No.

10] 709

170. On Some Magnetic Properties of Ilmenite at

Low Temperatures

By Shoichi KUME
Institute of Earth Science,KyotoUniversity
(Comm.by M. MATUYAMA, M.J.A.,Dec. 12, 1955)

Thermo-magnetic study of the members of the solid solution

between ilmenite (Fe0Ti02) and hematite (Fe203), first established
by E. Pouillard,1' has recently been taken as a subject of importance
in the field of rock magnetism by such authors as T. Nagata, S.
Akimoto, S. Uyeda, 2' J. R. Balsley, A. F. Buddington, 3' R. Chevallier,
S. Mathieu, and E. A. Vincent.' S. Akimoto5' has revised the
Pouillard's magnetic observation by increasing the number of speci-
mens of ilmenite, and has discovered that the mineral containing
about 25 mole/ of hematite in it shows a remarkable ferrimagnetic
character. Their Curie points, lying between 250°C and 100°C, have
been found to be related linearly to their crystallographic param-
eters and chemical compositions.
In the papers6' written jointly by N. Kawai, S. Sasajima, and
the present writer, the results of investigation were concerned
mainly with magnetic characters of titanomagnetite series rather
than that of ilmenite-hematite series. Recently N. Kawai has ex-
panded the temperature range of thermo-magnetic analysis from
1300°K down to 80°K. By using the method of this analysis, S.
Sasajima*' has found that the relationship between Curie points and
crystallographic parameters of ilmenite holds good in a far wider
range than that obtained so far. The Curie point is lowered below
0°C when the amount of solute hematite diminishes from 25 mole/
toward the pure ilmenite. 100°K is the lowest value of Curie point
of the ilmenite, ever found by him, and the amount of ferric ion
in this mineral is 1.9 in atomic percentage per molecule.
In order to know how the intensity of magnetization of the
ilmenite varies from one specimen to another, the present writer has
carried out the measurement of 12 natural and synthesized ilmenites,
the latter being prepared in the following way. Adequate quantities
of fine powder of pure x-hematite, titanium dioxide, and metallic iron
were mixed as homogeneously as possible, pressed tightly together,
and enclosed in a fused silica tube under high vacuum. The enclosed
material was then submitted to a prolonged heat treatment in a
*) Thisfact wasreportedat the 18thAssemblyof Societyof TerrestrialMagnetism
and Electricity,1955.
710 S. KUME [Vol. 31,

furnace until the three kinds of the powders were turned into a
homogeneous ilmenite by heating. By changing the relative propor-
tion of the quantities of the powders to be mixed, ilmenite with
any desired chemical composition can be produced. The intensity
of magnetization of the specimen thus prepared was measured with
an aid of pendulum magnetometer designed by H. Takaki, to whom
the writer is indebted.
The specimens to be measured were fixed at the lower end of
the pendulum and were placed in a space between the truncated
pole pieces of an electromagnet, where was generated a magnetic
field of 14000 Oe with a field gradient, small but nearly constant
over the range in which the pendulum was allowed to move. By
cooling the specimens at that place down, to the boiling temperature
of nitrogen, and then measuring the deflection angle of the pendulum,
the intensity of magnetization at 80°K of the specimens was deter-

mined. The difference between the values of magnetization obtained

under 14000 Oe and 10000 Oe was so small that the values shown
in the above table could be regarded as the saturation magnetiza-
tion (Js) of these specimens. In the table, the Js values, represent-
ed in the unit of Bohr magneton (µ~) per molecule, are compared
with the data of chemical and X-ray analyses.
As can be seen from the distributions of the plots in Fig. 1,
the intensity Js increases as the Curie point and the ferric ion
concentration in the mineral decrease.
In order to account for this mode of variation, the Js of the
mineral with known ferric solute ions was calculated on a basis of
ferrimagnetism under the assumption that the solute ferric ions
with 5 µB and the solvent ferrous ions with 4 are the magnetic
ions responsible for the ferrimagnetism, and also that the magnetic
moment of the former is arrayed in the crystal lattice in the direc-
tion antiparallel with that of the latter, while ions of the same
kind are aligned in the same direction. The result reduced from
No. 10] On Some Magnetic Properties of Ilmenite at Low Temperatures 711

The broken line represents the theoretical relation calculated.

this simple model is illustrated by a broken line in the figure.

Several specimens, such as Nos. 1, 2, 3, 4,, and 7, whose Curie
points and ferric ion contents in the crystal are too low (in Fig.
1, the plots for these specimens are enclosed by a dotted circle),
have their intensity of magnetization conspicuously smaller than those
calculated. However, the slope of the thermo-magnetic curve, as
shown in Fig. 2, is still steep at 80°K, and therefore, the Js value
would increase on further cooling, and the value expected to occur
at absolute zero temperature would be greater than those obtained
at 80°K. Taking this expectation into consideration, the Js vs. com-
position relation obtained may be said to be consistent with that
calculated.
Since T. Nagata's7' and G. D. Nicholls'8' explanations, it has
hitherto been inferred that the pure ilmenite has a complete anti-
ferromagnetic character. S. Akimoto5' has remarked that, according
to his observation, the Js at the room temperature amounts up to
the maximum value when the ferric ion concentration in the solid
solution draws near to 12 atomic percentage per molecule, the
chemical composition of the mineral being represented by 2(Fe0Ti02)
•Fe203, an intermediate member on the series of the solid solu-
tion between Fe203 and Fe0Ti02.
712 S. KUME [Vol. 31,

But, the present results obtained at 80°K show that the Js is

still increasing despite the ferric ion concentration is reduced even
to 2.6 atomic percentage in the solid solution. Noteworthy is that
such a ferric ion poor ilmenite has, at low temperatures, remarkably
strong ferrimagnetic intensity tending up to 4µR per molecule, as
is shown in Fig. 1. This fact will be explained plausibly by assum-
ing that major magnetic atoms have parallel spin angular momentum
in the crystal lattice and, therefore, the crystal at low temperatures,
behaves rather likely as ferromagnetic than antiferromagnetic.
It seems to be of primary importance to carry on a further
examination at low temperatures down to that of liquid helium and
to determine the exact inter-relationship which the Js, the Curie
point and the chemical composition bear with each other on this
solid solution.
In conclusion, the writer wishes to express his hearty thanks
to Professor N. Kumagai and Lecturer N. Kawai under whose direc-
tion and advices this study has been carried out in the geological
laboratory. Thanks are also due to Professor H. Takaki of Kyoto
University and Professor T. Hirone of Tohoku University for many
stimulating discussions and guidances. The author also acknowledges
to Emeritus Professor M. Matuyama, M.J.A., for valuable sugges-
tions and continuous encouragements throughout the whole study.

References

1) E. Pouillard: Ann. Chimie, 5, 164 (1950).

2) T. Nagata, S. Akimoto, and S. Uyeda: Jour. Geomag. Geoele., 5, 168 (1953).
3) J. R. Balsley and A. F. Buddington: Jour. Geomag. Geoele., 6, 176 (1954).
4) R. Chevalier, S. Mathieu, and E. A. Vincent: Geochim. Cosmochim. Acta, 6, 27
(1954).
5) S. Akimoto: Jour. Geomag. Geoele., 6, 1 (1954); Jap. Jour. Geophys., 1, 1(1955).
6) N. Kawai, S. Kume, and S. Sasajima: Proc. Japan Acad., 30, 588, 864 (1954).
7) T. Nagata: Rock-Magnetism, Maruzen, Tokyo, 36 (1953).
8) G. D. Nicholls: Adv. Phys., 4, 113 (1955).