JPH0258230B2 - - Google Patents
Info
- Publication number
- JPH0258230B2 JPH0258230B2 JP61012660A JP1266086A JPH0258230B2 JP H0258230 B2 JPH0258230 B2 JP H0258230B2 JP 61012660 A JP61012660 A JP 61012660A JP 1266086 A JP1266086 A JP 1266086A JP H0258230 B2 JPH0258230 B2 JP H0258230B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- aqueous
- ammonia
- mixed
- oxalate
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000010955 niobium Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は一般式Sr1-xBaxNb2O6（ただし0.25≦
ｘ≦0.75を表わす）（以下Ｓ，Ｂ，Ｎと略記する）
で示される透光性焼結体の製造法に関する。[Detailed description of the invention] Industrial field of application The present invention is based on the general formula Sr 1-x Ba x Nb 2 O 6 (where 0.25≦
x≦0.75) (hereinafter abbreviated as S, B, N)
The present invention relates to a method for manufacturing a translucent sintered body shown in the following.
Ｓ，Ｂ，Ｎ透光性焼結体は圧電性を有すると共
に電気―光効果の特性を有するので、その特性を
利用する光シヤツター、光メモリーなどのオプト
エレクトロニツクス材料として有用なものであ
る。 S, B, N translucent sintered bodies have piezoelectricity and electro-optic effect characteristics, so they are useful as optoelectronic materials such as optical shutters and optical memories that utilize these characteristics. .
従来技術
従来のＳ，Ｂ，Ｎの焼結体の製造法としては、
その成分元素の酸化物粉末を混合し、この混合物
を仮焼した後、ホツトプレスする方法が知られて
いる。Conventional technology The conventional method for manufacturing sintered bodies of S, B, and N is as follows:
A method is known in which oxide powders of the component elements are mixed, the mixture is calcined, and then hot pressed.
しかしながら、該方法は高温で加圧しながら焼
結をしなければならないので、装置的に複雑なこ
と、複雑形状の焼結体が作りにくいこと、また大
量生産性にも欠け経済的にも不利などの多くの欠
点があつた。 However, since this method requires sintering at high temperatures and under pressure, it is complicated in terms of equipment, difficult to produce sintered bodies with complex shapes, lacks mass productivity, and is economically disadvantageous. had many shortcomings.
発明の目的
本発明は従来法における欠点を解消すべくなさ
れたもので、その目的は製造に際し不純物の混入
がなく、純度が高いものを容易に、かつ複雑な形
状のものも得られると共に多量生産に適するＳ，
Ｂ，Ｎ透光性焼結体の製造法に提供するにある。Purpose of the Invention The present invention was made in order to eliminate the drawbacks of conventional methods.The purpose of the present invention is to eliminate the contamination of impurities during production, easily obtain products of high purity, and to produce products with complex shapes as well as mass production. S suitable for,
The present invention provides a method for manufacturing a B,N translucent sintered body.
発明の構成
本発明者らは前記目的を達成すべく鋭意研究の
結果、Ｓ，Ｂ，Ｎの成分のしゆう酸塩がアルカリ
性の水溶液に全く不溶である特性を有することに
着目し、しゆう酸水溶液中でＳ，Ｂ，Ｎの成分を
混合し、この混合液にアンモニアを作用させて共
沈させると、均一でしかも高純度の微粒子粉末が
得られ、この共沈物を熱分解して得られた酸化物
粉末を酸素雰囲気中で焼結すると、透光性を有す
るＳ，Ｂ，Ｎ焼結体が得られることを知見し、こ
の知見に基いて本発明を完成した。Structure of the Invention As a result of intensive research to achieve the above object, the present inventors focused on the fact that oxalate salts of S, B, and N components have the property of being completely insoluble in alkaline aqueous solutions. When S, B, and N components are mixed in an acid aqueous solution and ammonia is applied to this mixed solution to cause coprecipitation, a homogeneous and highly pure fine particle powder is obtained, and this coprecipitate is thermally decomposed. It was discovered that a translucent S, B, N sintered body could be obtained by sintering the obtained oxide powder in an oxygen atmosphere, and the present invention was completed based on this knowledge.
本発明の要旨は、一般式Sr1-xBaxNb2O3（ただ
し、0.25≦ｘ≦0.75を表わす）で示される組成割
合のSr，Ba及びNbのしゆう酸塩水溶液の混合溶
液を作り、この混合水溶液にアンモニアを作用さ
せて沈殿物を生成させ、生成沈殿物を熱分解し成
形した後、酸素雰囲気中で焼結することを特徴と
するSr1-xBaxNb2O6（ただし、ｘは前記と同じ）
透光性焼結体の製造法にある。 The gist of the present invention is to prepare a mixed solution of an aqueous oxalate solution of Sr, Ba and Nb having a composition ratio represented by the general formula Sr 1-x Ba x Nb 2 O 3 (0.25≦x≦0.75). Sr 1-x Ba x Nb 2 O 6 is produced by treating this mixed aqueous solution with ammonia to generate a precipitate, thermally decomposing the resulting precipitate, shaping it, and then sintering it in an oxygen atmosphere . (However, x is the same as above)
A method for manufacturing a translucent sintered body.
Sr，Ba及びNbのしゆう酸塩水溶液は、例え
ば、Srイオン、Baイオンを含む水溶液とNbのし
ゆう酸溶液とを混合することによつて得られる。 The aqueous oxalate solution of Sr, Ba and Nb can be obtained, for example, by mixing an aqueous solution containing Sr ions and Ba ions and an oxalate solution of Nb.
Nbのしゆう酸溶液は例えば五塩化ニオブをし
ゆう酸水溶液に溶解したものあるいは五塩化ニオ
ブをアンモニア水で水酸化ニオブとし、これを熱
しゆう酸に溶解したものが用いられる。 The oxalic acid solution of Nb used is, for example, a solution in which niobium pentachloride is dissolved in an aqueous oxalic acid solution, or a solution in which niobium pentachloride is made into niobium hydroxide with aqueous ammonia and this is dissolved in hot oxalic acid.
また、Srイオン、Baイオンを含む水溶液とし
ては、例えばそれらの硝酸塩、塩酸塩、炭酸塩な
どの水あるいは酸に可溶な塩を水あるいは酸に溶
解させたものが使用される。 Further, as the aqueous solution containing Sr ions and Ba ions, for example, those obtained by dissolving water- or acid-soluble salts thereof such as nitrates, hydrochlorides, carbonates, etc. in water or acids are used.
しかし、この方法に限定されるものではなく、
Sr，Ba及びNbのしゆう酸塩水溶液の混合水溶液
であればよい。 However, it is not limited to this method,
Any mixed aqueous solution of oxalate aqueous solutions of Sr, Ba and Nb may be used.
このSr，Ba及びNbのしゆう酸塩混合液を室温
でアンモニアを作用させる。その方法はアンモニ
ア水を添加したりあるいはアンモニアガスを導入
することによつて行うことができる。これにより
白色沈殿物が生成する。 This oxalate mixture of Sr, Ba and Nb is treated with ammonia at room temperature. This method can be carried out by adding aqueous ammonia or introducing ammonia gas. This produces a white precipitate.
該沈殿物を800〜1000℃で熱分解する。この熱
分解は低温であることが望ましいが、低過ぎると
熱分解が不完全となり焼結体が破損し易くなり、
また高過ぎると粒子の成長が著しくなり焼結に悪
影響を及ぼすので、前記温度範囲であることが好
ましい。この熱分解により粒径約0.4μmの微粒子
が得られる。 The precipitate is pyrolyzed at 800-1000°C. It is desirable for this thermal decomposition to occur at a low temperature, but if the temperature is too low, the thermal decomposition will be incomplete and the sintered body will be easily damaged.
Furthermore, if the temperature is too high, the growth of particles will be significant, which will have an adverse effect on sintering, so it is preferable that the temperature is within the above range. This thermal decomposition yields fine particles with a particle size of approximately 0.4 μm.
この微粒子粉末を150〜1000Kg／cm2で一次成型
する。一次成型の圧力が高過ぎると成型体に歪み
が生ずるので、成型体が崩れない程度の低圧が好
ましい。従つて前記の範囲であることが好まし
い。得られた成型物をラバープレスにより
1.6ton／cm2以上の圧力で二次成型し、次いで酸素
雰囲気中で焼結する。この焼結は1150〜1400℃で
１〜100時間行う。 This fine particle powder is primarily molded at 150 to 1000 kg/cm 2 . If the primary molding pressure is too high, the molded body will be distorted, so it is preferable that the pressure be low enough to prevent the molded body from collapsing. Therefore, it is preferably within the above range. The obtained molded product is pressed using a rubber press.
Secondary molding is performed at a pressure of 1.6 ton/cm 2 or higher, and then sintered in an oxygen atmosphere. This sintering is performed at 1150-1400°C for 1-100 hours.
実施例
五塩化ニオブをアンモニア水中で水酸化物とし
て沈殿させ、得られた水酸化ニオブを熱しゆう酸
中に投入してしゆう酸ニオブ水溶液を作つた。こ
のしゆう酸ニオブ溶液中のNb濃度はNb2O5とし
て重量法で測定した結果、0.09188ｇ／c.c.であつ
た。Example Niobium pentachloride was precipitated as a hydroxide in aqueous ammonia, and the obtained niobium hydroxide was poured into hot oxalic acid to prepare an aqueous solution of niobium oxalate. The Nb concentration in this niobium oxalate solution was measured gravimetrically as Nb 2 O 5 and was found to be 0.09188 g/cc.
この溶液30c.c.をNbに対してそれぞれ1/4モル量
である1.0773ｇの硝酸ストロンチウムと1.3550ｇ
の硝酸バリウムを0.33Nの硝酸120c.c.に溶解して
作つた硝酸酸性の水溶液を混合した。 Add 30 c.c. of this solution to 1.0773 g of strontium nitrate and 1.3550 g of strontium nitrate, each having a 1/4 molar amount to Nb.
of barium nitrate was dissolved in 120 c.c. of 0.33 N nitric acid and mixed with a nitric acidic aqueous solution.
この混合液をアンモニア水中に滴下して白色沈
殿を得た。この白色沈殿を吸引ろ過し、100℃で
乾燥した後粉砕し、空気中で900℃で２時間熱分
解した。 This mixed solution was dropped into aqueous ammonia to obtain a white precipitate. This white precipitate was suction filtered, dried at 100°C, ground, and thermally decomposed in air at 900°C for 2 hours.
得られた熱分解物を500Kg／cm2の圧力で、直径
約８mm、厚さ４mmの円板上に１次成型した後、
2ton／cm2の静水圧下で二次成型した。次いでこれ
を1300℃で酸素ガスを流し２時間焼結した。得ら
れたものは透光性を示した。 The obtained thermal decomposition product was first molded onto a disk with a diameter of about 8 mm and a thickness of 4 mm at a pressure of 500 Kg/cm 2 .
Secondary molding was performed under hydrostatic pressure of 2 tons/cm 2 . Next, this was sintered at 1300°C for 2 hours by flowing oxygen gas. The obtained product showed translucency.
発明の効果
本発明の方法によると、従来法に比べて次のよ
うな優れた効果を有する。Effects of the Invention The method of the present invention has the following superior effects compared to conventional methods.
(1) しゆう酸塩水溶液からアンモニアを作用させ
て沈殿物を得、これを熱分解して原料粉末を得
るので、得られる粉末は均一でかつ高純度であ
る。(1) Ammonia is applied to an aqueous oxalate solution to obtain a precipitate, which is then thermally decomposed to obtain a raw material powder, so the resulting powder is uniform and highly pure.
(2) 得られるＳ，Ｂ，Ｎ焼結体は透光性である。(2) The resulting S, B, N sintered body is translucent.
(3) 高温、加圧による焼結でないため、装置も簡
単で、迅速かつ容易に、多量生産し得られ、従
つて安価に得られる。(3) Since sintering is not performed at high temperature and pressure, the equipment is simple, and mass production can be done quickly and easily, and therefore, it can be obtained at low cost.
Claims (1)
0.75）で示される組成割合のSr，Ba及びNbのし
ゆう酸塩水溶液の混合溶液を作り、この混合水溶
液にアンモニアを作用させて沈殿物を生成させ、
生成沈殿物を熱分解し、成形した後、酸素雰囲気
中で焼結することを特徴とするSr1-xBaxNb2O6
（ただしＸは前記と同じ）透光性焼結体の製造法。1 General formula Sr 1-x Ba x Nb 2 O 6 (0.25≦x≦
0.75) A mixed solution of an aqueous oxalate solution of Sr, Ba and Nb is prepared, and ammonia is applied to this mixed aqueous solution to form a precipitate.
Sr 1-x Ba x Nb 2 O 6 characterized by thermally decomposing the generated precipitate, shaping it, and then sintering it in an oxygen atmosphere.
(However, X is the same as above) A method for manufacturing a translucent sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61012660A JPS62171957A (en) | 1986-01-23 | 1986-01-23 | Manufacture of sr1-xbaxnb206 light transmissive sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61012660A JPS62171957A (en) | 1986-01-23 | 1986-01-23 | Manufacture of sr1-xbaxnb206 light transmissive sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62171957A JPS62171957A (en) | 1987-07-28 |
| JPH0258230B2 true JPH0258230B2 (en) | 1990-12-07 |
Family
ID=11811516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61012660A Granted JPS62171957A (en) | 1986-01-23 | 1986-01-23 | Manufacture of sr1-xbaxnb206 light transmissive sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62171957A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0294991A3 (en) * | 1987-06-10 | 1989-08-16 | Nippon Steel Corporation | Readily sinterable powder of perovskite type oxide containing group va element and laminated element obtained therefrom |
| WO2007139060A1 (en) | 2006-05-31 | 2007-12-06 | Murata Manufacturing Co., Ltd. | Translucent ceramic and electrooptical part |
| JP6249004B2 (en) * | 2015-10-06 | 2017-12-20 | Tdk株式会社 | Dielectric composition and electronic component |
-
1986
- 1986-01-23 JP JP61012660A patent/JPS62171957A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62171957A (en) | 1987-07-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |