JPS62283815A - Tetragonal compound represented by axti16-xmyga16+x)-yo56 and having tunnel structure - Google Patents
Tetragonal compound represented by axti16-xmyga16+x)-yo56 and having tunnel structureInfo
- Publication number
- JPS62283815A JPS62283815A JP12409586A JP12409586A JPS62283815A JP S62283815 A JPS62283815 A JP S62283815A JP 12409586 A JP12409586 A JP 12409586A JP 12409586 A JP12409586 A JP 12409586A JP S62283815 A JPS62283815 A JP S62283815A
- Authority
- JP
- Japan
- Prior art keywords
- heating
- oxide
- compound
- metal oxide
- decomposed
- 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.)
- Granted
Links
- -1 Tetragonal compound Chemical class 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 abstract 1
- 229910003083 TiO6 Inorganic materials 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 abstract 1
- 239000012212 insulator Substances 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 abstract 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000007716 flux method Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910005534 GaO2 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規化合物である一般式
％式％
（ただし、Ａはに、Ｒｂ及びＣｓから選ばれた１種また
は２種以上のアルカリ金属１ＭはＡＩ、Ｆｅ。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is a novel compound of the general formula % (wherein A is 1M of one or more alkali metals selected from Rb and Cs) , Fe.
及びＣｒから選ばれた１種または２種以上の３価金属、
Ｘ＝０．１〜２．０ 、 Ｙ＝０．ｌ〜１０を表わす）
で示される正方晶系のトンネル構造を有する化合物及び
その製造法に関する。該新規化合物は陽イオン伝導体、
イオン交換体、触媒、耐熱材及び断熱材として有用なも
のである。and one or more trivalent metals selected from Cr,
X=0.1~2.0, Y=0. (represents l to 10)
The present invention relates to a compound having a tetragonal tunnel structure shown in and a method for producing the same. The new compound is a cation conductor,
It is useful as an ion exchanger, a catalyst, a heat-resistant material, and a heat insulating material.
発明の目的
本発明の目的は前記のような有用な新規化合物を提供す
るにある。OBJECTS OF THE INVENTION It is an object of the present invention to provide useful new compounds as described above.
発明の構成
本発明の新規化合物は一般式
％式％（
し、Ａ、Ｍ、Ｘ、Ｙは前記と同じものを表わす）で示さ
れる化合物であり、Ｔｉ４＋はＴｉ○６八面体配位をと
り、Ｍ″′もＭＯ，八面体配位をとるが、Ｇａ３＋はＧ
ａ○４四面体配位をとり、それらの配位体の連鎖が八面
体４個と四面体４個で作る大きなトンネル構造を有する
ことを特徴とする化合物で、さらに、Ｔｉ０ｈ八面体の
Ｘ個を３価のＭＯ６八面体で置換することにより陽イオ
ン電荷調整のためＸ個のＡ原子がトンネル中に配位した
ものである。Structure of the Invention The novel compound of the present invention is a compound represented by the general formula % (where A, M, , M″′ also has MO, octahedral coordination, but Ga3+ has G
A compound characterized by having a○4 tetrahedral coordination and a chain of these coordinates having a large tunnel structure formed by 4 octahedrons and 4 tetrahedrons. By substituting trivalent MO6 octahedron, X A atoms are coordinated in the tunnel to adjust the cation charge.
本発明者は、さきに一般式
Ａｘ ＴＬａ −ｘ Ｇ ａ ｌｈ ＋ Ｘ Ｏｓｂ
（ただし、Ａは前記と同じものを表わす）で示される新
規化合物を提供した（特願昭乙（−３ｏＳＺＬＦ 号）
。The present inventor previously described the general formula Ax TLa −x Galh + X Osb
(However, A represents the same thing as above.) (Patent Application Sho-Otsu (-3oSZLF))
.
該化合物は優れた陽イオン伝導体、イオン交換体。The compound is an excellent cation conductor and ion exchanger.
耐熱材、断熱材として優れた特性を有するものであるが
、Ｇａが高価であり、工業性に問題である。Although it has excellent properties as a heat-resistant material and a heat insulating material, Ga is expensive and there are problems with industrial efficiency.
そこで、この結晶構造の中でＧａの占有する配位体のう
ち、少くともＧａｐ、八面体を他の安価な３価金属で置
換できれば製造コストも低減できると考え、鋭意研究の
結果、ＡＩ、Ｆｅ、Ｃｒ、の３価金属で置換え得られる
ことを究明し得た。この知見に基いて本発明を完成した
。Therefore, we thought that manufacturing costs could be reduced if at least the gaps and octahedrons among the coordination bodies occupied by Ga in this crystal structure could be replaced with other inexpensive trivalent metals, and as a result of intensive research, we found that AI, It has been found that it can be replaced with trivalent metals such as Fe and Cr. The present invention was completed based on this knowledge.
本発明の新規物質の構造は、一般式
ＡＸ Ｔｊ＋６− Ｘ Ｇ ａ ＋ｂ ＋ ｘ ０５６
と等しい構造を有するが、組成は一般式
％式％
Ｙは前記と同じものを表わす）で示すように異な％席で
Ｙ＝８）を占有するのみならず、Ｙ＝ｌＯ席を置換した
Ｘ分が付加されるためで、Ｘ＝２の場合はＹ＝１０とな
る。なお、Ｘ＝０．１より少ないと、正方品系トンネル
構造は得られない。The structure of the new substance of the present invention is represented by the general formula AX Tj+6- X Ga +b + x 056
However, the composition is not only occupied by the general formula % (Y represents the same as above), but also by occupying a different % seat (Y = 8), but also by This is because a minute is added, and when X=2, Y=10. Note that if X is less than 0.1, a square tunnel structure cannot be obtained.
図面（第１図）に基づいて、その構造を説明すると、第
１図（ａｌに示すように、正方品系に属し、大口径のト
ンネル構造をしている。四面体はすべてＧａＯ＆である
が、八面体の中で大口径トンネルの枠組を形成する八面
体は、ＴｉＯ２とＭＯ。The structure is explained based on the drawing (Figure 1). As shown in Figure 1 (al), it belongs to the tetragonal product system and has a tunnel structure with a large diameter. All of the tetrahedra are GaO&, The octahedrons that form the framework of the large-diameter tunnel are TiO2 and MO.
からなり、その割合はそれぞれ７０％と３０％の割合で
分布している。The percentages are distributed at 70% and 30%, respectively.
なお、大口径トンネル間のマトリックスは第１図（ｂｌ
に示すルチル構造と、第１図（Ｃ１に示すβ−ガリア構
造単位の連結からなり立っている。The matrix between large-diameter tunnels is shown in Figure 1 (bl
It consists of a rutile structure shown in Figure 1 (C1) connected to a β-gallium structural unit.
本発明の製造法としては、焼成法とフラックス法のいず
れでもよい。焼成法では粉末状結晶体が得られ、フラッ
クス法では針状または繊維状の結晶体が得られる。The manufacturing method of the present invention may be either a firing method or a flux method. The calcination method yields a powdered crystal, and the flux method yields an acicular or fibrous crystal.
焼成法
Ｋ ｚ Ｏ、Ｒｂ ２０及びＣｓ ｔ Ｏから選ばれた
アルカリ金属酸化物あるいは加熱により該アルカリ金属
酸化物に分解される化合物と、酸化チタンあるいは加熱
により酸化チタンに分解される化合物と、酸化ガリウム
あるいは加熱により酸化ガリウムに分解される化合物と
、酸化アルミニウム、酸化鉄及び酸化クロムから選ばれ
た三価金属化合物あるいは加熱により該三価金属酸化物
に分解される化合物とを、一般式
％式％
（ただし、Ａ、Ｍ、Ｘ、Ｙは前記と同じものを表わす）
で示される組成割合に混合し、該混合物を１０００℃以
上の温度で焼成する。Calcination method An alkali metal oxide selected from K z O, Rb 20 and Cs t O or a compound decomposed into the alkali metal oxide by heating, titanium oxide or a compound decomposed into titanium oxide by heating, Gallium or a compound decomposed into gallium oxide by heating, and a trivalent metal compound selected from aluminum oxide, iron oxide, and chromium oxide, or a compound decomposed into the trivalent metal oxide by heating, are expressed by the general formula %. % (However, A, M, X, Y represent the same as above)
The mixture is mixed at a composition ratio shown by , and the mixture is fired at a temperature of 1000° C. or higher.
フラックス法
に２０．ＲｂＺＯ及びＣ５２０から選ばれたアルカリ金
属酸化物あるいは加熱により該アルカリ金属酸化物に分
解される化合物と、Ｔ ｉＯｚあるいは加熱によりＴｉ
Ｏ２に分解される化合物と、ＧａｚＯ３あるいは加熱に
よりＣｒａｚｙ、、に分解される化合物と、ＡｌｔＯｎ
、ＦｅｚＯ３及びＣｒ２Ｏ，から選ばれた三価金属酸
化物あるいは加熱により咳三価金属酸化物とを、一般式
（Ａ ２０ ） −（Ｔ ｉ Ｏ□）５（Ｍｚ ｏｘ）
ｃ （Ｇ ａ ｚ Ｏｚ）＋ （ただし、Ａ、Ｍは前記
と同じ、ａ、 ｂ＝０．１〜２．Ｏ，ｃ、 ｄ ＝
０．１〜１．０を表わす）で示される組成割合に混合し
たものを結晶原料とし、一方Ｍ００３あるいは加熱によ
りＭｏＯ３に分解される化合物と、Ｋ、Ｒｂ。20 for flux method. An alkali metal oxide selected from RbZO and C520 or a compound decomposed into the alkali metal oxide by heating, and TiOz or TiOz by heating.
A compound that decomposes into O2, a compound that decomposes into GazO3 or Crazy by heating, and AltOn.
, FezO3 and Cr2O, or a trivalent metal oxide selected from the group consisting of the general formula (A 20 ) -(T i O□)5(Mz ox)
c (G az Oz) + (A, M are the same as above, a, b = 0.1 to 2. O, c, d =
0.1 to 1.0) is used as a crystal raw material, and on the other hand, M003 or a compound decomposed into MoO3 by heating, K, and Rb.
及びＣｓから選ばれたアルカリ金属酸化物あるいは加熱
により該アルカリ金属酸化物に分解される化合物とを、
一般式Ａｚ ０−ｎ（ＭｏＯ，）（ただし、Ａは前記と
同じ、ｎ＝１〜２を表わす）で示される組成割合に混合
したものをフラックス原料とし、結晶原料とフラックス
原料とをモル百分率が３０対７０〜１１ｔ９０の割合に
なるように混合し、該混合物を１２００〜１４００°Ｃ
で加熱溶融し、該溶融体を９００〜１０００°Ｃまで徐
冷して単結晶を育成する。and an alkali metal oxide selected from Cs or a compound that is decomposed into the alkali metal oxide by heating,
The flux raw material is mixed in the composition ratio shown by the general formula Az 0-n (MoO,) (where A is the same as above and represents n = 1 to 2), and the crystal raw material and the flux raw material are mixed in a molar percentage. The mixture was heated to 1200 to 1400°C.
The molten material is heated and melted at 900 to 1000° C. to grow a single crystal.
結晶原料とフラックス原料との混合割合は３０対７０〜
１０対９０の割合が適当である。The mixing ratio of crystal raw material and flux raw material is 30:70 ~
A ratio of 10:90 is appropriate.
また、９００〜１０００°Ｃまでは結晶育成のため、徐
冷することか必要である。In addition, slow cooling is required to 900 to 1000°C for crystal growth.
以下実施例を挙げ、その結晶の特性を示す。Examples will be given below to show the characteristics of the crystals.
実施例１゜
Ｋ２ Ｔｉ＋ａ Ｃｒ１ｏ Ｇ ａ ｏ ０５６粉末状
結晶体の製造
炭酸カリウム、二酸化チタン、酸化クロム、酸化ガリウ
ムの各粉末をモル比でＫ ｚ ＣＯ３： Ｔ ｉ Ｏ２
：Ｃｒｚ０３ ：Ｑａ２０３ ＝１ ：１４：５ ：
４の割合に混合し、この混合物約６ｇを白金ルツボに入
れ、１２５０°Ｃで３０分焼成した。Example 1 Production of K2 Ti+a Cr1o Gao 056 powder crystals Potassium carbonate, titanium dioxide, chromium oxide, and gallium oxide powders in molar ratio K z CO3: T i O2
:Crz03 :Qa203 =1 :14:5 :
Approximately 6 g of this mixture was placed in a platinum crucible and fired at 1250°C for 30 minutes.
この焼成物を摩砕混合し、更に１２５０°Ｃで２０時間
焼成した。得られた粉末状の結晶体は粉末Ｘ線回折法で
同定し、格子定数を測定した。This fired product was ground and mixed, and further fired at 1250°C for 20 hours. The resulting powdery crystalline material was identified by powder X-ray diffraction and its lattice constant was measured.
その結果はａ＝１８．１３９人、 Ｃ＝２．９９７８
人、単位容積■は９８７．３０人、計算密度は４．５７
ｇ／ａｍ３であった・
また、面指数（ｈｋｌ）、面間隔（６人）（ｄｏｂｓは
実測、ｄｃ続。は計算値）、Ｘ線に対する相対反射強度
（ｉｎｔｅｎｓｉｔｙ） （％）を示すと次の通りであ
った。The results are a=18.139 people, C=2.9978
People, unit volume ■ is 987.30 people, calculated density is 4.57
g/am3. In addition, the surface index (hkl), surface spacing (6 people) (dobs is actual measurement, DC continuous. is calculated value), and relative reflection intensity (intensity) (%) for X-rays are as follows. It was as follows.
２００ ９−０７０ ９＋０６４
４０２ ２ ０ ６．４１３
ｇ、４．？１ ２３ ＋
Ｏ５，７３６５ｊコ４ ２０４ ０
０ ４．５コ５
４＋５３７１４２０ ４−０５６ ４
．０５７ ３５１０ コ、５５
７ ３．５５Ｂ １０
５ ３ ０ ３．１１１
コ、１１ｏ ゴ００６０
０ コ、ｏ２３ コ、０
２コ ５＋ ０１ ２．９６
０ ２．９５９ ３６２０
’ １８６８ ２．８６７ ２５３０
＋ ２．６８Ｂ ２Ｊｌ！１３
１０３２ ＋ ２．５７７
１５７７ １５５５０ ２．５６
５ ２．５６６ １５６４０
２．５＋５ ２．５＋５ ５４ ＋
１ ２．４７９ ２．４８０
９０７ ３ ０ １コ８２
２．コ８１ ５４ ３
＋ ２ｊ１２ ２．コ
１コ １゜５２ ゴ
２．２４１ ２．２４０
１５１１２０− １２００
２．２００ ５６ ６ ０
２．１３Ｂ １１３８５６１
＋ ２ｊ１５ ２ｊ１５
５９ ＋ ０ １００コ
２．００４ コア
０ ＋ Ｌ９６＋２ １．９６１２
３６ ５ ＋ １．８
３６６ １．８３６７
５７４ ＋ １．１３００１
＋、ｌ３００ｉ ４０１０２０
、、 Ｌ７７８７ １．７７９０ ２
９５０ １＋７＋１ｉ１８ １＋７６
＋７ ２１１ ３ ＋
１．７ココ１ １．７ココ４３７ ６
１ １．６４５コ Ｌ
６４５２ ４０＋０６０ １．
５５５４ Ｌ５５５５ ３１０ ＋
Ｉ Ｌ５４６７ １＋５４６７
１０なお、一般式ＫｘＴｉ＋ｂ−ｘＣｒｖＧ
ａ（＋ｂ＋ｘ）−ｖｏ、ｂにおいてＸの値を０．１〜２
．０まで変動させても、またＹの値を０．１〜１０まで
変動させても同様な′熱処理で合成できた。200 9-070 9+064
402 2 0 6.413
g, 4. ? 1 23 +
O5,7365jko4 204 0
0 4.5ko5
4+5371420 4-056 4
．． 057 3510 Ko, 55
7 3.55B 10
5 3 0 3.111
Ko, 11o Go0060
0 ko, o23 ko, 0
2 pieces 5+ 01 2.96
0 2.959 3620
' 1868 2.867 2530
+2.68B 2Jl! 13
1032 + 2.577
1577 15550 2.56
5 2.566 15640
2.5+5 2.5+5 54 +
1 2.479 2.480
907 3 0 1ko82
2. ko81 54 3
+ 2j12 2. ko1ko 1゜52 go
2.241 2.240
151120-1200
2.200 56 6 0
2.13B 1138561
+ 2j15 2j15
59 + 0 100 pieces
2.004 core
0 + L96+2 1.9612
36 5 + 1.8
366 1.8367
574 + 1.13001
+, l300i 401020
,, L7787 1.7790 2
950 1+7+1i18 1+76
+7 211 3 +
1.7 here 1 1.7 here 437 6
1 1.645 pieces L
6452 40+060 1.
5554 L5555 310 +
I L5467 1+5467
10 Furthermore, the general formula KxTi+b-xCrvG
a(+b+x)-vo, set the value of X at b to 0.1 to 2
．． Even when the value of Y was varied up to 0, and even when the value of Y was varied from 0.1 to 10, it was possible to synthesize by the same heat treatment.
また、Ｋの代りにＲｂ、Ｃｓを用いても同様にそれぞれ
対応した結晶体が得られた。Further, even when Rb and Cs were used in place of K, corresponding crystals were similarly obtained.
実施例２゜
ＫｚＴｉ＋４ＡＬＧａ＋２０６．粉末状結晶体ノ製３ｊ
ａ炭酸カリウム、二酸化チタン、酸化アルミニウム、酸
化ガリウムの粉末を、モル比でＫ ｚ ＣＯ：１： Ｔ
ｉ０ｚ ： Ａ！□ｏ：＋ ： Ｇａ２０ｚ ＝
１ ： １４ ：３二６の割合で混合した。その混合物
６ｇを白金ルツボに入れ、１２５０°Ｃで３０分焼成し
た。この焼成物を摩砕混合して更に１２５０’ｃで２０
時間焼成して製造した。Example 2゜KzTi+4ALGa+206. Made of powdered crystal 3j
a Powders of potassium carbonate, titanium dioxide, aluminum oxide, and gallium oxide in a molar ratio of K z CO:1:T
i0z: A! □o:+: Ga20z=
They were mixed in a ratio of 1:14:326. 6 g of the mixture was placed in a platinum crucible and fired at 1250°C for 30 minutes. This fired product was ground and mixed and further heated at 1250'c for 20
Manufactured by baking for hours.
得られた粉末状結晶体は粉末Ｘ線回折法で同定し、格子
←定数を測定した。その結果はａ−１８，０５７（人）
、 ｃ ＝２．９８１３ （入）、単位容積Ｖは９
７２．１２ （人３）、計算密度は４．５１ （ｇ／ｃ
ｍ３）であった。The obtained powdered crystalline material was identified by powder X-ray diffraction method, and the lattice constant was measured. The result is a-18,057 (people)
, c = 2.9813 (in), unit volume V is 9
72.12 (person 3), calculated density is 4.51 (g/c
m3).
また、その面指数１面間隔、相対強度は次の表の通りで
あった。Further, the plane index, plane spacing, and relative strength were as shown in the following table.
なお、一般式Ｋ ＸＴ ｉ＋ｂ −ｘＡ Ｉｖ Ｇ ａ
（＋ｂ ？ Ｘ）−ｙＯ６，において、Ｘの値を０．１
〜２．０．Ｙの値を０．１〜１０まで変動させても同様
な熱処理で合成できた。また、カリウムに代えてＲｈ、
Ｃｓを用いても同様にそれぞれ対応した結晶体が合成で
きた。In addition, the general formula K XT i+b −xA Iv Ga
(+b?X)-yO6, set the value of X to 0.1
~2.0. Even if the value of Y was varied from 0.1 to 10, the synthesis could be performed using the same heat treatment. Also, instead of potassium, Rh,
Corresponding crystals were similarly synthesized using Cs.
実施例３゜
Ｋ２Ｔｉ＋４ＦｅｔＣｒａ＋ａＯｓｂ粉状結晶体の製造
炭酸カリウム、二酸化チタン、酸化鉄、酸化ガリウムの
粉末を、モル比でＫｚＣＯｚ ： Ｔｉ０ｚ ’Ｆ
ｅｚＯ３：ＧａｚＯｓ ＝ｔ ： １４ ： ２ ：
７の割合で混合した。その混合物６ｇを白金ルツボに入
れ、１２５０℃で３０分間焼成した。Example 3 Production of K2Ti+4FetCra+aOsb powder crystals Powders of potassium carbonate, titanium dioxide, iron oxide, and gallium oxide were mixed in a molar ratio of KzCOz:Ti0z'F
ezO3:GazOs=t: 14: 2:
They were mixed at a ratio of 7. 6 g of the mixture was placed in a platinum crucible and fired at 1250° C. for 30 minutes.
この焼成物を摩砕混合して更に１２５０℃で２０時間焼
成して製造した。This fired product was ground and mixed, and then fired at 1250° C. for 20 hours to produce a product.
得られた粉末状結晶体は粉末Ｘ線回折法で同定し、その
格子定数を測定した。The obtained powdered crystalline material was identified by powder X-ray diffraction method, and its lattice constant was measured.
その結果はａ ＝１８．１８２ （人） 、 ｃ ＝
２．９７９ （人）。The result is a = 18.182 (people), c =
2.979 (people).
単位容積■は９８４．９５ （人３）、計算密度は４．
７９（ｇ／ａｍ’ ）であった。The unit volume ■ is 984.95 (3 people), and the calculated density is 4.
79 (g/am').
また、その面指数１面間隔、相対強度は次の表の通りで
あった。Further, the plane index, plane spacing, and relative strength were as shown in the following table.
１ １ ０ １２．８６ １２
．８７ ５２０ ０ ９．
０９１ ９．１００ ４５２
２０ ６．４２Ｂ ６．４３
９ １３ １ ０ ５．７５
０ ５．７４８ １ｓ４２０
４．０６６ ４．０６２
２５ １ ０ ３．５６６
３．５６７ ５５ ３ ０
３．１１８ ３．１１８
１００６ ０ ０ ３．０３０
３．０２９ ５１ ０ １
２．９４０ ２．９４０
５６ ２０ １８７５
２．８７５ ２０５ ５ ０
２．５７１ ２．５７３
１５６ ４ ０ ２．５２１
２．５２１ ５７ ３ ０
２．３８７ ２．３８６
５８ ２ ０ １２０５
２．２０５ ５６ ６ ０
２．１４３ ２ｊ４３
５７ ５ ０ ２．１１４
２．１１３ ３９ １ ０
２．００８ １００９
２１０ ２ ０ １．７Ｂ２
９ １．７８２１ ２９ ５
０ １．７６６０ １．７６
５７ ２８ ８ ０ １．６
０７１ １．６０８１ ２１０
６ ０ １．５５９１ １
．５５８７ １なお１一般式Ｋ）（Ｔｊ、
＋６− 、ＦｅＹＧ ａ（１６＋ Ｘ）−ｖＯ２，にお
いて、Ｘの値を０．１〜２．０．Ｙの値を０．１〜１０
まで変動しても同様な熱処理で合成できた。1 1 0 12.86 12
．． 87 520 0 9.
091 9.100 452
20 6.42B 6.43
9 13 1 0 5.75
0 5.748 1s420
4.066 4.062
25 1 0 3.566
3.567 55 3 0
3.118 3.118
1006 0 0 3.030
3.029 51 0 1
2.940 2.940
56 20 1875
2.875 205 5 0
2.571 2.573
156 4 0 2.521
2.521 57 3 0
2.387 2.386
58 2 0 1205
2.205 56 6 0
2.143 2j43
57 5 0 2.114
2.113 39 1 0
2.008 1009
210 2 0 1.7B2
9 1.7821 29 5
0 1.7660 1.76
57 28 8 0 1.6
071 1.6081 210
6 0 1.5591 1
．． 5587 1 Note 1 General formula K) (Tj,
+6-, FeYG a(16+X)-vO2, the value of X is 0.1-2.0. Y value from 0.1 to 10
It was possible to synthesize by the same heat treatment even if the temperature was changed to .
また、Ｋの代りにＲｂ、Ｃ３を用いても同様にそれぞれ
対応した結晶体が得られた。Furthermore, even when Rb and C3 were used instead of K, corresponding crystals were similarly obtained.
実施例４゜
Ｋ １． ｏＴ ｉｔｓ Ａ ｌｚ Ｇ ａ ｏＯ６ｈ
針状単結晶の製造炭酸カリウム、二酸化チタン、酸化ア
ルミニウム、酸化ガリウムの粉末を、モル比でに２ＣＯ
，：ＴｉＯｘ ： Ａｌ２Ｏ：ｌ ： ＧａｚＯｉ
＝ ｌ ： １ ：０．４ ：０．６の割合で混合
して結晶成分とした。Example 4゜K 1. oT its A lz G aoO6h
Production of acicular single crystals Powders of potassium carbonate, titanium dioxide, aluminum oxide, and gallium oxide were mixed in a molar ratio of 2CO
, :TiOx : Al2O:l : GazOi
= l : 1 : 0.4 : 0.6 ratio was mixed to obtain a crystal component.
一方、炭酸カリウムと酸化モリブデンの粉末を、モル比
でＫ２ＣＯ２： Ｍｏｏｔ ＝ ｌ ：１．５の割合で
混合してフラックス成分とした。On the other hand, powders of potassium carbonate and molybdenum oxide were mixed at a molar ratio of K2CO2:Moot=l:1.5 to form a flux component.
結晶成分とフラックス成分をモル百分率で２０：８０の
割合で混合して出発原料とした。A starting material was prepared by mixing a crystal component and a flux component at a molar percentage of 20:80.
その出発原料１５０ｇを白金ルツボに入れ、炭化珪素発
熱体電気炉で、１３００°Ｃに１０時間保持して溶解し
、その後、１０００℃まで１時間４°Ｃ／ｈの速度で徐
冷した。徐冷後はルツボを取出して大気中で放冷した。150 g of the starting material was placed in a platinum crucible, held at 1300°C for 10 hours to melt in a silicon carbide heating element electric furnace, and then gradually cooled to 1000°C for 1 hour at a rate of 4°C/h. After slow cooling, the crucible was taken out and left to cool in the atmosphere.
該ルツボを沸とう水で処理してフラックスを溶解して結
晶を取出した。The crucible was treated with boiling water to dissolve the flux and take out the crystals.
得られた結晶体はＸ線粉末回折法で同定した結Ｔｉｅ−
ｘｏ＋６の単結晶とα−Ａ１□０３の粉末状結な単結晶
は長さ１０龍、直径１００μｍであった。The obtained crystalline material was identified by X-ray powder diffraction method.
The single crystal of xo+6 and the powdered single crystal of α-A1□03 had a length of 10 mm and a diameter of 100 μm.
なお、ＡＩに代えＦｅ、Ｃｒを用いても同様に育成でき
、また、ＫｚＯ（７）代りにＲｂｚＯ，Ｃ５ｚＯを用い
てもそれぞれ対応した結晶体が得られた。It should be noted that similar growth was possible using Fe and Cr instead of AI, and corresponding crystals were obtained when RbzO and C5zO were used instead of KzO(7).
発明の効果
本発明は、陽イオン伝導体、イオン交換体、耐熱性断熱
材料、触媒等として有用な新規化合物を安価に提供し得
られる優れた効果を有する。Effects of the Invention The present invention has the excellent effect of providing novel compounds useful as cation conductors, ion exchangers, heat-resistant heat insulating materials, catalysts, etc. at low cost.
第１図は本発明化合物の結晶構造図で、ａは全体の結晶
構造図、ｂはＴｉｅ、配位体で示すルチル構造単位、Ｃ
はＭｏｂ（Ｍ＝Ｇ ａ 、 ＡＩ 、 Ｃｒ 。
Ｆｅ）とＧａＯ２の配位体で示すβ−ガリア構造単位を
示す。
後 藤 優°−０：
娼）ｆニー”１ｌ−ｉｌ、Ｉ
・！FIG. 1 is a diagram of the crystal structure of the compound of the present invention, in which a is the overall crystal structure, b is Tie, a rutile structural unit represented by a coordinate, and C
indicates a β-gallium structural unit represented by a coordination of Mob (M=Ga, AI, Cr.Fe) and GaO2. Yu Goto°-0: prostitute) f knee”1l-il, I・!
Claims (1)
＋＿Ｘ＿）＿−＿ＹＯ＿５＿６（ただし、ＡはＫ、Ｒｂ
及びＣｓから選ばれた１種または２種以上のアルカリ金
属、ＭはＡｌ、Ｆｅ、及びＣｒから選ばれた１種または
２種以上の３価金属、Ｘ＝０．１〜２．０、Ｙ＝０．１
〜１０を表わす）で示される正方晶系のトンネル構造を
有する化合物。 ２）Ｋ＿２Ｏ、Ｒｂ＿２Ｏ及びＣｓ＿２Ｏから選ばれた
アルカリ金属酸化物あるいは加熱により該アルカリ金属
酸化物に分解される化合物と、酸化チタンあるいは加熱
により酸化チタンに分解される化合物と、酸化ガリウム
あるいは加熱により酸化ガリウムに分解される化合物と
、酸化アルミニウム、酸化鉄及び酸化クロムから選ばれ
た三価金属化合物あるいは加熱により該三価金属酸化物
に分解される化合物とを、一般式 Ａ＿ＸＴｉ＿１＿６＿−＿ＸＭ＿ＹＧａ＿（＿１＿６＿
＋＿Ｘ＿）＿−＿ＹＯ＿５＿６（ただし、Ａ、Ｍ、Ｘ、
Ｙは前記と同じものを表わす）で示される組成割合に混
合し、該混合物を１０００℃以上の温度で焼成すること
を特徴とする一般式 Ａ＿ＸＴｉ＿１＿６＿−＿ＸＭ＿ＹＧａ＿（＿１＿６＿
＋＿Ｘ＿）＿−＿ＹＯ＿５＿６（ただし、Ａ、Ｍ、Ｘ、
Ｙは前記と同じものを表わす）で示される正方晶系のト
ンネル構造を有する化合物の製造法。 ３）Ｋ＿２Ｏ、Ｒｂ＿２Ｏ及びＣｓ＿２Ｏから選ばれた
アルカリ金属酸化物あるいは加熱により該アルカリ金属
酸化物に分解される化合物と、 ＴｉＯ＿２あるいは加熱によりＴｉＯ＿２に分解される
化合物と、Ｇａ＿２Ｏ＿３あるいは加熱によりＧａ＿２
Ｏ＿３に分解される化合物と、Ａｌ＿２Ｏ＿３、Ｆｅ＿
２Ｏ＿３及びＣｒ＿２Ｏ＿３から選ばれた三価金属酸化
物あるいは加熱により該三価金属酸化物とを、一般式 （Ａ＿２Ｏ）＿ａ（ＴｉＯ＿２）＿ｂ（Ｍ＿２Ｏ＿３）
＿ｃ（Ｇａ＿２Ｏ＿３）＿ｄ （ただし、Ａ、Ｍは前記と同じ、ａ、ｂ＝ ０．１〜２．０、ｃ、ｄ＝０．１〜１．０を表わす）で
示される組成割合に混合したものを結晶原料とし、一方
ＭｏＯ＿３あるいは加熱によりＭｏＯ＿３に分解される
化合物と、Ｋ、Ｒｂ、及びＣｓから選ばれたアルカリ金
属酸化物あるいは加熱により該アルカリ金属酸化物に分
解される化合物とを、一般式Ａ＿２Ｏ・ｎ （ＭｏＯ＿３）（ただし、Ａは前記と同じ、ｎ＝１〜２
を表わす）で示される組成割合に混合したものをフラッ
クス原料とし、結晶原料とフラックス原料とをモル百分
率が３０対７０〜１０対９０の割合になるように混合し
、該混合物を１２００〜１４００℃で加熱溶融し、該溶
融体を９００〜１０００℃まで徐冷して単結晶を育成す
ることを特徴とするＡ＿ＸＴｉ＿１＿６＿−＿ＸＭ＿Ｙ
Ｇａ＿（＿１＿６＿＋＿Ｘ＿）＿−＿ＹＯ＿５＿６（た
だし、Ａ、Ｍ、Ｘ、Ｙは前記と同じものを表わす）で示
される正方晶系のトンネル構造を有する化合物の製造法
。[Claims] 1) General formula A_XTi_1_6_-_XM_YGa_(_1_6_
+_X_)_-_YO_5_6 (However, A is K, Rb
and one or more alkali metals selected from Cs, M is one or more trivalent metals selected from Al, Fe, and Cr, X = 0.1 to 2.0, Y =0.1
~10) having a tetragonal tunnel structure. 2) An alkali metal oxide selected from K_2O, Rb_2O, and Cs_2O or a compound decomposed into the alkali metal oxide by heating, titanium oxide or a compound decomposed into titanium oxide by heating, and gallium oxide or a compound decomposed into titanium oxide by heating. A compound decomposed into gallium and a trivalent metal compound selected from aluminum oxide, iron oxide, and chromium oxide or a compound decomposed into the trivalent metal oxide by heating are expressed by the general formula A_XTi_1_6_-_XM_YGa_(_1_6_
+_X_)_-_YO_5_6 (However, A, M, X,
The general formula A_XTi_1_6_-_XM_YGa_(_1_6_
+_X_)_-_YO_5_6 (However, A, M, X,
A method for producing a compound having a tetragonal tunnel structure represented by (Y represents the same as above). 3) An alkali metal oxide selected from K_2O, Rb_2O and Cs_2O or a compound decomposed into the alkali metal oxide by heating, TiO_2 or a compound decomposed into TiO_2 by heating, and Ga_2O_3 or Ga_2 by heating.
Compounds decomposed into O_3, Al_2O_3, Fe_
A trivalent metal oxide selected from 2O_3 and Cr_2O_3 or the trivalent metal oxide by heating, with the general formula (A_2O)_a(TiO_2)_b(M_2O_3)
_c(Ga_2O_3)_d (A, M are the same as above, a, b = 0.1 to 2.0, c, d = 0.1 to 1.0) were mixed at the composition ratio shown. On the other hand, MoO_3 or a compound decomposed into MoO_3 by heating, and an alkali metal oxide selected from K, Rb, and Cs or a compound decomposed into the alkali metal oxide by heating are used as crystal raw materials. Formula A_2O・n (MoO_3) (where A is the same as above, n = 1 to 2
) is used as a flux raw material, the crystal raw material and the flux raw material are mixed so that the molar percentage is 30:70 to 10:90, and the mixture is heated to 1200 to 1400 ° C. A_XTi_1_6_-_XM_Y characterized by heating and melting at 900 to 1000°C and slowly cooling the melt to grow a single crystal.
A method for producing a compound having a tetragonal tunnel structure represented by Ga_(_1_6_+_X_)_-_YO_5_6 (A, M, X, and Y represent the same as above).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12409586A JPS62283815A (en) | 1986-05-29 | 1986-05-29 | Tetragonal compound represented by axti16-xmyga16+x)-yo56 and having tunnel structure |
| US07/013,433 US4818735A (en) | 1986-02-14 | 1987-02-11 | Tetragonal system tunnel-structured compound AX(GA8MYGA(8+X)-YTI16-X0 56), and cation conductor and heat insulating material composed thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12409586A JPS62283815A (en) | 1986-05-29 | 1986-05-29 | Tetragonal compound represented by axti16-xmyga16+x)-yo56 and having tunnel structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283815A true JPS62283815A (en) | 1987-12-09 |
| JPH0242772B2 JPH0242772B2 (en) | 1990-09-26 |
Family
ID=14876799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12409586A Granted JPS62283815A (en) | 1986-02-14 | 1986-05-29 | Tetragonal compound represented by axti16-xmyga16+x)-yo56 and having tunnel structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283815A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02277823A (en) * | 1989-04-19 | 1990-11-14 | Natl Inst For Res In Inorg Mater | Production of fiber or filmy product of compound with tetragonal tunnel structure represented by axga16+xti16-xo56 |
| JPH0333219A (en) * | 1989-06-27 | 1991-02-13 | Natl Inst For Res In Inorg Mater | Production of fiber or film of barium titanogallate |
-
1986
- 1986-05-29 JP JP12409586A patent/JPS62283815A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02277823A (en) * | 1989-04-19 | 1990-11-14 | Natl Inst For Res In Inorg Mater | Production of fiber or filmy product of compound with tetragonal tunnel structure represented by axga16+xti16-xo56 |
| JPH0478735B2 (en) * | 1989-04-19 | 1992-12-14 | Kagaku Gijutsucho Mukizaishitsu Kenkyushocho | |
| JPH0333219A (en) * | 1989-06-27 | 1991-02-13 | Natl Inst For Res In Inorg Mater | Production of fiber or film of barium titanogallate |
| JPH0478736B2 (en) * | 1989-06-27 | 1992-12-14 | Kagaku Gijutsucho Mukizaishitsu Kenkyushocho |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0242772B2 (en) | 1990-09-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |