JPS6045130B2 - Compound belonging to the monoclinic system represented by 4NiO・6Fe↓2O↓3・9GeO↓2 (Ni↓4Fe↓1↓2Ge↓9O↓4↓0) and its production method - Google Patents
Compound belonging to the monoclinic system represented by 4NiO・6Fe↓2O↓3・9GeO↓2 (Ni↓4Fe↓1↓2Ge↓9O↓4↓0) and its production methodInfo
- Publication number
- JPS6045130B2 JPS6045130B2 JP56065033A JP6503381A JPS6045130B2 JP S6045130 B2 JPS6045130 B2 JP S6045130B2 JP 56065033 A JP56065033 A JP 56065033A JP 6503381 A JP6503381 A JP 6503381A JP S6045130 B2 JPS6045130 B2 JP S6045130B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- monoclinic system
- 9geo
- 4nio
- germanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Inorganic Compounds Of Heavy Metals (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Description
【発明の詳細な説明】
本発明は新規化合物である４Ｎｉ０−６Ｆｅ、Ｏｓ・９
ＧｅＯ。DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel compounds 4Ni0-6Fe, Os・9
GeO.
（Ｎｉ、Ｆｅ、Ｏ°。Ｏ、Ｏ）で示される単斜晶系に属
する化合物およびその製造法に関する。従来、４Ｆｅ０
−６Ｆｅ。The present invention relates to a compound belonging to the monoclinic system represented by (Ni, Fe, O°.O, O) and a method for producing the same. Conventionally, 4Fe0
-6Fe.
ｏ。・ ９ＣｅＯ、で示される単斜晶系に属する化合物
は、本出願人によつて既に合成されており、その結晶構
造があきらかにされている。この化合物には、２価イオ
ンの鉄が４個、３価イオンの鉄が１２個、４価イオンの
ゲルマニウムが９個存在しており、黒色である。ゲルマ
ニウムは、４組の酸素によつて囲まれ、鉄イオンは５目
の酸素によつて囲まれたものと、４個の酸素によつて囲
まれたものとがある。その結晶構造を第１表に示す。第
１表
Ａをｏｍｘｙ２
Ｇｅ（１）０２１９９７（７）−００２０１５（６）０
２３２５１（６）Ｇｅ（２）０３７１５１（６）Ｏ、２
５２０５（６）Ｏ、４８８２８（６）Ｆｅ（１）００７
０５０（８）０３５７１α８）０１０７２６（８）Ｆｅ
（２）０３４２７Ｃｊ、８）０．６１６２０（８）Ｏ、
１３６５０（８）Ｆｅ（３）Ｏ、１９４９１（８）Ｏ、
６１６４ｅＡ８）０３７３３４（８）Ｏ（１）Ｏ、０４
９０（４）Ｏ、１２３４（４）０１３３（４）Ｏ（２）
Ｏ、０８８１（４）Ｏ、５９８７（４）０１２７５（４
）Ｏ（３）０２９６７（（４）Ｏ、３６８２（４）００
９７９（４）Ｏ（４）０２９５７（４）Ｏ、８７１０（
４）Ｏ、１１４Δ４）Ｏ（５）Ｏ、２０２５（４）Ｏ、
３８１７（４）０３５９４（４）Ｏ（６）Ｏ、１７２９
（４）Ｏ、８５９９（４）Ｏ、３７０（ｊ４）Ｏ（７）
Ｏ、４０９４（４）０１１０４（４）Ｏ、３６１５（４
）Ｏ（８）０４３２３（４）Ｏ、６５０８（４）０３８
０Ｃｊ、イ本発明は、前記、４ＦｅＯ−６Ｆｅ２Ｏ３・
９ＧｅＯ２化合物のＦｅＯの代わりに、ＮｉＯを置き
換えた新規な単斜晶系に属する化合物およびその製造法
を提供するにある。o. - A compound belonging to the monoclinic system represented by 9CeO has already been synthesized by the applicant, and its crystal structure has been clarified. This compound contains 4 divalent iron ions, 12 trivalent iron ions, and 9 tetravalent germanium ions, and is black in color. Germanium is surrounded by 4 pairs of oxygens, and iron ions are surrounded by 5 pairs of oxygens, and some are surrounded by 4 pairs of oxygens. Its crystal structure is shown in Table 1. Table 1 A as omxy2 Ge(1)021997(7)-002015(6)0
23251(6)Ge(2)037151(6)O,2
5205(6)O, 48828(6)Fe(1)007
050(8)03571α8)010726(8)Fe
(2) 03427Cj, 8) 0.61620(8)O,
13650(8)Fe(3)O, 19491(8)O,
6164eA8)037334(8)O(1)O,04
90(4)O, 1234(4)0133(4)O(2)
O, 0881 (4) O, 5987 (4) 01275 (4
)O(3)02967((4)O,3682(4)00
979(4)O(4)02957(4)O, 8710(
4)O, 114Δ4)O(5)O, 2025(4)O,
3817(4)03594(4)O(6)O, 1729
(4) O, 8599 (4) O, 370 (j4) O (7)
O, 4094 (4) 01104 (4) O, 3615 (4
)O(8)04323(4)O,6508(4)038
0Cj, A The present invention provides the above-mentioned 4FeO-6Fe2O3.
An object of the present invention is to provide a novel compound belonging to the monoclinic system in which NiO is substituted for FeO in a 9GeO2 compound, and a method for producing the same.
本発明の４ＮｉＯ−６Ｆｅ。4NiO-6Fe of the present invention.
ｏ。・ ９ＧｅＯ。（Ｎｉ、Ｆｅ、。Ｇｅ９Ｏ、Ｏ）で
示される単斜晶系に属する化ゝ合物は、この化合物中、
ニッケルはＮｉ゜゛イオン、鉄はＦｅ３本イオン、ゲル
マニウムはＱ゛゛イオンとして存在している。この化合
物は結晶構造唆し、単斜晶系に属し、その空間群はＰ２
ｌ／ｃ℃る。格子定数は、ＡＯ＝８．３９９±０．００
２（Ａ）、恥＝８．３２８±０．』（Ａ）、ＣＯ＝９．
１８５±０．００２（Ａ）およびβ＝１１７。±０．０
２（０）である。ゲルマニウムは４個の酸素によつて囲
まれてり、鉄とニッケルは４個の酸素によつて囲まれも
のと、６個の酸素によつて囲まれたものとがる。o.・9GeO. The compound belonging to the monoclinic system represented by (Ni, Fe, .Ge9O, O) has the following compounds:
Nickel exists as a Ni゜゛ ion, iron as an Fe3 ion, and germanium as a Q゛゛ ion. This compound has a crystal structure, belonging to the monoclinic system, and its space group is P2.
l/c°C. The lattice constant is AO=8.399±0.00
2(A), shame=8.328±0. ”(A), CO=9.
185±0.002 (A) and β=117. ±0.0
2(0). Germanium is surrounded by 4 oxygen atoms, and iron and nickel are surrounded by 4 oxygen atoms and 6 oxygen atoms.
単位格子内には、４Ｎ１０−６Ｆ′Ｅ２Ｏ３・９Ｇｅ０
２して化学式を表現した場合、１化学式存在す冫陰イオ
ンである酸素は緻密構造をとつている。この結晶の面指
数（Ｈｋｌ）、面間隔ｄ（Ａ（ＤＯは実測値を、Ｄｃは
計算値を示す）およびＸ：に対する相対強度１（％）は
、第２表の示すとりである。 −
・−ｖυ 乙０５この単斜晶系に属する化合物
は、磁性材料ならびに半導体材料および触媒として有用
なものである。In the unit cell, 4N10-6F'E2O3・9Ge0
2 When expressed as a chemical formula, oxygen, which is the negative ion that exists in one chemical formula, has a dense structure. The planar index (Hkl), interplanar spacing d (A (DO indicates the measured value, Dc indicates the calculated value), and relative strength 1 (%) with respect to X: of this crystal are shown in Table 2. -
-vυ Otsu05 Compounds belonging to this monoclinic system are useful as magnetic materials, semiconductor materials, and catalysts.
この化合物は、次の方法によつて製造し得られる。This compound can be produced by the following method.
金属ニッケルあるいは酸化ニッケルもしくはフ加熱され
ることにより酸化ニッケルに分解される化合物と、金属
鉄あるいは酸化鉄もしくは加熱されることにより酸化鉄
に分解される化合物と、ゲルマニウムあるいはゲルマニ
ウム酸化物もしくは加熱されることにより分解されて２
酸化ゲルマニ２ウムを生ずる化合物とを、ニッケル、鉄
、ゲルマニウムの割合が原子比で４対１謝９になるよう
に混合して、８００℃以上の温度で加熱することによつ
て製造することが出来る。本発明に用いる出発物質は、
市販のものをそのまま使用してもよいが、出発物質相互
間の化学反応を速やかに進行させるためには、粒径がち
いさい程よく、特には１０μｍ以下てあることが好まし
い。Metallic nickel or nickel oxide or a compound that decomposes into nickel oxide when heated; metallic iron or iron oxide or a compound that decomposes into iron oxide when heated; and germanium or germanium oxide or a compound that decomposes into iron oxide when heated. Decomposed by 2
It can be produced by mixing nickel, iron, and germanium with a compound that produces germanium oxide in an atomic ratio of 4:1 x 9, and heating the mixture at a temperature of 800°C or higher. I can do it. The starting materials used in the present invention are:
Commercially available products may be used as they are, but in order to speed up the chemical reaction between the starting materials, it is preferable that the particle size is as small as possible, particularly 10 μm or less.
また磁性材料、電気材料として用いる場合には、不純物
の混入をきらうので、出発原料は、純度が高ければ高い
ほど好ましい。これらの原料をそのまま、あるいはアル
コール類、もしくはアセトンと共に充分に混合する。こ
れらの混合割合は、ニッケル、鉄、ゲルマニウムの割合
が、原子比として４対１謝９の割合である。この割合を
はずすと目的とする化合物を得ることは出来ない。この
混合物を、大気中あるいは酸化性雰囲気もしくは鉄およ
びニッケルが３価イオン状態および２価イオン状態から
還元され得ない程度の還元雰囲気のもとで、８００℃以
上の温度で加熱する。加熱時間は、１日もしくはそれ以
上である。加熱の際の昇温速度には制約はない。反応終
了後は、０℃に急冷するか、あるいは、炉外に急激にひ
きだせばよい。得られた４Ｎｉ０６Ｆ′Ｅ２Ｏ３９Ｇｅ
Ｏ２（Ｎｌ４Ｆｅｌ２Ｇｅ９Ｏ４Ｏ）化合物は黒色であ
る。Further, when used as a magnetic material or an electric material, the higher the purity of the starting material, the more preferable it is, since contamination with impurities is to be avoided. These raw materials are thoroughly mixed as they are or together with alcohol or acetone. The mixing ratio of these materials is such that the atomic ratio of nickel, iron, and germanium is 4:1 x 9. If this ratio is exceeded, the target compound cannot be obtained. This mixture is heated at a temperature of 800° C. or higher in air or under an oxidizing atmosphere or a reducing atmosphere such that iron and nickel cannot be reduced from their trivalent and divalent ionic states. The heating time is one day 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 of the furnace. Obtained 4Ni06F'E2O39Ge
The O2(Nl4Fel2Ge9O4O) compound is black.
粉末Ｘ線回折法によつて、結晶構造を有することがわか
つた。混合物の試料重量および加熱後の試料の重量を秤
量することによつて、化合物の化学量論数が決定された
。実施例
純度９９．９％以上のニッケル酸化物（ＮｉＯ）粉末、
純度９９．９％以上の酸化鉄（Ｆｅ２Ｏ３）粉末、およ
び９９．９９％以上の酸化ゲルマニウム（ＧｅＯ２）粉
末を、モル比で４対６対９の割合に秤量し、乳鉢内でエ
チルアルコールを加えて充分に混合し、平均粒径数μｍ
の微粉末混合物を得た。It was found to have a crystalline structure by powder X-ray diffraction. The stoichiometry of the compound was determined by weighing the sample weight of the mixture and the weight of the sample after heating. Example Nickel oxide (NiO) powder with a purity of 99.9% or more,
Iron oxide (Fe2O3) powder with a purity of 99.9% or more and germanium oxide (GeO2) powder with a purity of 99.99% or more were weighed at a molar ratio of 4:6:9, and ethyl alcohol was added in a mortar. Mix thoroughly to obtain an average particle size of several μm.
A fine powder mixture was obtained.
該混合物を白金ルツボ内にみたし、１１００℃に設定さ
れた箱型シリユニツト炉内に入れ、５日間加熱し、その
後、試料を炉外にとりだし、室温まで急速に冷却した。
得られた試料は、４Ｎ１０−６Ｆｅ２０３・９Ｃｅ０２
（Ｎｉ４Ｆｅｌ。Ｇｅ９Ｏ４Ｏ）であり、単斜晶系に属
する化合ノ物であつた。その結晶の性状は、第２表に示
すとおりである。加熱前後の試料の重量の変化を秤量し
、実験誤差範囲内での一致をみた。The mixture was placed in a platinum crucible, placed in a box-shaped silicon unit furnace set at 1100°C, and heated for 5 days, after which the sample was taken out of the furnace and rapidly cooled to room temperature.
The obtained sample was 4N10-6Fe203・9Ce02
(Ni4Fel.Ge9O4O), and was a compound belonging to the monoclinic system. The properties of the crystal are shown in Table 2. The change in weight of the sample before and after heating was measured, and agreement was found within the experimental error range.
Claims (1)
＿４Ｆｅ＿１＿２Ｃｅ＿９Ｏ＿４＿０）で示される単斜
晶系に属する化合物２ 金属ニッケルあるいは酸化ニッ
ケルもしくは加熱されることにより酸化ニッケルに分解
される化合物と、金属鉄あるいは酸化鉄もしくは加熱さ
れることにより酸化鉄に分解される化合物と、ゲルマニ
ウムあるいはゲルマニウム酸化物もしくは加熱されるこ
とにより分解されて２酸化ゲルマニウムを生ずる化合物
とを、ニッケル、鉄、ゲルマニウムの割合が原子比で４
対１２対９になるように混合して、８００℃以上の温度
で加熱することを特徴とする、４ＮｉＯ・６Ｆｅ＿２Ｏ
＿３・９ＧｅＯ＿２（Ｎｉ＿４Ｆｅ＿１＿２Ｇｅ＿９Ｏ
＿４＿０）で示される単斜晶系に属する化合物の製造法
。1 4NiO・6Fe_2O_3・9GeO_2(Ni
Compound 2 belonging to the monoclinic system represented by _4Fe_1_2Ce_9O_4_0) Metallic nickel or nickel oxide, or a compound that decomposes into nickel oxide when heated, and metallic iron or iron oxide, or a compound that decomposes into iron oxide when heated. Compound and germanium, germanium oxide, or a compound that decomposes to produce germanium dioxide when heated, in which the proportion of nickel, iron, and germanium is 4 in atomic ratio.
4NiO・6Fe_2O, characterized by mixing in a ratio of 12:9 and heating at a temperature of 800°C or higher.
_3・9GeO_2(Ni_4Fe_1_2Ge_9O
_4_0) A method for producing a compound belonging to the monoclinic system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56065033A JPS6045130B2 (en) | 1981-04-27 | 1981-04-27 | Compound belonging to the monoclinic system represented by 4NiO・6Fe↓2O↓3・9GeO↓2 (Ni↓4Fe↓1↓2Ge↓9O↓4↓0) and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56065033A JPS6045130B2 (en) | 1981-04-27 | 1981-04-27 | Compound belonging to the monoclinic system represented by 4NiO・6Fe↓2O↓3・9GeO↓2 (Ni↓4Fe↓1↓2Ge↓9O↓4↓0) and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57179040A JPS57179040A (en) | 1982-11-04 |
| JPS6045130B2 true JPS6045130B2 (en) | 1985-10-08 |
Family
ID=13275253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56065033A Expired JPS6045130B2 (en) | 1981-04-27 | 1981-04-27 | Compound belonging to the monoclinic system represented by 4NiO・6Fe↓2O↓3・9GeO↓2 (Ni↓4Fe↓1↓2Ge↓9O↓4↓0) and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6045130B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0322930U (en) * | 1989-07-11 | 1991-03-11 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308239A (en) * | 1992-02-04 | 1994-05-03 | Air Products And Chemicals, Inc. | Method for reducing NOx production during air-fuel combustion processes |
-
1981
- 1981-04-27 JP JP56065033A patent/JPS6045130B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0322930U (en) * | 1989-07-11 | 1991-03-11 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57179040A (en) | 1982-11-04 |
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