JPS5943410B2 - Compound having hexagonal layered structure represented by ErFeMnO↓4 and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound ErFeMnO4 having a hexagonal layered structure and a method for producing the same.

Conventionally, a compound having a hexagonal layered structure represented by YFe204 is known.

This compound is a compound in which divalent and trivalent iron ions are surrounded by five-coordinated oxygen ions, and Y has six-coordinated oxygen ions around them, as shown by Y゜+Fe2+Fe3+0 yo. Yes, it has magnetism. The present invention provides a novel compound in which Er3+ is substituted for Y3+ and Mn2+ is substituted for Fe2+ in the Y'+Fe'+Fe°+01- compound, and a method for producing the same.

In the compound represented by ErFeMnO4 of the present invention, iron is Fe3+ ion, manganese is Mn2+, E
r exists as a trivalent ion, Er3+Fe3+
It can be expressed as Mn2+0Z-.

This crystal has a hexagonal layered structure as shown in FIG. The largest circle is oxygen, the middle circle is Er, and the smallest black circle is Fe.
and Mn. Fe and Mn are entered randomly. Divalent ions of manganese and trivalent ions of iron are surrounded by five-coordinated oxygen ions and occupy the same position crystallographically. Furthermore, Er has six-coordinated oxygen atoms around it. Oxygen, an anion, has a dense structure. a, b
, and c indicate the position within the unit cell. Planar index (hkt) and interplanar spacing (dX) of this crystal (d°C is measured,
dc indicates a calculated value), relative reflection intensity for X-rays (I
%) are shown in Table 1. And the space group is R1-fold,
Its crystal habit is plate-like, and its lattice constant is as follows. a0
=3.4800±0.0002(X)c0=25.54
5±O, 003(X) Table 1 hkι do [Alldc
CAIIC]0038.5378.515630064
．． 2614.257411012.9942.9931
0000 9 2.8 40 2.8 38 4810
4 2.727 2.726 921 05 2.5
96 2.596 7610 7 2.3238 2.
3238 221 0 8 2.19 20 2.19
17 291010 1.9485 1.9487 4
91 10 1.7399 1.7400 54113
1.7045 1.7048 231 013 1.
6 46 0 1.6 46 0 131 16 1.
61101.610722 This compound is useful as a magnetic material as well as a semiconductor material.

This compound can be produced by the following method.

Erbium oxide (Er2O,), manganese oxide (M
nO) and iron oxide (Fe2O3) in a molar ratio of approximately 1:2:1, and heating the mixture at a temperature of 900°C or higher in a non-oxidizing atmosphere. can. Commercially available erbium oxides used in the present invention may be used as they are, but in order to speed up the reaction between the oxides, the smaller the particle size, the better, particularly preferably 10 μm or less.

Furthermore, when using it as a magnetic material, it is preferable to avoid contamination with impurities, so it is preferable that the raw material is of high purity and that it has been calcined in air at about 1000° C. for several hours. Manganese oxide of ordinary reagent grade level may be used. The grain size is preferably 10 μm or less for the same reason as the erbium oxide. Further, it is preferable to calcinate in a mixed gas of carbon dioxide and hydrogen (mixture ratio: 1:1 by volume) at 1000° C. for 1 day, and then rapidly cool it to 0° C., because the reaction speeds up. The iron oxide may be of special reagent grade. As mentioned above, the particle size is preferably 10 μm or less. Moreover, it is preferable to calcined in air at 800° C. for one day. These raw materials as they are,
Alternatively, add alcohol, acetone, etc. and mix thoroughly. The mixture contains Er2O3, MnO, and Fe2O3 in a molar ratio of 1:2:1.

If this ratio is exceeded, the desired layered compound cannot be obtained. These mixtures are sealed in a quartz or glass container and heated under a non-oxidizing atmosphere.

Since manganese is in a divalent state, in an oxidizing atmosphere (for example, in the atmosphere), manganese will be oxidized and become trivalent, so it is necessary to be in a non-oxidizing atmosphere. The heating temperature may be 900°C or higher, and the heating time is 10 minutes or more, preferably 1 hour or more. There are no restrictions on the rate of temperature increase during heating. After the reaction is completed, it may be rapidly cooled to 0°C or rapidly drawn out into the atmosphere. The obtained ErFeMnO4 compound has a black metallic luster and has a powder X
It was found by line diffraction that it has a crystalline structure.

The valence of iron ions in the compound was determined by measuring the Mössbauer effect, and the valence of manganese ions was determined by gravimetric analysis, which measures the change in weight of the sample when it is heated in air. Example: Erbium 1ide (Er2O) with purity of 99.9(f) or higher
3) Powder, manganese oxide (MnO) with a purity of 99.9% or more
) Powder and iron oxide (Fe2O) with a purity of 99.9% or more
3) Powders were weighed at a molar ratio of 1:2:1, acetone was added in a mortar, and the mixture was thoroughly mixed to obtain a fine powder mixture with an average particle size of several μm.

The mixture was placed in a transparent quartz tube (inner diameter 8m0) and the inside of the tube was lowered to a vacuum level of 1mmHg using a vacuum pump.
It was maintained for a period of time and then melted and sealed with a gas burner. 1000 of this
Set to ℃? The sample was placed in a box-shaped siliconite furnace and heated for about 1 day, after which the sample was removed and rapidly cooled to room temperature. What was obtained was a hexagonal layered compound of ErFeMnO4. The properties of the crystal were as shown in Table 1.

[Brief explanation of the drawing]

The drawing is a diagram of an ErFeMnO2 crystal of the present invention.

Claims (1)

[Claims] 1. A compound having a hexagonal layered structure represented by ErFeMnO_4. 2 Erbium oxide (Er_3O_3), manganese oxide (MnO) and iron oxide (Fe_2O_3) are mixed in a molar ratio of approximately 1:2:1, and this mixture is heated at 900°C or higher in a non-oxidizing atmosphere. A method for producing a compound having a hexagonal layered structure represented by ErFeMnO_4, which comprises heating at a certain temperature.