Sintering of Alumina at Temperatures of

1400°C. and Below

by IVAN B. CUTLER, CYRIL BRADSHAW, CARL J. CHRISTENSEN, and EDMOND P. HYATT
Department of Ceramic Engineering, University of Utah, Salt Lake City, Utah

Previous investigators have indicated that

both small particles and the addition of certain
oxides promote the sintering of alumina at tem-
peratures below 17OOOC. By utilizing combina-
tions of oxides and small particle size, the sin-
tering temperature of 96% alumina bodies was
reduced in this investigation to the 1300° to
140OOC. range. It i s proposed that this low-tem-
perature sintering i s aided by the formation of a
liquid phase. Thin sections of the alumina
sintered at low temperatures revealed bodies
with small grain size whose bulk densities were
above 3.80 gm. per cc.

1. Introduction
XPERIMENTATION as well as theory has indicated that the

E sintering temperature can be lowered if small particles are

utilized in forming the object to be sintered. Wilder
and Fitzsimmonsl have shown the applicability of this prin-
4.0B
MnO 3.0
4
2.0
.
I.o
0
Ti Oe
ciple in the sintering of alumina. Experimentation has also Fig. 1. Diagram of the system MnO-AhOa-TiOt showing compositions
indicated that certain additives promote sintering a t lower prepared for testing.
temperatures. These materials often form solid solutions
with defect lattices that assist diffusional processes. The
present authors believe that sintering may also be accelerated
by the formation of a liquid phase.
The influence of additives on the sintering of alumina has
been studied by Smothers and Reynolds2 and by Cahoon and
Christensen.3 Their experimental results confirm earlier re-
ports4 that titanium, manganese, and copper oxides are par-
ticularly effective in promoting crystal growth and sintering
of alumina. I n attempting to lower the sintering temperature
of alumina, Yamauchi et aL5 studied the effect of MnO and
TiOz alone and in combination. Unfortunately, the alumina
utilized by Yamauchi was contaminated with silica and his
results with MnO and TiOz combined did not deviate far
from the results with MnO and Ti02 alone. Other investi-
gator9 have also reported using MnO and TiOz in combina-
tion but not below 1700°C.
-

Presented at the Fifty-Eighth Annual Meeting, The American

Ceramic Society, New York, N. Y., April 23, 1956 (Basic Science
Division, No. 2). Received July 9, 1956; revised copy received
October 26, 1956.
This research was sponsored by the Bay State Abrasive Prod-
ucts Company, Westboro, Mass. Fig. 2. Compositions studied in the system Cu20-Ah03-TiO~.
At the time this work was done, the authors were, respectively,
associate professor, assistant, professor, and research assistant,
Department of Ceramic Engineering, University of Utah. Ed-
mond P. Hyatt is now production manager a t Electro-Ceramics,
Inc., Salt Lake City, Utah.
D. R. Wilder and E. S. Fitzsimmons, “Further Study of steme vom Standpunkt der Physikalischen Chemie). Springer-
Sintering Phenomena,” J . Am. Ceram. SOC.,38 [2] 66-71 (1955). Verlag, Berlin, 1948. 280 pp.; Ceram. Abstr., 1949, October, p.
* W. J. Smothers and H. J. Reynolds, “Sintering and Grain 233g.
Growth of Alumina,” J . Am. Ceram. SOC.,37 [12] 58&95 (1954). Toshiyoshi Yamauchi, Hideo Tagai, and Renichi Kondo,
3 H . P. Cahoon and C. J. Christensen, “Sintering and Grain “Sintering of Alumina Porcelain,” J . Japan Ceram. Assoc., 57
Growth of Alpha-Alumina,” J . Am. Ceram. SOC.,39 [lo] 337-44 [641] 137-40 (1949); Ceram. Abstr.. 1951, January, p. 12b.
(1956). (a) H. N. Baumann, Jr., and R. C. Benner, “Aluminous Ma-
4 ( a )T. G. McDougal, A. H. Fessler, and Karl Schwartzwalder, terial,’’ U. s.Pat. 2,360,841, October 24, 1944; Ceram. Abstr., 24
“Insulator for Spark Plugs,” U. S. Pat. 2,152,656, April 4, 1939; [ l ] 3 (1945).
Ceram. Abstr., 18 [61 159 (1939). ( b ) S. P. Robinson, “Recrystallized Alumina Pebbles,” U. S.
( b ) Eugen Ryschkewitsch, One Component Oxide Ceramics Pat. 2,685,528, August 3, 1954; Ceram. Abstr., 1954, November,
on Basis of Physical Chemistry (Oxydkeramik der Einstoffsy- p. 202i.
134
April 195'7 Sintering of A lumina at 1400°C. and Below 135

16OO0C.
I7OO0C.

2.*f
i
2.6
ID 0.0 0.6 0.4 0.2 mMn
O
2.0%
2.6 I I .5 I .o 0.5 0 MnO

0 0.2 0.4 0.6 0.0 1.0%Ti02 0 Q.5 I .o I .5 2.0%TiO,

Additive (wt.%) Additive (wt. %)

Fig. 4. Bulk densities of sintered alumina with 2% MnO-Ti02 additive.
Fig. 3. Bulk densities of sintered alumina with 1% MnO-Ti02 additive.

4.01 I I I I I I I I I I I I I I I 1

2.0
2.6
30
t
0
2 .o
I .o
1.0
2 .o
iO%MnO
3.0%T i 4
26
4.0 3.0 2 .o I.o
9 13OO0C

0% MnO
0 I .o 2.0 3.O 4.0%Ti 0,
A d d i t i v e (wt. x) Additive (&.%I
Fig. 5. Bulk densities of sintered alumina with 3% MnO-Ti02 additive. Fig. 6. Bulk densities of sintered alumina with 4% MnO-Ti02 additive.

The purpose of this investigation was to show the effect of

combinations of manganese and titanium oxides and of copper weight of the combinations of manganese and titanium
and titanium oxides as additives to alumina for the purpose of oxides or of copper and titanium oxides, the alumina was sin-
lowering the sintering temperature of alumina. With 4 tered to maximum density in the range 1300" to 1400OC.
136 Journal of The '4 merican Ceramic Society-Cutler, Bradshaw, Christensen, and IIyatt Vol. 40, No. 4
4.0 I

1400% 0 )16OO0C
1500*C 3.q)
1600*C
1300% B l700'C
1700% " 23 1500%
9-
2 3.6- -
\

0 I.O%?iO*
Additive (wt.%)
2.6h I I I
1% 2% 3% 4Y. Additive Fig. 8. Bulk densities of sintered alumina with 1 % CunO-Ti02 additive.

Additive (wt.%)
Fig. 7. Bulk densities of sintered alumina with 0 to 4% MnO-Ti02
additive. Weight r a t i o MnOITiOs = 58/42.

1 1600. C
1700%
4.0 1
"'1
1600%.
1700%

1500'C

1400*C

\i
1400%

130OOC

2.8 I I

2
I A
Y1300.C
A0 CUL0
3% 2
0
I 0 cu*0
I
Additive (wt. %)
2 3% Ti O2

I .o Fig. 10. Bulk densities of sintered alumina with 3% CuzO-TiOz additive.

0
2.0Ye 2.07. Ti 0,
Additive (wt."/,)
Fig. 9. Bulk densities of sintered alumina with 270 CuzO-Ti02
additive.
A-14) wet ground 48 hours in rubber-lined gallon-size ball
mills containing alumina balls was used as the basic raw ma-
terial. To this finely divided alumina, weighed amounts of
reagent-grade TiOz, MnOz, and CuzO were added according
II. Experimental Procedure to the compositions shown in Figs. 1 and 2. Each batch was
The effect of manganese, copper, and titanium oxides on the milled for 1 hour, filtered, dried, and pressed into pellets with
sintering of alumina was studied by making up the composi- the aid of an organic binder. A pressure of approximately
tions shown in Figs. 1 and 2. High-purity alumina (Alcoa 15 tons per sq. in. was used to form the pellets.
April 1957 Sintering of Alumina at 1400" C. and Below

3.8 1600°C
1700°C

3.6
I 500°C

v 3.4
0
\

-
E
CI,

~ 3.2
+
.-
u) 1400°C

2.8 1300°C

2.6
4 3 2 I 0% cu20
0 I 2 3 4 % Ti02
Additive (wt.%) 2.6l I I I I
0 0.5
.. 1.0 I .5 2.0
- _
Fig. 1 1 . Bulk densities of sintered alumina with 4% CunO-Ti02 0 0.5 1.0 1.5 20 2.5% Ti&
additive.
Additive (wt. %)
Fig. 12. Bulk densities of sintered alumina with 0 to 5% CuaO-Ti02
additive.

Each member of the series of bodies was fired to tempera-

tures of 1500", L4OO0, 1500°, l G O O O , and 1700°C. Each
temperature was maintained under neutral to oxidizing con- per hour. Pellets were fired in a semimuffle, natural-gas-
ditions for 1 hour. The rates of heating and cooling were not fired kiln; consequently, loss of volatile constituents such as
maintained constant, but varied between 50" and 100°C. copper oxide from the surface of the pellets was qualitatively

4.0% ~~0 3.5% M ~ O 3.0% MnO 2.5% MnO 2.0% MU0 1.5% M u 0 1.0% MnO o.5% Mno O% Mno
0% T ~ O ~ 0.5% T ~ O ~ 1.0% TiOz 1.5% Ti02 2.0% TiOz 2.5% TiOz 3.0% Ti02 3.5% 4@& Tioz

Fig. 13. Photomicrographs of sintered alumina with 4% MnO-Ti02 additive (X37).

138 Journal of The American Ceramic Society-Cutler,
4.0% CuzO 3.0% CuzO
0% Ti02 1.0% Ti02
Fig. 14. Photomicrographs of sintered alumina with 470 CuzO-Ti02 additive (X46).
observed. The bulk density of each pellet was determined
with the aid of a mercury hydrometer similar to the one em-
ployed by Clark and White.’ Thin sections were cut from
the center of each pellet and photographs were taken with the
aid of a polarizing microscope.
111. Results
The results of the density determinations are shown in
Figs. 3 through 12. The reported densities are felt to be
significant to +0.005 gm. per cc.
The thin sections were photographed under the crossed
Nicols of a polarizing microscope. The important photo-
micrographs are arranged in sequence in Figs. 13 and 14.
Poor resolution resulted from the thin sections of pellets fired
at low temperatures because of insufficient grain growth com-
pared with the thickness of the section.
P. W. Clark and J. White, “Some Aspects of Sintering,”
Trans. Brit. Ceram. SOC.,49 [7] 305-33 (1950); Ceram. Abstr.,
1952, June, p. 118f.
Bradshaw, Christensen, and Hyatt Vol. 40, No. 4
2.0% cp20 1.0% CuzO 0 % CuzO
2.0% T10z 3.0% Ti02 4.0% TiOz
IV. Discussion of Results
It is clearly evident from the density determinations
(Figs. 3 through 12) that the combination of manganese and
titanium oxides or of copper and titanium oxides is more effec-
tive in aiding sintering (densification) than either of the oxides
alone. It is proposed that at least one of the contributing
factors in this remarkable effect is the formation of a eutectic
liquid between the manganese, titanium, and aluminum
oxides and between the copper, titanium, and aluminum
oxides.
The pellets were fired on coarse alumina setting sand. At
temperatures above 1300°C. evidence was observed of a liquid
draining from the pellets. The setting sand immediately be-
low the pellet was sintered hard and was black in color, indi-
cating the presence of the eutectic mixture. The difference in
strength between the sintered black setting sand and the sur-
rounding white sand made it easy to observe the sharp bound-
ary between the two areas. It was difficult to separate the
dark-colored setting sand from pellets fired 300°C. above the
temperature of maximum density.
For the low-firing bodies containing copper and titanium
oxides or manganese and titanium oxides it is postulated that
April 19.57 Oxidation of Manganese Ferrite
a liquid is responsible for the low-temperature sintering.
No phase diagram is available to indicate eutectics between
these components, but the physical evidence of a “bleed-
ing” liquid that drains away from the sintered pellets justi-
fies the conclusion of eutectic liquids formed from copper,
titanium, and aluminum oxides and from manganese, titanium,
and aluminum oxides.
Although the compositions shown in Figs. 1 and 2 were cal-
culated on the basis of MnO, CuzO, and TiOz, it is not the in-
tention to infer that MnO, CuzO, and TiOz are the active
chemical species. Possibly MnzOa and Ti203 are more im-
portant. No kiln atmospheres other than neutral to oxidiz-
ing were utilized. The determination of the mechanism of
sintering and grain growth is left to future research.
The photomicrographs of thin sections reproduced in Figs.
13 and 14 clearly indicate that recrystallization into large
crystals is a function of composition as well as of temperature.
Composition influences grain size much more a t a high firing
Oxidation of Manganese Ferrite
by R. S. WElSZ
RCA Laboratories, Radio Corporation of America, Princeton, N e w Jersey
The oxidation of manganese ferrite (MnFez04)
in air has been studied in the temperature range
750’ to 1150°C. Between 1050” and 1150” a
homogeneous oxidation takes place, resulting in a
spinel phase of a defect type containing up to
10% of the manganese in the trivalent state.
At 1050’ and below, bixbyite (Mnz03)and hema-
tite (Fez03) are precipitated. The kinetics
indicate that initially a diffusion-limited homo-
geneous reaction takes place, followed by precipi-
tation and grain growth. At lower temperatures,
well-defined Widmanstatten precipitates are
formed ; at higher temperatures, recrystalliza-
tion alters these precipitates. The oxidation
of manganese ferrite can be strongly retarded by
a ceramic glaze, offering a practical method of
preparing the material by air firing.
I. Introduction
HE FERRITES are a widely used class of ceramic materials,
T exhibiting valuable and varied magnetic properties.‘
Among the ferrites, MnFez04occupies a unique position as
a permeable magnetic material because of its large saturation
induction’ and its small magnetic anisotropy.2 It is there-
fore a major constituent of television deflection components.
Received August 10, 1956.
At the time this work was done, the author was research
engineer, RCA Laboratories, Radio Corporation of America.
He is now director of research on ferromagnetics, International
Telemeter Corporation. Los Angeles, Calif.
139
temperature than a t low firing temperatures. For this
reason, bodies having compositions that reach maximum
density a t low firing temperatures (1300’ to 1400’C.) have
small grains.
V. Conclusions
Combinations of manganese and titanium oxides and of
copper and titanium oxides are more effective in lowering the
sintering temperature of alumina than either oxide alone.
Evidence is presented to indicate the presence of a liquid
which accelerates densification. A minimum of grain growth
was observed for compositions containing 3 to 4% additions
and fired at temperatures from 1300’ to 1400’C.
Acknowledgments
The authors gratefully acknowledge the suggestions and
encouragement offered by S. S. Kistler, dean of the College of
Engineering, University of Utah.
Further, manganese oxide and iron oxide, together with
magnesium oxide, are the starting materials for producing
ferrites with a square hysteresis essential for memory
devices.
Since manganese can exist in different valence states with
different numbers of electrons, having different spin and
orbital angular one might expect this dif-
ference to be an important factor in controlling the properties
of manganese-containing ferrites. Indeed, it has been found
that the permeability, p , of MnFezOais drastically decreased
by oxidation of the divalent m a n g a n e ~ e . ~On the other hand,
trivalent manganese is apparently required for manganese-
magnesium ferrites to have a square hysteresis loop5 The
‘ ( a ) R. L. Harvey, I. J. Hegyiand H. W. Leverenz, “Ferromag-
netic Spinels for Radio Frequencies,” RCA Rev., 11 [3] 321-63
(1950).
( b ) Irwin Gordon, “Preparation and Properties of a Ceramic
Permanent Magnet,” Am. Ceram. SOC.Bull., 35 [5] 173-75 (1956).
(c) E. W. Gorter, “Some Properties of Ferrites in Connection
with Their Chemistry,” Proc. Inst. Radio Engrs., 43 1121 194,5
73 (1955).
* R. S. Weisz, “Magnetic Anisotropy Constants of Ferromag-
netic Spinels,” Phys. Rev.,96 [3] 800-801 (1954).
“ ( a ) I. J. Hegyi, “Ferromagnetic Spinels with Rectangular
Hysteresis Loops,” A p p l . Phys., 25 [2] 176-78 (1954).
( b ) E. Albers-Schoenberg, “Ferrites for Microwave Circuits
and Digital Computers,” ibid., 25 [2] 152-54 (1954).
George Economos, “Magnetic Ceramics: 11, Properties of
Magnetite and Manganese Ferrite Fired in Various Atmospheres,”
J. A m . Ceram. SJC.,34 [8] 292-97 (1955).
5 P. K. Bnltzer, “Magnetostriction in Ferrites Possessing a
Square Hysteresis Loop,” Conf. on Magnetism, pp. 247-49 (pub-
lishek by the American Institute of Electrical Engineers,
New York, 1955. 370 pp.).