrystalline ceramics to 320 – 350 W/(m·K) for single
A number of properties of alumina ceramics strongly de-
crystals). The thermal coefficient of linear expansion
pend on impurity content of the initial powder. Commer-
(TCLE) of Al2O3 is higher than that of other ceramic materi-
cially produced Al2O3 powders typically contain such impu-
als (sintered carbides, nitrides, mullite, cordierite, etc.).
rities, as silicon, calcium, magnesium, sodium, and potas-
The stable crystalline phase of a-Al2O3 (corundum) has sium oxides. SiO2, CaO, Na2O, and K2O melt at a lower tem-
a hexagonal structure. Its oxygen anions are densely packed perature compared to Al2O3, and form liquids during
into a hexagonal sublattice, while much smaller in size alu- sintering. These liquids promote formation of a more dense
minum cations occupy 2/3 of the octahedral interstitial cen- ceramics, but lower its mechanical properties at high temper-
ters of the oxygen sublattice. A natural raw material contain- atures (strength, creep resistance). The most common impu-
ing up to 98% of Al2O3 or pure corundum is also called alu- rity is SiO2 (silica). Glasses, formed from oxide impurities,
mina. Upon crystallization from aqueous solutions or dehy- typically segregate along the grain boundaries of the sintered
dration of aluminum hydroxides, metastable crystalline material. The raw material impurities, such as Na2O, are ob-
phases (cubic g-Al2O3, etc.) are formed. Above 1000°C, the viously undesirable, since they worsen the properties of alu-
metastable phases transform into a-Al2O3, and to complete mina ceramics (mechanical, thermal conductivity, etc.). The
recrystallization, temperatures of up to 1450°C may be re- sintering of pure Al2O3 occurs in accordance with the
quired. The metastable phases of Al2O3 have limited applica- solid-phase mechanism. Only a very limited quantity of com-
tion, mainly as sorbents, catalyst carriers, and raw materials mercial products can be classified as obtained under the
for obtaining a-Al2O3. solid-phase sintering conditions. It was shown that corundum
Aluminum hydroxide has two stoichiometric composi- ceramics with the purity of 99.98% and lower contains thin
tions: Al(OH)3 = Al2O3·3H2O and AlO(OH) = Al2O3·H2O amorphous films comprising SiO2–CaO–Al2O3 along the
(the latter is also called oxyhydroxide). Each of these com- grains boundaries.
pounds exists in two crystalline forms — a and g. Besides, Some impurities are introduced to Al2O3 as special addi-
there is an amorphous aluminum hydroxide, which has a tives. The introduction of additives leads to a decrease in the
sintering temperature, which simplifies the ceramics fabrica-
variable composition of Al2O3·nH2O. The chemical activity
tion process and reduces its cost. The most popular modifier
decreases according to the following sequence: amorphous
introduced in small quantities (1 – 3 wt.% or less, in the
hydroxide > bayerite a-Al(OH)3 > gibbsite (hydrargillite)
amount of up to several basis points (bps)) is MgO, which
g-Al(OH)3 > boehmite g-AlO(OH) > diaspore a-AlO(OH). suppresses the abnormal growth of corundum grains. The ab-
The corundum ceramics has high chemical resistance in normal grain growth is caused by many impurities, when
both, oxidizing and reducing atmospheres in acidic or alka- their concentration exceeds the solubility limit in corundum
line media. The inertness of Al2O3 is associated, in particu- (~0.03 wt.% of SiO2, ~0.003 wt.% of CaO, etc.). Unlike
lar, with the fact that its heat of formation is higher than that MgO, other modifying additives usually facilitate liq-
of the majority of other oxides (ZrO2, Cr2O3, TiO2, SiO2, uid-phase sintering. This often occurs due to direct introduc-
MgO, etc.). tion or in-situ formation of rather low-melting point eutectics
The Al2O3 products are fabricated using typical for tech- during sintering, for example an Al2O3–ZrO2 system
nical ceramics techniques. A finely ground Al2O3 powder eutectic. The maximum reduction in sintering temperature of
having a particle size of about 0.2 – 5.0 mm and usually com- corundum (to 1300°C) during a liquid-phase mechanism is
bined with an organic binder, is pressed in a die, followed by made possible by the MnO–TiO2 additive [13]. The intro-
drying and baking at 1500 – 1800°C. A temporary organic duced modifiers are usually accumulated along the grain
binder can either be added to the entire volume of boundaries of corundum during sintering, which limits the
Al2O3 powder, or incorporated by way of forming granules, grain growth of the produced ceramics, and hence, provides
which are subsequently dried and pressed. The sintering tem- high mechanical characteristics. At the same time, such addi-
Aluminum Oxide and Alumina Ceramics (Review). Part 1 27

tive as, for example, TiO2 causes an increase instead of re- MgAl2O4 (Tm = 2135°C), and aluminum titanate Al2TiO5
duction in the grain size of corundum ceramics. (Tm = 1860°C), respectively. All these compounds have their
ZrO2 in the form of partially stabilized (typically, by add- individual values, and for example, are manufactured in the
ing about 3 wt.% of Y2O3) tetragonal ZrO2 can be introduced form of ceramics. Upon introduction of oxide additives dur-
to Al2O3 in considerable quantities (10 – 30 wt.%), so that ing Al2O3 sintering, these compounds can be formed as sepa-
the sintered product represents a Al2O3-ZrO2 composite, usu- rate phases. In addition, of great practical importance are
ally designated as ZTA. ZrO2 additives significantly improve calcium aluminate CaAl2O4 (fire-resistant cement,
the strength and impact resistance characteristics. Generally Tm = 1870°C) and yttrium aluminate Y3Al5O12 (yttrium-alu-
speaking, the composition of Al2O3–ZrO2 ceramics may vary minum garnet, Tm = 1970°C). In all considered binary sys-
within the entire range from Al2O3 to ZrO2. Examples in- tems eutectics are present. Those include eutectics with the
clude composites with filler consisting of Al2O3 particles in lowest melting temperature in the system (Tm): 1390°C
the amount of 0 to 30 mol. % in a matrix made up of com- (C12A7–CA), 1590°C (SiO2-mullite), 1725°C (TiO2–Al2TiO5),
pletely stabilized ZrO2 containing the 10 mol. % of Y2O3 1870°C (Al2O3–ZrO2, 40 wt.% of ZrO2), and 1995°C
[14]. The Al2O3–ZrO2 system ceramics is used to produce (MgO–spinel) [4, 16, 17]. Another type of the phase diagram
cutting tools and abrasives. Recently, the Japanese research- is typical for the Al2O3–Cr2O3 system containing a continu-
ers succeeded in obtaining ceramics comprising 75 mol. % ous sequence of solid solutions [18].
of ZrO2 (with 1.5 mol.% of Y2O3) and 25 mol.% of Al2O3 Alumina ceramics is produced in quite wide range of pu-
with very high mechanical properties (sf ³ 1350 MPa and rity (basic Al2O3 content) depending on the application spe-
K1c ³ 15.5 MPa·m0.5) [15]. However, analyzing zirconia-co- cifics. For example, high-purity corundum ceramics
rundum ceramics with dominating ZrO2 phase content ex- (99.5 – 99.8%) can be used at the maximum temperature
tends beyond the scope of this review. (Tmax) ranging from 1750 to 1900°C [19, 20]. Ceramics con-
A possibility of obtaining Al2O3–ZrO2 composites is taining 94 – 97% of Al2O3 can be easily metallized. Table 2
caused by the fact that Al2O3 does not form compounds with shows the properties of Al2O3 ceramics depending on purity,
ZrO2. As opposed to this, other practically important binary and for comparison purposes, the properties of ceramics
Al2O3-oxide systems typically contain stable compounds. In based on partially stabilized zirconia (PSZ) according to
Al2O3–SiO2, Al2O3–MgO, and Al2O3–TiO2 systems, such German standard “Ceramic and Glass Insulating Materials”
compounds are: mullite 3Al2O3·2SiO2 (aluminum (1999). In corundum ceramics, an increase in density and
metasilicate5, Tm = 1890°C), magnesium aluminate spinel thermal conductivity, as well as improvement in mechanical
properties (E, s, K1c, H) are observed as the impurity content
5
There are also metastable aluminum orthosilicates Al2SiO5 (silli- decreases. The properties of ceramics, especially mechani-
manite, andalusite, and kyanite). cal, are directly determined by the material microstructure,

TABLE 2. Properties of alumina ceramics with different Al2O3 and PSZ contents according to DIN EN 60672 [1] (open porosity (W) of all ma-
terials is equal to zero).
Property <90% Al2O3 92 – 96% Al2O3 99% Al2O3 >99% Al2O3 PSZ

g, g/cm3 >3.2 3.4 – 3.8 3.5 – 3.9 3.75 – 3.98 ³5 – 6

Tmax *1 , ° C 1400 – 1500 1400 – 1500 1400 – 1500 1400 – 1700 900 – 1600
sf, MPa >200 230 – 400 280 – 400 300 – 580 500 – 1000
E, GPA >200 220 – 340 220 – 350 300 – 380 200 – 210
K1c, MPa·m0.5 3.5 – 4.5 4 – 4.2 4 – 4.2 4 – 5.5 5.8 – 10.5
HV*2, GPa 12 – 15 12 – 15 12 – 20 17 – 23 11 – 12.5
TCLE*3, ppm/K 6–8 6–8 6–8 7–8 10 – 12.5
l*4, W/(m·K) 10 – 16 14 – 25 16 – 28 19 – 30 1.5 – 3.0
e, Ohm·cm 1012 – 1013 1012 – 1014 1012 – 1015 1012 – 1015 108 – 1013
Ebr, kV/mm 10 15 – 25 15 17 —
er 9 9 – 10 9 9 —
tand (at 1 MHz) 1 – 10 – 3 1 – 10 – 3 1 – 10 – 3 1 – 10 – 3 —

*1 Typical values.
*2 Under 100g load.
*3 At 30 – 600°C.
*4 At 30 – 100°C.
28 A. M. Abyzov

TABLE 3. ISO 6474-1 requirements for high-purity corundum ce- which is why the correlation between the properties and ma-
ramics used in implants for surgery [21]. terial composition may be challenging. Corundum ceramics
Property*1 Type A Type B has better electrical insulation properties (r, Ebr), and l, as
Composition, wt.%:
well as E and H than zirconia ceramics, however, the latter
has better sf and K1c. It should be noted that providing a
Basic Al2O3 ³99.7 ³99.5
fine-grained strong microstructure of corundum ceramics
MgO additive £0.2 £0.2 poses a challenging technological task due to the natural ten-
(SiO2 + CaO + Na2O) impurities £0.1 £0.3 dency of a-Al2O3 crystallites to grow at high temperatures.
g, g/cm3 ³3.94 ³3.90 In case of commercially available strong constructional ce-
d, mm £2.5 £3.5 ramics (see Section “Alumina ceramics manufacturers”), the
size of the grains (crystallites) constitutes from one to several
STD d, % £25 £25
microns. In case of transparent ceramics intended for optical
*2 *2
æ ³ 300 ö æ ³ 150 ö applications, the size of a-Al2O3 crystallites usually consti-
sf, MPa ç ÷ ç ÷
è ³ 500 ø è ³ 250 ø tutes tens of microns, although the main condition of trans-
Weibull modulus for sf ³8 ³8 parency of corundum ceramics is the low residual porosity
K1c *3 , MPa·m0.5 ³2.5 — (<0.1%). For example, it is possible to obtain transparent
Al2O3 samples with submicron granularity [5]. The fact that
HV, GPa (at 1 kg load) ³18 ³17 the technology for producing alumina ceramics has been re-
*1 d — average size of grains (crystallites); STD — standard devia- fined quite well is reflected in the international standards
tion. ISO 6474-1:2010 and ISO 6474-2:2012 for medical applica-
*2 Numerator — when testing a plate using two coaxial rings. De- tion products, which regulate the composition and
nominator — during four-point flexure. microstructure parameters, as well as mechanical properties
*3 When testing by SEVNB, SEPB, or SCF methods, i.e., when cre- of corundum ceramics and ZTA. Tables 3 and 4 provide data
ating a cut, crack, or dent on one side of the sample. from these standards.
There are some occasional statements in the literature
suggesting that the cost of alumina ceramics is low. In order
TABLE 4. ISO 6474-2 requirements for ZTA ceramics used in im-
to quantitatively assess its cost and compare it with the cost
plants for surgery [22]. of other materials, the author used Ref. [23], which contained
prices of products of the same format and identical or com-
Property Type X Type S
parable sizes for substrates made of dense ceramics and other
Composition, wt.%: technical materials. The results of such comparison are pro-
Al2O3 60 – 90 60 – 90
(ZrO2 + HfO2) 10 – 30 10 – 30
HfO2 content in ZrO2 £5 £5 TABLE 5. Cost of substrates from various nonmetallic materials
(sampled indicative data) [23].
prescribed additives £10 £10
impurities £0.2 £0.2 Material Substrate size, mm Price per 1 pc., USD

Relative density, % ³99 ³99 Al2O3 10 ´ 10 ´ 0.5 10 – 13

ZrO2: 25.4 ´ 25.4 ´ 0.5 20
d, mm £1.5 £1.5 Al2O3 (high purity – 99.9%) 50.8 ´ 50.8 ´ 0.5 300 – 350
STD d, % £25 £25 Al2O3 (sapphire) 10 ´ 10 ´ 0.5 22 – 35*
Al2O3:
12.7 ´ 12.7 ´ 0.5 35 – 50*
d, mm £0.6 £0.6
AlN 25.4 ´ 25.4 ´ 0.5 25 – 40
STD d, % £40 £40
sf, MPa *1 *1 SiO2 (quartz glass) 10 ´ 10 ´ 0.5 18
æ ³ 600 ö æ ³ 450 ö
ç ÷ ç ÷ Si3N4 10 ´ 10 ´ 1 70
è ³ 1000 ø è ³ 750 ø
Weibull modulus for sf ³8 ³8 SiC 25.4 ´ 25.4 ´ 1 85
K1c*2, MPa·m0.5 ³4.0 ³3.5 BN (pyrolytic) 10 ´ 10 ´ 1 80
HV, GPa (at 1 kg load) ³16.0 ³15.5 C (pyrolytic graphite) 10 ´ 10 ´ 0.5 50
C (highly oriented pyrolytic 10 ´ 10 ´ 1 300 – 600
*1 Numerator — when testing a plate using two coaxial rings. De- graphite)
nominator — during four-point flexure.
*2 When testing by SEVNB, SEPB, or SCF methods, i.e., when cre- * Varies depending on crystallographic orientation of
ating a cut, crack, or dent on one side of the sample. the plate (in planes A, C, M, or R).
Aluminum Oxide and Alumina Ceramics (Review). Part 1 29

vided in Table 5, where materials are arranged according to 10 mm (larger size corresponds to higher baking tempera-
their cost level. As it turned out, the average cost of a regular ture). The products of commercial production of Al2O3 are
corundum ceramics is indeed several times lower than the subdivided into the following:
cost of other ceramics (AlN, Si3N4, SiC) as well as materials – transition aluminum oxides (transition aluminas), i.e.
obtained by chemical vapor deposition (CVD) method metastable forms of Al2O3 (all, except for a-Al2O3). Their
(pyrolytic BN, graphite). However, the cost of high-purity characteristic properties include high specific surface reach-
corundum ceramics is close or even higher than that of a sin- ing 400 m2/g and internal porosity. The transition aluminas
gle-crystal Al2O3 – sapphire (per unit volume of the material) are non-selective adsorbents. Transformation of transition
despite the fact that the purity of sapphire and its production oxides into a-Al2O3 during heat treatment is irreversible;
temperature are higher, than in any alumina ceramics.
– calcined (fired) alumina for ceramics and refractory
The main raw source of Al2O3 is bauxite, which mainly materials production, which represents a final product of
consists of the hydrated forms of Al2O3 (gibbsite, boehmite, thermal decomposition of aluminum hydroxides. The baking
diaspore). Bauxite contains on average from 45 to 60 wt.% process is conducted in drum and tunnel furnaces in a
of Al2O3 (hydroxide basis), 10 to 30 wt.% of Fe2O3, and the fluidized layer. The process yields a brittle polycrystalline
balance – SiO2, CaO, TiO2 and H2O. Currently, about 90 or
a-Al2O3. There is a wide range of technical grades of cal-
95 % of the global supply of aluminum hydroxide is pro-
cined Al2O3 – from pure grade to grades containing large
duced according to the Bayer process suggested in 1887.
amounts of sodium (so-called b-alumina Na2O(11Al2O3).
Bauxite ore is crushed and treated with alkaline solutions of
Na(OH) and Ca(OH)2. At the first stage, aluminum hydrox- The morphology of a-Al2O3 crystallites strongly depends on
ides are converted into sodium aluminate NaAlO2. During the mineralizer nature. For example, fluorine produces flat,
this process, only silica gets dissolved, while CaO, Fe2O3, hexagon-shaped crystallites, boron produces rounded crys-
and TiO2 remain as part of an insoluble residue. Silica is re- tallites, and boron chloride produces round dense crystals.
moved the subsequent slow heating, when Na2Si(OH)6 pre- Unlike transition Al2O3, the particles of calcined Al2O3 are
cipitate is formed. The remaining clear solution of nonporous, so that the specific surface of the material
NaAl(OH)4 is cooled, diluted with water, and neutralized matches the external surface of the particles. Technical grade
with carbon dioxide. As a result, Al(OH)3 is selectively pre- calcined Al2O3 is classified based on the particle size, crys-
cipitated from the solution without the dissolved silica resi- tallite morphology (angular, rounded, flat), sodium content,
dues. Aluminum trihydrate Al(OH)3 (gibbsite) is calcined at and to a lesser extent, others impurities. Depending on the
250 – 1300°C yielding anhydrous Al2O3. The main portion sodium impurity content, the calcined Al2O3 has the follow-
of the globally produced aluminum hydroxide is used for ing grades: standard grade, containing 0.3 to 0.7 wt.% of
smelting of metallic aluminum (by using metallurgical grade Na2O; intermediate grade, containing 0.1 to 0.3 wt.% of
Al2O3). Al(OH)3 is partially used to make fillers of compos- Na2O; low-sodium grade (0.03 to 0.10 wt.% of Na2O), and
ite materials, fire retardant compositions, chemicals, etc., high-purity grade with extremely low sodium content
while the rest of Al(OH)3 serves as a raw material for pro- (<0.01 wt.% of Na2O; such Al2O3 grade is obtained from alu-
ducing non-metallurgical grade Al2O3, i.e., alumina ceram- minum hydroxide using other than the Bayer process tech-
ics, refractory materials, etc. Obtaining an oxide from hy- nologies). Calcined Al2O3 is mostly used as a raw material
droxide comes down to heat treatment. The characteristics of for producing ceramics, refractory materials, glasses, enam-
calcined Al2O3 vary quite significantly depending on baking els, tiles, and porcelain. Unground calcined Al2O3 typically
conditions. At low baking temperatures (300 – 800°C), tran- has the particle size of 50 – 150 mm, while more fine grades
sitional forms of Al2O3 are formed (metastable crystalline are obtained by using additional grinding. The finely ground
modifications of d-, g-, h-, k-, c- and q-Al2O3). As a result of calcined Al2O3 used to produce ceramics and refractory ma-
high-temperature baking at 1000 – 1300°C, a-Al2O3 corun- terials, which demonstrates good sintering ability (allows ob-
dum is formed. Chemical and phase transitions from alumi- taining dense ceramics at relatively low sintering tempera-
num hydroxides to corundum [2] are shown below: tures (~1600°C)), is called reactive alumina;
– lamellar (tabular) alumina, also called sintered alu-
Gibbsite g-Al(OH)3 280° C 800° C 1000° C
® c-Al2O3 ® k-Al2O3 ® a-Al2O3
mina, is produced by sintering baked Al2O3 at above
Bayerite a-Al(OH)3 280° C 830° C 1000° C
® h-Al2O3 ® q-Al2O3 ® a-Al2O3 1600°C. On an industrial scale, sintering is usually carried
Boehmite g-AlO(OH) 450° C 800° C 920° C 1050° C
® g-Al2O3 ® d-Al2O3 ® q-Al2O3 ® a-Al2O3 out in high shaft-type furnaces with gas burners in the middle
Diaspore a-AlO(OH) 500° C
® a-Al2O3 zone. Initially, 20 mm spheres are prepared by clumping a
The main impurity in aluminum oxide produced by the mixture of crushed calcined Al2O3, active Al2O3 micro-
Bayer process is sodium, which limits a number of technical powder, and suitable organic binder to ensure the highest
applications of the product. To catalyze crystallization of possible density of the raw material. Typically, boron
a-Al2O3, halogen-containing compounds called mineralizers trichloride is also added to remove sodium in the form of
(BF3, BCl3) are used. In addition, mineralizers form volatile NaCl during heating. Before feeding into the furnace, the
NaCl, which removes sodium when evaporating. The crys- spheres are dried. Sintering is conducted in a continuous
tallite size of the formed a-Al2O3 typically varies from 0.5 to manner at an operating temperature of 1900 – 1950°C (al-
30 A. M. Abyzov

ways below the melting point of a-Al2O3 — 2050°C). The ducing a-Al2O3 — directly from bauxite ore, when bauxite
process lasts for about 15 h until the spheres come out of the mixed with a reducing agent (anthracite, oil coke) and
furnace base. The apparent density of 3.55 g/cm3, residual precipitator (iron dust) is melted at 2100°C in electric arc
porosity of up to 5 vol.%, and sphere shrinkage of 20 vol.% furnaces. The process includes reduction of iron oxide, silica,
are achieved. The sintered spheres are crushed and ground, and to a lesser extent, titanium oxide. In this case, a valuable
and iron-enriched material is removed by magnetic separa- by-product in the form of titanium-containing iron alloy with
tion. The product is classified based on the particle size. silicon called ferrosilicon is formed. The main product is
Lamellar Al2O3 can be up to 99.8 wt.% pure and contain low brown electrocorundum representing corundum containing a
percentage of sodium (Na2O < 0.1 wt.%). The product repre- considerable amount of titanium. The grades of brown
sents a polycrystalline material with large lamellar hexa- electrocorundum include the brittle (friable) grade, contain-
gon-shaped crystals measuring 200 – 300 (m in size and has ing 1.5 wt.% of TiO2, and standard grade, containing 3 wt.%
low residual porosity. The commercial product may contain of TiO2. The crack resistance of brown electrocorundum is
additives, which lower the melting point of Al2O3 to higher, than that of the white corundum, since due to the
1700 – 1850°C, and can be ground down to small fractions; presence of titanium, the size of Al2O3 crystallites decreases.
– white fused alumina. Above 2050°C, pure Al2O3 Standard grade brown corundum has higher strength than the
melts forming a non-conductive liquid, which solidifies into friable grade. Following the domestic tradition, brown
electrocorundum is called normal.
a massive corundum upon cooling. Re-melted a-Al2O3 is
Electrocorundum is used primarily for producing abra-
called white fused Al2O3. It has a fine-grained microstructure
sive tools (in combination with a binder), for polishing and
with distinctly expressed crystal faces. On a small industrial
sandblasting treatment (in loose form), and to a lesser extent,
scale, with production of single crystals weighing about 1 kg,
for producing refractory materials. Accordingly, at the last
re-melting of Al2O3 can be performed by the Verneil method
stage of production, the ingots are crushed and classified
(melting an oxide powder in the hydrogen-oxygen torch
based on the particle size. To improve parameters of
flame, while supplying the melt to the rotating pedestal lo-
electrocorundum (hardness, strength, thermal resistance), the
cated below).
following dopants can be introduced to the material at the
But generally, under large-scale production, inclined melting stage: Ti, Cr, Zr, Mg, and Si. Table 6 summarizes
electric arc furnaces with three ac-electrodes are used, in electrocorundum grades according to the standards and tech-
which heating is caused by the heat generated by electric dis- nical specifications of the 1970s [18]6, which, however, are
charge. After melting and homogenization, Al2O3 melt is still used by the Russian suppliers of abrasives. According to
poured into molds and allowed to cool down slowly until the Ref. [26] the impurity content is as follows, wt.%: in normal
separation from the walls occurs. b-Al2O3 (NaAl11O17) rep- electrocorundum, grades 13A and 14A — TiO2 ³ 1.8,
resents the main impurity in white fused alumina due to so- Fe2O3 £ 0.3 – 1.3, CaO £ 0.5 – 1.3 (ranges correspond to dif-
dium concentration in certain areas. However, at 2100°C so- ferent granularity); in white electrocorundum, grade 25A —
dium evaporates, and formed pores are useful. In the domes- Fe2O3 £ 0.03 – 0.05, SiO2 £ 0.1 – 0.2, Na2O £ 0.2 – 0.3. To
tic literature, synthetic corundum produced in electric arc improve mechanical strength of the product, about 2 wt.% of
furnaces is called electrocorundum;
– brown electrocorundum (brown fused alumina, 6
According to Ref. [18], the composition, density and hardness of
brown corundum). Besides thermal dehydration of alumi- the specified corundum abrasives may differ somewhat from the
num hydroxides, there is another commercial method of pro- data provided in Table 6.

TABLE 6. Domestic grades of electrocorundum for abrasive applications [24, 25].

Electrocorundum Grade Al2O3 content, wt.% g, g/cm3 H*, GPa Color

Normal 12A, 13A, 14A, 15 A, 16A 91 – 96 3.8 – 3.9 18.6 – 19.6 Brown,
from light to dark
White 22A, 23A, 24A, 25A 96 – 99 3.9 – 3.95 19.6 – 24.5 White
Single-crystal (monocorundum) 43A, 44A, 45A 98 – 99 3.94 – 4.00 22.6 – 23.5 White
Titanous 37A 91 – 98 3.96 – 4.00 19.6 – 22.6 Gray-blue
Chromous 32A, 33A, 34A 91 – 98 3.95 – 4.00 19.6 – 22.6 From pink to ruby
Zirconium 38A 60 – 75 4.05 – 4.15 22.6 – 23.5 Gray-pink
Chromium-Titanous 91A, 92A, 93A, 94A, 95A 60 – 75 — 19.6 – 22.6 —
Magnesium-Siliceous 96A 60 – 75 — — —

* Microhardness.
Aluminum Oxide and Alumina Ceramics (Review). Part 1 31

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