JPH0333652B2 - - Google Patents
Info
- Publication number
- JPH0333652B2 JPH0333652B2 JP62129065A JP12906587A JPH0333652B2 JP H0333652 B2 JPH0333652 B2 JP H0333652B2 JP 62129065 A JP62129065 A JP 62129065A JP 12906587 A JP12906587 A JP 12906587A JP H0333652 B2 JPH0333652 B2 JP H0333652B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxide
- heating
- thulium
- metallic
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Description
産業上の利用分野
本発明は光機能材料、半導体材料及び触媒材料
として有用な新規化合物であるTmGaZn7θ10で示
される六方晶系の層状構造を有する化合物および
その製造法に関する。
従来技術
従来、(Yb3+Fe3+θ3)oFe2+θ(nは整数を示す)
で示される六方晶系の層状構造を有する化合物は
本出願人によつて合成され知られている。
YbFe2θ4、Yb2Fe3θ7、Yb3Fe4θ10及び
Yb4Fe5θ13の六方晶系としての格子定数、Ybθ1.5
層、Feθ1.5層、Fe2θ2.5層の単位格子内における層
数を示すと表−1の通りである。
これらの化合物は酸化鉄(Feθ)1モルに対し
て、YbFeθ3がnモルの割合で化合していると考
えられる層状構造を持つ化合物である。
INDUSTRIAL APPLICATION FIELD The present invention relates to a compound having a hexagonal layered structure represented by TmGaZn 7 θ 10 , which is a new compound useful as an optical functional material, a semiconductor material, and a catalyst material, and a method for producing the same. Conventional technology Conventionally, (Yb 3+ Fe 3+ θ 3 ) o Fe 2+ θ (n indicates an integer)
The compound having a hexagonal layered structure represented by is synthesized by the applicant and is known. YbFe 2 θ 4 , Yb 2 Fe 3 θ 7 , Yb 3 Fe 4 θ 10 and
Lattice constant of Yb 4 Fe 5 θ 13 as a hexagonal system, Ybθ 1.5
Table 1 shows the number of layers in the unit cell, Feθ 1.5 layer, and Fe 2 θ 2.5 layer. These compounds have a layered structure in which n moles of YbFeθ 3 are combined with 1 mole of iron oxide (Feθ).
【表】
発明の目的
本発明は(YbFeθ3)oFeθの化学式において、n
=1/7に相当しYb3+の代わりにTm3+をFe3+の代
わりにGa3+を、Fe2+の代わりにZn2+を置きかえ
て得られる新規な化合物を提供するにある。
発明の構成
本発明のTmGaZn7θ10で示される化合物は、イ
オン結晶モデルでは、Tm3+(Ga3+Zn2+)
Zn6 2+θ10 2-として記載され、その構造はTmθ1.5
層、(Ga3+Zn2+)θ2.5層およびZnθ層の積層によつ
て形成されており、著しい構造異方性を持つてい
ることがその特徴の一つである。Zn2+の1/7は
Ga3+と共に(Ga3+、Zn2+)θ2.5層を作り、残りの
6/7はZnθ層を作つている。六方晶系としての格
子定数は次の通りである。
a=3.300±0.001(Å)
c=72.11±0.01(Å)
この化合物の面指数(hkl)、面間隔(d(Å))
(dpは実測値、dcは計算値を示す)およびX線に
対する相対反射強度(I%)を示すと表−2の通
りである。
この化合物は光機能材料、半導体材料および触
媒材料等に有用なものである。[Table] Purpose of the Invention The present invention is based on the chemical formula of (YbFeθ 3 ) o Feθ, where n
= 1/7 and is obtained by replacing Tm 3+ in place of Yb 3+ , Ga 3+ in place of Fe 3+ , and Zn 2+ in place of Fe 2+ . . Structure of the Invention In the ionic crystal model, the compound represented by TmGaZn 7 θ 10 of the present invention is Tm 3+ (Ga 3+ Zn 2+ )
Zn 6 2+ θ 10 2- , whose structure is Tmθ 1.5
It is formed by stacking a (Ga 3+ Zn 2+ ) θ 2.5 layer and a Znθ layer, and one of its characteristics is that it has significant structural anisotropy. 1/7 of Zn 2+ is
Together with Ga 3+ , (Ga 3+ , Zn 2+ ) θ 2.5 layers are formed, and the remaining 6/7 forms a Zn θ layer. The lattice constants as a hexagonal crystal system are as follows. a=3.300±0.001 (Å) c=72.11±0.01 (Å) Planar index (hkl), interplanar spacing (d (Å)) of this compound
(d p is an actual measured value, d c is a calculated value) and the relative reflection intensity (I%) for X-rays is shown in Table 2. This compound is useful for optical functional materials, semiconductor materials, catalyst materials, and the like.
【表】【table】
【表】【table】
【表】
この化合物は次の方法によつて製造し得られ
る。
金属ツリウムあるいは酸化ツリウムもしくは加
熱により酸化ツリウムに分解される化合物と、金
属ガリウムあるいは酸化ガリウムもしくは加熱に
より酸化ガリウムに分解される化合物と、金属亜
鉛あるいは酸化亜鉛もしくは加熱により酸化亜鉛
に分解される化合物と、Tm、GaおよびZnの割
合が原子比で1対1対7の割合で混合し、該混合
物を600℃以上の温度で大気中、酸化性雰囲気中
あるいはTmおよびGaが各々3価イオン状態、
Znが2価イオン状態より還元されない還元雰囲
気中で加熱することによつて製造し得られる。
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、化学反応を速やかに進行さ
せるためには粒径が小さい方がよく、特に10μm
以下であることが好ましい。
また、光機能材料、半導体材料として用いる場
合には不純物の混入をきらうので、純度の高いこ
とが好ましい。出発物質が加熱により金属酸化物
を得る化合物としては、それぞれの金属の水酸化
物、炭酸塩、硝酸塩等が挙げられる。
原料はそのまま、あるいはアルコール類、アセ
トン等と共に充分に混合する。
原料の混合割合は、Tm、Ga、及びZnの割合
が原子比で1対1対7の割合であることが必要で
ある。これをはずすと目的とする化合物の単一相
を得ることができない。
この混合物を大気中、酸化性雰囲気中あるいは
TmおよびGaが各々3価イオン状態、Znが各々
2価イオン状態から還元されない還元雰囲気中で
600℃以上のもとで加熱する。加熱時間は数時間
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。加熱終了後急冷するか、あるいは
大気中に急激に引き出せばよい。
得られたTmGaZn7θ10化合物の粉末は無色であ
り、粉末X線回折法によつて結晶構造を有するこ
とが分かつた。その結晶構造は層状構造であり、
Tmθ1.5層、(Ga、Zn)θ2.5層、およびZnθ層の積
重ねによつて形成されていることが分かつた。
実施例
純度99.99%以上の酸化ツリウム(Tm2θ3)粉
末、純度99.9%以上の酸化ガリウム(Ga2θ3)粉
末、試薬特級の酸化亜鉛(Znθ)粉末をモル比で
1対1対14の割合に秤量し、めのう乳鉢内でエタ
ノールを加えて、約30分間混合し、平均粒径数μ
mの微粉末混合物を得た。該混合物を白金管内に
封入し、1450℃に設定された管状シリコニツト炉
内に入れ、4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、TmGaZn7θ10単一相であり、
粉末X線回折法によつて面指数(hkl)、面間隔
(dp)および相対反射強度(%)を測定した。
その結果は表−2の通りであつた。
六方晶系としての格子定数は
a=3.300±0.001(Å)
c=72.11±0.01(Å)
であつた。
上記の格子定数および表−2の面指数(hkl)
より算出した面間隔(dc(Å))は、実測の面間隔
(do(Å))と極めてよく一致していた。
発明の効果
本発明は光機能材料、半導体材料及び触媒とし
て有用な新規化合物を提供する。[Table] This compound can be produced by the following method. Metallic thulium or thulium oxide or a compound that is decomposed into thulium oxide by heating; Metallic gallium or gallium oxide or a compound that is decomposed into gallium oxide by heating; Metallic zinc or zinc oxide or a compound that is decomposed into zinc oxide by heating. , Tm, Ga, and Zn are mixed in an atomic ratio of 1:1:7, and the mixture is heated at a temperature of 600°C or higher in the air, in an oxidizing atmosphere, or when Tm and Ga are each in a trivalent ion state,
It can be produced by heating in a reducing atmosphere in which Zn is not reduced from a divalent ion state. Commercially available starting materials used in the present invention may be used as they are, but in order for the chemical reaction to proceed quickly, it is better to have a small particle size, especially 10 μm.
It is preferable that it is below. Further, when used as an optical functional material or a semiconductor material, it is preferable to have high purity since contamination with impurities is avoided. Examples of compounds whose starting materials yield metal oxides by heating include hydroxides, carbonates, and nitrates of the respective metals. The raw materials are thoroughly mixed as they are or together with alcohols, acetone, etc. The mixing ratio of the raw materials needs to be such that the ratio of Tm, Ga, and Zn is 1:1:7 in atomic ratio. If this is removed, a single phase of the target compound cannot be obtained. This mixture is stored in the air, in an oxidizing atmosphere, or
In a reducing atmosphere where Tm and Ga are each in a trivalent ion state and Zn is not reduced from a divalent ion state,
Heat at 600℃ or higher. Heating time is several hours or more. There are no restrictions on the rate of temperature increase during heating. After heating, it can be rapidly cooled, or it can be rapidly drawn out into the atmosphere. The obtained TmGaZn 7 θ 10 compound powder was colorless and was found to have a crystalline structure by powder X-ray diffraction. Its crystal structure is layered,
It was found that it was formed by stacking a Tmθ 1.5 layer, a (Ga, Zn)θ 2.5 layer, and a Znθ layer. Example Thulium oxide (Tm 2 θ 3 ) powder with a purity of 99.99% or more, gallium oxide (Ga 2 θ 3 ) powder with a purity of 99.9% or more, and reagent grade zinc oxide (Znθ) powder in a molar ratio of 1:1:14 Add ethanol in an agate mortar and mix for about 30 minutes until the average particle size is several microns.
A fine powder mixture of m was obtained. The mixture was sealed in a platinum tube, placed in a tubular siliconite furnace set at 1450°C, and heated for 4 days, after which the sample was taken out of the furnace and rapidly cooled to room temperature. The obtained sample is TmGaZn 7 θ 10 single phase,
Planar index (hkl), planar spacing (d p ), and relative reflection intensity (%) were measured by powder X-ray diffraction.
The results were as shown in Table-2. The lattice constants as a hexagonal crystal system were a=3.300±0.001 (Å) and c=72.11±0.01 (Å). The above lattice constants and the surface index (hkl) in Table 2
The calculated interplanar spacing (d c (Å)) was in excellent agreement with the actually measured interplanar spacing (do (Å)). Effects of the Invention The present invention provides novel compounds useful as optical functional materials, semiconductor materials, and catalysts.
Claims (1)
を有する化合物。 2 金属ツリウムあるいは酸化ツリウムもしくは
加熱により酸化ツリウムに分解される化合物と、
金属ガリウムあるいは酸化ガリウムもしくは加熱
により酸化ガリウムに分解される化合物と、金属
亜鉛あるいは酸化亜鉛もしくは加熱により酸化亜
鉛に分解される化合物と、Tm、GaおよびZnの
割合が原子比で1対1対7の割合で混合し、該混
合物を600℃以上の温度で大気中、酸化性雰囲気
中あるいはTmおよびGaが各々3価イオン状態、
Znが2価イオン状態より還元されない還元雰囲
気中で加熱することを特徴とするTmGaZn7θ10で
示される六方晶系の層状構造を有する化合物の製
造法。[Claims] A compound having a hexagonal layered structure represented by 1 TmGaZn 7 θ 10 . 2 Metallic thulium or thulium oxide or a compound that is decomposed into thulium oxide by heating,
The atomic ratio of metallic gallium or gallium oxide or a compound decomposed to gallium oxide by heating, metallic zinc or zinc oxide or a compound decomposed to zinc oxide by heating, and Tm, Ga, and Zn is 1:1:7. The mixture is heated to a temperature of 600°C or higher in the air, in an oxidizing atmosphere, or when Tm and Ga are each in a trivalent ion state,
1. A method for producing a compound having a hexagonal layered structure represented by TmGaZn 7 θ 10 , which comprises heating in a reducing atmosphere in which Zn is not reduced beyond a divalent ion state.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12906587A JPS63295425A (en) | 1987-05-26 | 1987-05-26 | Compound shown by tmgazn7o10 and having hexagonal lamellar strucuture and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12906587A JPS63295425A (en) | 1987-05-26 | 1987-05-26 | Compound shown by tmgazn7o10 and having hexagonal lamellar strucuture and its production |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63295425A JPS63295425A (en) | 1988-12-01 |
JPH0333652B2 true JPH0333652B2 (en) | 1991-05-17 |
Family
ID=15000216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12906587A Granted JPS63295425A (en) | 1987-05-26 | 1987-05-26 | Compound shown by tmgazn7o10 and having hexagonal lamellar strucuture and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63295425A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS606894A (en) * | 1983-06-24 | 1985-01-14 | 株式会社東芝 | Nuclear fuel aggregate |
-
1987
- 1987-05-26 JP JP12906587A patent/JPS63295425A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS606894A (en) * | 1983-06-24 | 1985-01-14 | 株式会社東芝 | Nuclear fuel aggregate |
Also Published As
Publication number | Publication date |
---|---|
JPS63295425A (en) | 1988-12-01 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term |