JPS5943413B2 - Compound having hexagonal layered structure represented by TmFeMnO↓4 and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound TmFeMnO4 having a hexagonal layered structure and a method for producing the same.

Conventionally, YFe.

Compounds having a hexagonal layered structure represented by q are 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 it, as shown by Y3+Fe2+Fe3+q-. It has magnetism. The present invention provides Y3+ of the Y3+Fe2+Fe3+O24□ compound.
The purpose of the present invention is to provide a novel compound in which T+ is replaced with Mn2+ and Mn2+ is replaced with T+, and a method for producing the same.
In the compound represented by mFeMnO4, iron exists as Fe3+ ion, manganese exists as Mn2+, and Tm exists as trivalent ion, and T+ Fe゜±Mn″fo
It can be represented as H-.

This crystal has a hexagonal layered structure as shown in FIG. The largest circle is oxygen, the middle circle is Tnl, and the smallest black circle is F.
e and Mn are shown. 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. Moreover, Tm has six-coordinated oxygen around it. Oxygen, an anion, has a dense structure. a,
b and c indicate positions within the unit cell. The plane index (hKl) and plane spacing (dA) (do) of this crystal were measured,
dc indicates a calculated value), relative reflection intensity for X-rays (I
%) are shown in Table 1.

The space group is R''3m, the crystal habit is plate-like, and the lattice constants are as follows: ao ■ 3.4694±O, O
OO2(A)Q225.562±O, OO3(Λ)1st
Table hKldoCA] dcI' A] I [%] OO3
8.55O8.52168OO64.264 4.2
6 O 3 41O1 2.9 8 5 2.9 8
4 1O O1O 2 2.9 2 7 2.9 2
5 3O O 9 2.8 4O 2.8 4 O 4
71O 4 2.7 2 O 2.719 9 51O
5 2.5 91 2.5 9 O 6 71O 7
2.3 2 O 3 2.3 2 O 2 181O
8 2.1889 2.1888 281O1O 1.
9473 1.9469 3211O l, 7345
1.7347 46113 1.7OO31.6998
131O131.64561.645311 This compound is useful as a magnetic material as well as a semiconductor material.

This compound can be produced by the following method.

Thulium oxide (TjO3), manganese oxide (MnO
) and iron oxide (Fe2O:3) in a molar ratio of approximately 1:2.
The mixture was mixed in a ratio of 1 to 1 and the mixture was
It can be produced by heating at a temperature of 00°C or higher. As the thulium oxide used in the present invention, commercially available products may be used as they are, but in order to promote the reaction between the oxides quickly, the smaller the particle size, the better.
It is preferable that it is 0ttm or less.

When used as a magnetic material, since contamination with impurities is to be avoided, the raw material should preferably be of high purity and should have been calcined in air at about 1000° C. for several hours. Manganese oxide of ordinary reagent grade level may be used. The particle size is preferably 10 μm or less for the same reason as the thulium oxide. Preferably, the material is calcined in a mixed gas of carbon dioxide and hydrogen (mixing ratio: 1:1 by volume) at 1000° C. for one day, and then rapidly cooled to 0° C., since the reaction speeds up. The iron oxide may be of special reagent grade. The particle size is 10 μm as above.
It is preferable that it is below. Moreover, it is preferable to calcined in air at 800° C. for one day. These raw materials are thoroughly mixed as they are or with alcohol, acetone, etc. added. These mixing ratios are Tm2O3, MnOlFe2O
3 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 TmFeMnO4 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 Thulium oxide (to Tj) powder with a purity of 99.9% or more, manganese oxide (MnO) powder with a purity of 99.9% or more, and iron oxide Ce2O3) powder with a purity of 99.9% or more in a molar ratio of 1: The mixture was weighed at a ratio of 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 8 mm), and the vacuum inside the tube was lowered to 163 degrees Hg using a vacuum pump.
It was maintained for a period of time and then melted and sealed with a gas burner. 1000 of this
The sample was placed in a box-shaped siliconite furnace set at .degree. C. and heated for about 1 day, after which time the sample was removed and rapidly cooled to room temperature. What was obtained was a hexagonal layered compound of TmFeMnO4. The properties of the crystal were as shown in Table 1.

[Brief explanation of the drawing]

The drawing is a diagram of a TmFeMnO4 crystal of the present invention. The largest circle indicates oxygen, the middle circle indicates Tml, and the smallest black circle indicates Fe and Mn.

Claims (1)

[Scope of Claims] 1 A compound having a hexagonal layered structure represented by TmFeMnO_4. 2 Thulium oxide (Tm_2O_3), manganese oxide (MnO) and iron oxide (Fe_2O_3) are mixed in a molar ratio of about 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 TmFeMnO_4, which comprises heating at a certain temperature.