Refractories and Industrial Ceramics Vol. 43, Nos.

5 – 6, 2002

RAW MATERIALS
UDC 549.731.1

A STUDY OF CHROMITE DUNITES

L. B. Khoroshavin,1 T. M. Golovina,1 E. V. Bobrov,1 and M. Ya. Vol’kinshtein1

Translated from Ogneupory i Tekhnicheskaya Keramika, No. 5, pp. 48 – 50, May, 2002.

Results of a study of chromite dunites with different concentrations of chromite — from 10 to 20% Cr2O3 —
are reported. Thermomechanical properties of control specimens are determined. Chromite dunites require
precalcination for their use in the manufacture of forsterite-chromite components for thermal power units of
ferrous and, especially, nonferrous metallurgy.

Dunites, olivinites, and serpentinites, low in Cr2O3 — (ii) Kut-dunites: 33.9% MgO and 17.7% Cr2O3;
not in excess of 3% — have found wide application in the re- (iii) Kach-dunites: 27.3% MgO and 20.9% Cr2O3.
fractory industry. For example, dunites of provenance from Kut-dunites are the most refractory in the as-recovered
the Solov’evogorskoe, Kytlymskoe, Uktusskoe, Inaglinskoe state — 1710°C, whereas Ala-dunites and Kach-dunites are
and other deposits contain Cr2O3 at concentrations of less less heat-resistant — 1480 and 1450°C, respectively.
than 1% [1]. Even in the waste of beneficiated chrome ores Kut-dunites are high in aluminum oxide (17.7%) and are
(Kempirsaiskoe deposit) the concentration of Cr2O3 does not characterized by an optimum Al2O3-to-Cr2O3 ratio of 1 : 1,
exceed 2% [2]. which, using them as mixture components, increases the
With a view toward expanding the potential supply of wear resistance of magnesian spinelide refractories.
raw materials to the refractory industry, dunites of the Ural Ala-dunites are characterized by a low calcination loss,
region with an increased content of chromite (Cr2O3 to which allows their use without precalcination in the refrac-
10 – 20%), that is, chromite dunites, were used in this study. tory manufacture.
1. Chromite dunites of provenance from the Kutuzov-
skoe deposit (Verkhne-Tagilskii massif) are dense rocks of
dark-gray color, with reserves of about 5.2 million tons. TABLE 1. Chemical Composition and Refractoriness of Chromite
Dunites
2. Chromite dunites of provenance from the Alapaev-
skoe deposit (Alapaevskii massif) are dense or laminated Kut-dunite Ala-dunite Kach-dunite
rocks colored bright green to dark green, with reserves of Characteristic
as-re- as-re- as-re-
about 10 million tons. calcined calcined calcined
ceived ceived ceived
3. Chromite dunites of provenance from the Kach-
1. Chemical com-
kinskoe deposit (Pervomaiskii massif) are dense rocks of
position, wt.%:
bright-brown color, with reserves of about 3.1 million tons.2
MgO 30.2 33.92 37.54 38.63 25.13 27.32
The chemical composition of the chromite dunites is
SiO2 21.1 23.70 33.04 33.99 29.55 32.12
given in Table 1.
Chromite dunites, by the concentration of magnesium Cr2O3 15.8 17.75 10.30 10.60 19.30 20.98
and chromium in them, can be arranged in the following order: Fe2O3 6.06 6.81 10.96 11.28 13.95 15.17
(i) Ala-dunites: 38.6% MgO and 10.6% Cr2O3; Al2O3 15.2 17.07 4.89 5.03 3.52 3.83
CaO 0.91 1.02 Traces – Traces –
1 TiO2 No data 0.14 0.14 0.15 0.16
Eastern Institute of Refractories Research and Production Associ-
ation Joint-Stock Co., Ekaterinburg, Russia; Uraltsvetmetrazvedka Dmcalc 11.0 – 2.81 – 7.98 –
Joint-Stock Co., Ekaterinburg, Russia. Total 100.27 100.27 99.68 99.58 99.58
2
For brevity, henceforth dunites of provenance from the Kutuzov-
skoe, Alapaevskoe, and Kachkinskoe deposits are denoted as 2. Refractori-
Kut-dunites, Ala-dunites, and Kach-dunites, respectively. ness, °C 1710 – 1480 – 1450 –

205
1083-4877/02/0506-0205$27.00 © 2002 Plenum Publishing Corporation
206 L. B. Khoroshavin et al.

TABLE 2. Thermomechanical Properties of Chromite Dunite Spe- To assess the potential use of chromite dunites for the
cimens Calcined at 1450°C manufacture of refractories, control specimens were tested.
Concentra- Properties Dunites as-received were crushed in a jaw crusher and
tion of 20% ground in a ball mill to obtain the needed size fraction; the
Chromite sintered
dunites periclase sc , Pop , rap , powder thus prepared was pressed into specimens with or
Dl, %
powder MPa % g/cm3 without 20% sintered periclase powder added. The speci-
added, % mens were fired at 1450°C for 2 h.
Kut-dunite – 108.2 6.6 3.23 – 11.8 The thermomechanical properties of chromite-dunite
20 40.2 33.9 2.55 – 3.9 specimens are given in Table 2.
Ala-dunite – 116.0 13.1 3.10 – 12.0 The compressive strength of calcined periclase-free
20 64.9 30.9 2.40 – 8.4 specimens is rather high, amounting to 108 – 150 MPa. This
Kach-dunite – 150.0 13.2 3.08 – 14.9 indicates a high degree of sintering of the specimens exhibit-
20 40.6 32.3 2.48 – 7.4 ing a compact microstructure.
Periclase powder added to dunites causes a decrease in
compressive strength. Still, the compressive strength remains
Kach-dunites are high in iron oxides (15.2%), and their rather high — 40 – 65 MPa.
use requires the addition of a larger amount of sintered The sintered periclase-free specimens have a low poro-
periclase powder. sity of 6.6 – 13.2%, which shows that the corresponding ma-
Kut- and Kach-dunites require precalcination at about terial can be used for fabricating high-density components
1400°C without or with an addition of 20 – 30% sintered from it. The addition of sintered periclase powders increases
periclase powder. the porosity to 33.9%.
The phase composition of chromite dunites is as follows: The sintered periclase-free specimens exhibit a high li-
Kut-dunites: chromite 2[(Mg, Fe)5 × Al(Si, Al) 4 × O10(H)8 ], near shrinkage — 12 – 15%, virtually the same both length-
pennine Mg5Al(OH)8 × Si3AlO10, chromite (Mg, Fe2+ ) wise and crosswise. The addition of 20% periclase powder
(Cr, Al, Fe3+ )2 × O4, of the chromopicotite type causes a sharp decrease in shrinkage, by a factor of 2 – 4.
(Mg, Fe)(Cr, Al)2 × O4. The data obtained show that dunites, for their use in ther-
mal power units of nonferrous metallurgy, must necessarily
Ala-dunites: serpentine Mg6(OH)8 × (Si4 × O10 ), chromo-
picotite, pennine. be precalcined at 1400°C with no sintered periclase powder
Kach-dunites: serpentine, chromopicotite. added.
On the whole, chromite dunites exhibit a different degree For the thermal power units employed in ferrous and
of serpentinization with the calcination loss Dmcalc = nonferrous metallurgy, chromite dunites must necessarily be
2.81 – 11.0%. calcined with sintered periclase powder added to them. Pre-
As shown by differential thermal analysis, chromite ference should be given to periclase powders prepared from
dunites undergo similar thermal transformations on heating: magnesites high in SiO2 and low in CaO, not higher than 2%
– below 110°C — adsorption water is removed; (recovered from the Savinskoe deposit or the like).
– at 650 – 695°C, serpentine undergoes endothermal de- Sintered chromite dunites can be used for fabrication of
hydration to yield metaserpentine [3]: high-quality forsterite-chromite components with 8 – 15%
Cr2O3 according to State Standard GOST 14832–96, on a
3MgO2SiO2 × 2H2O ® 2MgO2SiO2 + 2H2O­; competitive basis with chromites available from foreign
serpentine metaserpentine manufacturers. Forsterite-chromite components have a wide
– at 815 – 870°C, metaserpentine rearranges exother- range of application, especially in nonferrous metallurgy.
mally its crystal lattice to form forsterite and clinoenstatite:
CONCLUSIONS
3MgO2SiO2 ® 2MgOSiO2 + MgOSiO2.
metaserpentine forsterite clionenstatite 1. Chromite dunites — low, medium, and high in Cr2O3
In this process, the amount of clinoenstatite formed in- (10.3, 15.8, and 20.9%, respectively) have been studied.
creases from Kut-dunites to Kach-dunites. Chemical and phase compositions and heat resistance have
Chromite when heated to 1000°C virtually undergoes no been determined and processes occurring in dunites during
phase transformation. heating have been discussed.
The calcination loss was complete on reaching 800°C. 2. Thermomechanical properties of chromite dunites
To summarize, heating chromite dunites results in the re- have been determined. Prior to use, chromite dunites must
moval of chemically bound water and the formation of re- necessarily be precalcined at about 1400°C, without or with
fractory compounds — forsterite (tm = 1890°C) and clino- sintered periclase powder low in calcium oxide (not in ex-
enstatite (tm = 1557°C). ceed of 2%) added to them.
A Study of Chromite Dunites
3. The calcined chromite dunites can be used for fabri-
cation of competitive forsterite-chromite components, with a
potentially wide application in ferrous and nonferrous metal-
lurgy.
REFERENCES
1. L. B. Khoroshavin and T. M. Golovina, “Geological characte-
rization of the Ural magnesia-silicate raw materials,” in:
207
Refractories at the Turn of the Century, Coll. of Res. Papers [in
Russian], Ural University Publishers, Ekaterinburg (2001),
pp. 49 – 64
2. G. I. Antonov, L. M. Yakobchuk, and V. Yu. Prokudin, “The
waste from beneficiated chrome ores studied for its potential use
in the refractory industry,” Ogneup. Tekh. Keram., No. 2, 21 – 23
(1994).
3. L. B. Khoroshavin, V. A. Perepelitsyn, and V. A. Kononov, Mag-
nesia Refractories. Handbook [in Russian], Intermet Engi-
neering, Moscow (2001).