JPH0262496B2 - - Google Patents
Info
- Publication number
- JPH0262496B2 JPH0262496B2 JP61226191A JP22619186A JPH0262496B2 JP H0262496 B2 JPH0262496 B2 JP H0262496B2 JP 61226191 A JP61226191 A JP 61226191A JP 22619186 A JP22619186 A JP 22619186A JP H0262496 B2 JPH0262496 B2 JP H0262496B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- perovskite
- solid solution
- composite oxide
- oxide solid
- 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
- 239000006104 solid solution Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003754 zirconium Chemical class 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000000919 ceramic Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 12
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 11
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 11
- 239000002609 medium Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000003746 solid phase reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- GDEBSAWXIHEMNF-UHFFFAOYSA-O cupferron Chemical compound [NH4+].O=NN([O-])C1=CC=CC=C1 GDEBSAWXIHEMNF-UHFFFAOYSA-O 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- XOYUVEPYBYHIFZ-UHFFFAOYSA-L diperchloryloxylead Chemical compound [Pb+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O XOYUVEPYBYHIFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- VJPLIHZPOJDHLB-UHFFFAOYSA-N lead titanium Chemical compound [Ti].[Pb] VJPLIHZPOJDHLB-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ペロブスカイト型鉛含有複合酸化物
固溶体の製造方法に関するものである。
The present invention relates to a method for producing a perovskite-type lead-containing complex oxide solid solution.
ペロブスカイト型結晶構造を有するチタン酸
鉛、ジルコニウム酸鉛及びチタン酸ジルコニウム
酸鉛は、誘電体セラミツクス、圧電体セラミツク
ス、焦電体セラミツクス、抵抗体セラミツクス、
半導体セラミツクス等の分野に広く使用されてい
る。
このような鉛含有複合酸化物固溶体を合成する
最も一般的な製造方法は、酸化鉛、二酸化チタン
及び二酸化ジルコニウム成分を、高温で固相反応
させる、いわゆる酸化物法である。
しかしながら、このような固相反応によつて得
られる生成物は、Ｘ線回折によれば、組成的に極
めて不均質であるという欠点を有している。
この為に、固相反応で得られる複合酸化物固溶
体においては、この生成物は粉砕し、鉛成分の調
整をしながら再度焼成するという複雑で費用のか
かる操作を反復しなければならない欠点がある。
特に、鉛含有複合酸化物固溶体の場合、鉛成分
の高温における蒸発は激しく、いまだに相平衡図
のモポトロピクバウンダリにおける相図は完全に
定まつてない状態である。
更に、この固相反応で得られた複合酸化物固溶
体は、高温での熱覆歴をうけていることに関連し
て、粒経が粗大で、他の原料や副原料との均一混
和性に欠け、反応性にも劣るという欠点を有して
いる。
そこで、上記のような固相反応における欠点を
改善する為に、溶液法でチタン酸ジルコニウム酸
鉛を製造することが知られている。
例えば、1965年、J.Cana.Ceramic.Soc.、
V.34、P103のV.M.McNamaraによる報告に記載
されている通り、鉛、ジルコニウム、チタンの硝
酸溶液を混合し、硝酸アンモニア水溶液の上にス
プレーすることによつて、チタン酸ジルコニウム
酸鉛の共沈物を作り、それをもつて650℃で焼成
し、チタン酸ジルコニウム酸鉛を得ている。
又、1980年、Ceramic Bulletin、V.59、No.4
のS.Venkataramaniによる研究結果では、基本
的には固相反応を用いながら、反応成分の一つで
あるZr02を液相法で作り、それを用いることによ
つて500℃にてチタン酸ジルコニウム酸鉛を得て
いる。
又、1984年、Communication of American
Ceramic Society、Ｃ−２の掛川による報告で
は、塩化チタンと塩化ジルコニウム水溶液の混合
液にCupferronを添加し、そこで得られた沈澱物
を900℃で焼成し、TiとZrとの混合物を作り、こ
れとPbOとを1100℃で固相反応させ、チタン酸ジ
ルコニウム酸鉛の粉末を得ている。
又、1984年、Ferroelectrics、V.54、P171の
Pedroduramによると、チタンとジルコニウムの
テトラブトオキサイド混合液をPbOと混合するこ
とによつて、非晶質共沈物を作り、それを750℃
に焼成し、チタン酸ジルコニウム酸鉛を得てい
る。
又、1986年、窯業協会誌94(6)545ページの山村
によると、鉛、ジルコニウム及びチタンの硝酸塩
水溶液を出発源として、これにシユウ酸エタノー
ルの混合液を反応させ、これから得られた沈澱物
を800〜1100℃で熱分解させ、チタン酸ジルコニ
ウム酸鉛を得ている。
しかしながら、これらを考察すると、シユウ酸
塩法を除いた諸方法は、基本的に固相法と変わり
なく、ただ反応温度を下げる為の出発成分の一部
分に易反応性のものを使つていることに特徴があ
るにすぎず、これらの方法では固相反応で問題に
される点全べてを解決できない。
一方、シユウ酸塩法も、結果的には、高温によ
る熱分解の工程を必要としている欠点がある。
Lead titanate, lead zirconate and lead zirconate titanate having a perovskite crystal structure can be used for dielectric ceramics, piezoelectric ceramics, pyroelectric ceramics, resistor ceramics,
Widely used in fields such as semiconductor ceramics. The most common manufacturing method for synthesizing such a lead-containing composite oxide solid solution is the so-called oxide method, in which lead oxide, titanium dioxide, and zirconium dioxide components are subjected to a solid phase reaction at a high temperature. However, the product obtained by such a solid-phase reaction has the disadvantage of being highly heterogeneous compositionally according to X-ray diffraction. For this reason, the complex oxide solid solution obtained by solid phase reaction has the disadvantage that the product must be crushed and fired again while adjusting the lead content, which is a complicated and expensive operation. . In particular, in the case of a lead-containing composite oxide solid solution, the lead component evaporates rapidly at high temperatures, and the phase diagram at the mopotropic boundary of the phase diagram is still not completely determined. Furthermore, the composite oxide solid solution obtained by this solid-phase reaction has a coarse grain size due to the fact that it has been subjected to a thermal cycle at high temperatures, making it difficult to mix uniformly with other raw materials and auxiliary raw materials. It has the drawbacks of poor reactivity and poor reactivity. Therefore, in order to improve the above-mentioned drawbacks in the solid phase reaction, it is known to produce lead zirconate titanate by a solution method. For example, in 1965, J.Cana.Ceramic.Soc.
Co-precipitation of lead zirconate titanate by mixing a nitric acid solution of lead, zirconium and titanium and spraying it onto an aqueous ammonium nitrate solution as described in the report by VM McNamara in V.34, p103. This is then fired at 650℃ to obtain lead zirconate titanate. Also, 1980, Ceramic Bulletin, V.59, No.4
According to research results by S.Venkataramani, basically using a solid phase reaction, one of the reaction components, Zr0 2 , was produced by a liquid phase method, and by using it, zirconium titanate was produced at 500℃. Obtaining acid lead. Also, 1984, Communication of American
In a report by Kakegawa of Ceramic Society, C-2, Cupferron was added to a mixed solution of titanium chloride and zirconium chloride, and the resulting precipitate was calcined at 900°C to create a mixture of Ti and Zr. and PbO are subjected to a solid phase reaction at 1100°C to obtain lead zirconate titanate powder. Also, 1984, Ferroelectrics, V.54, P171
According to Pedroduram, an amorphous coprecipitate was created by mixing a titanium and zirconium tetrabutoxide mixture with PbO, which was heated to 750°C.
lead zirconate titanate. Furthermore, in 1986, according to Yamamura in Ceramics Association Journal 94(6), page 545, an aqueous solution of nitrates of lead, zirconium, and titanium was used as a starting source, and a mixture of oxalic acid and ethanol was reacted with it, and the resulting precipitate was Lead zirconate titanate is obtained by thermally decomposing it at 800-1100℃. However, if we consider these, the methods other than the oxalate method are basically the same as the solid phase method, only that they use easily reactive materials as part of the starting components to lower the reaction temperature. However, these methods cannot solve all the problems encountered in solid-phase reactions. On the other hand, the oxalate method also has the drawback of requiring a thermal decomposition process at high temperatures.
本発明者は、例えば三塩化チタン又は四塩化チ
タン等の水溶性チタン塩、例えばオキシ塩化ジル
コニウム、塩化ジルコニウム、オキシ硝酸ジルコ
ニウム又は硫酸ジルコニウム等の水溶性ジルコニ
ウム塩及び例えば硝酸鉛又は過塩素酸鉛等の水溶
性鉛塩をアルカリ性水溶液体中に分散させて攪拌
または静置下に水熱反応させると、徴細な粉経
で、比較的大きい比表面積を有する微細なペロブ
スカイト型結晶構造を有する鉛含有複合酸化物固
溶体が得られることを見出だし、本発明を成し遂
げたのである。
尚、水溶性鉛塩、水溶性チタン塩及び水溶性ジ
ルコニウム塩を、アルカリ性水溶性溶液媒体中に
混合させ、攪拌または静置下に水熱反応（例えば
約50〜300℃のような比較的低い温度での反応。
但し、50〜100℃の温度では常圧下で、100〜300
℃の温度では自生圧力下）させるペロブスカイト
型チタンジルコニウム酸鉛の製造に際して、アル
カリ性水溶液媒体として約１〜18NのNaOH又は
KOHを用いることが望ましい。
特に、アルカリ性水溶液媒体として約５〜15N
のKOH又はNaOHを用いた場合には、ペロブス
カイト型構造への結晶度化は高く、しかも粉化性
に優れたものが得られ、セラミツクスへの焼結用
原料として特に有用な鉛含有複合酸化物固溶体が
得られる。
尚、約１〜18NのKOH又はNaOHが発揮する
役割の重要性は、第１図に示す鉛含有複合酸化物
固溶体のＸ線回折像を参照することによつて理解
できる。
この第１図において、Ａは、出発原料混合物、
即ち四塩化チタン、オキシ塩化ジルコニウム及び
酸化鉛を純水の媒体に混合し、水熱反応させたと
きの生成物のＸ線回折像を表わし、Ｂは、上記原
料をKOH2N水溶液中で、Ｃは、KOH4N水溶液
媒中で、Ｄは、KOH6N水溶液媒中、Ｅは、
KOH8N水溶液媒体中で、Ｆは、KOH10N水溶
液媒体中で、Ｇは、KON15N水溶液媒中でそれ
ぞれ200℃、24時間反応させた結果得られた反応
生成物のＸ線回折像を示すものであり、Ｂ〜Ｇは
実施例10〜15に対応するものである。
これらのＸ線回折像を参照すると、純水を媒体
として使用した場合は、チタン酸ジコルニウム酸
鉛化合物は生成されず、NaOH又はKOHの水溶
液を媒体として使用することによつて、反応速度
はNaOH及びKON水溶液の媒体濃度によつて変
るが、いずれの場合ともチタン酸ジルコニウム酸
鉛固溶体特有のＸ線回折ピークが得られ、そし
て、NaOH又はKOHの水溶液の媒体濃度が6Nを
越えると、ペロブスカイト型チタン酸ジルコニウ
ム酸鉛複合酸化物固溶体特有のＸ線回折ピークが
完全な形で得られていることが理解できる。
又、本発明においてチタン酸鉛とジルコニウム
酸鉛の固溶範囲が全固溶範囲において生成可能で
あることの重要性は、第２図のＸ線回折像を参照
することにより明白となる。
すなわち、四塩化チタン水溶液、オキシ塩化ジ
ルコニウム水溶液及び硝酸鉛を用いて、出発原料
混合比をPb（Zr0.1Ti0.9）O3からPb（Zr0.9Ti0.1）O3
までにジルコニウムとチタンのモル比を0.1モル
ごとに変え、10N、KOH水溶液媒体中で200℃、
24時間反応させて得られた反応生成物のＸ線回折
像を第２図に示す。
尚、第２図中、Ａは、出発組成比をPb（Zr0.1
Ti0.9）O3とした場合、Ｂは出発組成比をPb（Zr0.2
Ti0.6）O3とした場合、Ｃは、出発組成比をPb
（Zr0.3Ti0.7）O3とした場合、Ｄは、、出発組成比
をPb（Zr0.4Ti0.6）O3とした場合は、Ｅは、出発組
成比をPb（Zr0.5Ti0.5）O3とした場合、Ｆは、出発
組成比をPb（Zr0.6Ti0.4）O3とした場合、Ｇは、出
発組成比をPb（Zr0.7Ti0.3）O3とした場合、Ｈは、
出発組成比をPb（Zr0.8Ti0.2）O3とした場合、Ｉ
は、出発組成比をPb（Zr0.9Ti0.1）O3とした場合の
反応生成物のＸ線回折像を示すものである。
これらのＸ線回折像を参照すると、いずれの場
合とも固相反応で研究されているジルコニウムと
チタンの全固溶体実験結果とも非常に良く一致
し、上記原料を出発原料とし、出発組成比を変え
てKOH水溶液媒体中において水熱反応させるこ
とによつて、チタン酸ジルコニウム酸鉛のペロブ
スカイト型鉛含有複合酸化物固溶体が、その全固
溶範囲において、その生成が顕著となつている事
実が理解される。
本発明によるペロブスカイト型複合酸化物固溶
体は、第１図及び第２図からも明らかなように、
結晶化度が大きく、しかも結晶粒子間の歪が少な
いという利点を有している。この特徴の故に、こ
の複合金属酸化物固溶体は、焼成等の熱覆歴を受
けた場合にも、凝結することが少なく、粉化性に
顕著に優れているのであつて、この事実は後述す
る例を参照することにより直ちに明白となろう。
しかも、本発明による鉛含有複合酸化物固溶体
の走査形電子顕微鏡写真によると、本発明による
鉛含有複合酸化物の固溶体は、前述したペロブス
カイト型微結晶を有すると共に、粒経が0.1ミク
ロン以下であり、更にBET比表面積が10m2／ｇ
以上、特に20m2／ｇ以上であるという特徴を有す
る。
尚、公知方法では、粒経が１ミクロンよりも小
さいペロブスカイト型酸化物固溶体を得ることは
到底困難であり、また非晶質のものや前駆体の場
合には非較的大きい比表面積を有するとしても、
ペロブスカイト型の結晶に転化すると、その比表
面積は５m2／ｇよりもかなり小さい値となる。
これに対して、本発明による鉛含有複合酸化物
固溶体は、結晶でありながら、10m2／ｇ以上、特
に20m2／ｇ以上の大きな比表面積有する。
そして、本発明による鉛含有複合酸化物固溶体
は、上述した特性を有することにより、セラミツ
クスの製造に用いたとき、予想外の顕著な作用効
果を示す。
先ず、この複合酸化物固溶体は、１次粒経が微
細で、しかも表面活性が大きい為、１次粒子が柔
らかく、凝集した２次粒子の形で存在し、その為
プレス成形、押出成形、テープキヤスト、ホツト
プレス等の手段で、容易に所望形状のセラミツク
ス構造体を成形できる。
しかも、この鉛含有複合酸化物は、１次粒経が
微細で、表面活性が大であり、しかもペロブスカ
イト型結晶構造となつている為、約900〜1000℃
のような低温で焼成可能であり、このような低温
の焼結によつても、緻密で、機械的強度に優れた
ペロブスカイト型セラミツクス体を形成できる。
又、本発明による鉛含有複合酸化物固溶体から
形成されるセラミツクス体は、理論密度の95％〜
98％にも達する密度を有する。
更に、本発明による鉛含有複合酸化物固溶体は
上述した優れた焼結特性を有し、低温で焼結可能
であることにも関連して、焼結時の粒成長が著し
く抑制され、例えば粒成長抑制剤の配合なしに
も、諸特性に優れたペロブスカイト製セラミツク
ス体を得ることが出来る。
又、本発明による鉛含有複合酸化物固溶体は、
ペロブスカイト型結晶でありながら、粒経が微細
で、表面活性が大であるという性質を有して、セ
ラミツクス以外の用途、例えば排ガス浄化用触
媒、電極触媒等の分野にも有利に使用し得る。
実施例 １〜16
ペロブスカイト型チタン酸ジルコニウム酸鉛複
合酸化物固溶体の製造方法は下記の方法に従う。
尚、製造条件としては下記に示した範囲内で任
意に選ぶことが出来る。
反応生成物のスラリ濃度：10〜500g／
反応温度：50〜300℃
反応時間：10分〜144時間
撹拌速度：200rpm以下
ペロブスカイト型鉛含有複合酸化物の具体的製
造方法としては、表１に示すペロブスカイト型固
溶体成分のモル割合に従つて調整された。
そして、各水溶性金属塩水溶液を容積比として
10倍のKOH又はNaOH水溶液媒体と混合し、マ
ントルヒータ付ステンレス製オートクレーブ（内
容積３）に上記水溶性金属塩水溶液とKOH又
はNaOH水溶液の混合液を注入したのち、200℃
に加熱し、１日水熱処理して水熱反応を施し、ろ
過性に優れたペロブスカイト型結晶の鉛含有複合
酸化物固溶体の反応生成物スラリー16種類を調整
した。
次いで、ここに得た生成物ヒスラーをろ過した
のち、イオン交換水を用いて数回洗い、最後にケ
ーキとして回収した後、100℃の温度において２
時間以上乾燥し、それぞれのペロブスカイト型微
結晶の鉛含有複合酸化物の微粉末16種類を得た。
ここに、それぞれ得たペロブスカイト型鉛含有
酸化物固溶体粉末について、結晶系及びBET比
表面積を測定したので、その結果を表１に併せ表
示した。
The inventor has discovered that water-soluble titanium salts such as titanium trichloride or titanium tetrachloride, water-soluble zirconium salts such as zirconium oxychloride, zirconium chloride, zirconium oxynitrate or zirconium sulfate, and water-soluble zirconium salts such as lead nitrate or lead perchlorate, etc. When a water-soluble lead salt is dispersed in an alkaline aqueous solution and subjected to a hydrothermal reaction while stirring or standing still, a lead-containing compound with a fine perovskite-type crystal structure with a fine powder diameter and a relatively large specific surface area is produced. They discovered that a complex oxide solid solution could be obtained and accomplished the present invention. In addition, water-soluble lead salt, water-soluble titanium salt, and water-soluble zirconium salt are mixed in an alkaline aqueous solution medium, and a hydrothermal reaction (for example, at a relatively low temperature of about 50 to 300°C) is performed while stirring or standing still. Reaction at temperature.
However, at a temperature of 50 to 100℃ and under normal pressure,
In the production of perovskite-type lead titanium zirconate (under autogenous pressure at temperatures of
Preferably, KOH is used. In particular, about 5 to 15N as an alkaline aqueous medium
When KOH or NaOH is used, a product with high crystallinity to a perovskite structure and excellent powderability is obtained, making it a lead-containing composite oxide that is particularly useful as a raw material for sintering ceramics. A solid solution is obtained. The importance of the role played by about 1-18N KOH or NaOH can be understood by referring to the X-ray diffraction image of the lead-containing complex oxide solid solution shown in FIG. In this FIG. 1, A is a starting material mixture;
That is, titanium tetrachloride, zirconium oxychloride, and lead oxide are mixed in a medium of pure water and subjected to a hydrothermal reaction, and B represents the X-ray diffraction image of the product. , in KOH4N aqueous medium, D is in KOH6N aqueous medium, E is,
In a KOH8N aqueous solution medium, F is a KOH10N aqueous solution medium, and G is an X-ray diffraction image of a reaction product obtained as a result of reaction at 200°C for 24 hours in a KON15N aqueous solution medium, respectively, B to G correspond to Examples 10 to 15. Referring to these X-ray diffraction images, when pure water is used as a medium, lead titanate dicolinate compound is not produced, and when an aqueous solution of NaOH or KOH is used as a medium, the reaction rate is that of NaOH. Although it varies depending on the medium concentration of NaOH or KON aqueous solution, in both cases, an X-ray diffraction peak peculiar to lead zirconate titanate solid solution is obtained, and when the medium concentration of NaOH or KOH aqueous solution exceeds 6N, perovskite type It can be seen that the X-ray diffraction peak peculiar to the lead zirconate titanate composite oxide solid solution was obtained in a complete form. Further, the importance of being able to produce lead titanate and lead zirconate in the entire solid solution range in the present invention becomes clear by referring to the X-ray diffraction image shown in FIG. That is, using a titanium tetrachloride aqueous solution, a zirconium oxychloride aqueous solution, and lead nitrate, the starting raw material mixture ratio was changed from Pb(Zr 0.1 Ti 0.9 )O 3 to Pb(Zr 0.9 Ti 0.1 )O 3
The molar ratio of zirconium and titanium was changed in steps of 0.1 mol, and the mixture was heated at 200 °C in a 10 N, KOH aqueous medium.
FIG. 2 shows an X-ray diffraction image of the reaction product obtained after 24 hours of reaction. In Fig. 2, A indicates the starting composition ratio of Pb (Zr 0.1
When Ti 0.9 ) O 3 is used, B has a starting composition ratio of Pb(Zr 0.2
When Ti 0.6 ) O 3 , C has a starting composition ratio of Pb
(Zr 0.3 Ti 0.7 ) O 3 , then D is, and the starting composition ratio is Pb (Zr 0.4 Ti 0.6 ) O 3 , E is the starting composition ratio, Pb (Zr 0.5 Ti 0.5 ) O 3 In this case, F is the starting composition ratio of Pb(Zr 0.6 Ti 0.4 )O 3 , G is the starting composition ratio of Pb(Zr 0.7 Ti 0.3 )O 3 , and H is
When the starting composition ratio is Pb(Zr 0.8 Ti 0.2 ) O 3 , I
shows an X-ray diffraction image of the reaction product when the starting composition ratio is Pb(Zr 0.9 Ti 0.1 )O 3 . Referring to these X-ray diffraction images, in each case, they agree very well with the experimental results of all solid solutions of zirconium and titanium, which have been studied in solid phase reactions. It is understood that the formation of a perovskite-type lead-containing complex oxide solid solution of lead zirconate titanate is remarkable in the entire solid solution range by a hydrothermal reaction in a KOH aqueous solution medium. . As is clear from FIGS. 1 and 2, the perovskite-type composite oxide solid solution according to the present invention has the following properties:
It has the advantage of high crystallinity and little distortion between crystal grains. Because of this characteristic, this composite metal oxide solid solution is less likely to condense even when subjected to a thermal history such as sintering, and has excellent powdering properties.This fact will be discussed later. It will become immediately clear by reference to an example. Moreover, according to a scanning electron micrograph of the lead-containing composite oxide solid solution according to the present invention, the lead-containing composite oxide solid solution according to the present invention has the above-mentioned perovskite-type microcrystals and has a grain size of 0.1 micron or less. , and the BET specific surface area is 10m 2 /g.
As mentioned above, it is particularly characterized in that it is 20 m 2 /g or more. In addition, with known methods, it is extremely difficult to obtain a perovskite-type oxide solid solution with a grain size of less than 1 micron, and in the case of amorphous materials or precursors, they have a relatively large specific surface area. too,
When converted into perovskite-type crystals, the specific surface area becomes considerably smaller than 5 m 2 /g. In contrast, the lead-containing composite oxide solid solution according to the present invention has a large specific surface area of 10 m 2 /g or more, particularly 20 m 2 /g or more, although it is a crystal. Since the lead-containing composite oxide solid solution according to the present invention has the above-mentioned properties, it exhibits unexpectedly significant effects when used in the production of ceramics. First of all, this composite oxide solid solution has a fine primary particle size and high surface activity, so the primary particles are soft and exist in the form of aggregated secondary particles. A ceramic structure having a desired shape can be easily formed by casting, hot pressing, or the like. Moreover, this lead-containing composite oxide has a fine primary grain size, high surface activity, and has a perovskite crystal structure, so it can be heated to temperatures of approximately 900 to 1000℃.
It is possible to sinter at such a low temperature, and even by sintering at such a low temperature, a perovskite ceramic body that is dense and has excellent mechanical strength can be formed. Furthermore, the ceramic body formed from the lead-containing composite oxide solid solution according to the present invention has a theoretical density of 95% to
It has a density of up to 98%. Furthermore, the lead-containing composite oxide solid solution according to the present invention has the above-mentioned excellent sintering properties and can be sintered at low temperatures, so grain growth during sintering is significantly suppressed, such as grain growth. A perovskite ceramic body with excellent properties can be obtained without adding a growth inhibitor. Further, the lead-containing composite oxide solid solution according to the present invention is
Although it is a perovskite type crystal, it has the properties of fine grain size and high surface activity, and can be advantageously used in fields other than ceramics, such as exhaust gas purification catalysts and electrode catalysts. Examples 1 to 16 A perovskite-type lead zirconate titanate composite oxide solid solution was produced according to the following method. Incidentally, the manufacturing conditions can be arbitrarily selected within the range shown below. Slurry concentration of reaction product: 10 to 500 g / Reaction temperature: 50 to 300°C Reaction time: 10 minutes to 144 hours Stirring speed: 200 rpm or less The specific method for producing the perovskite-type lead-containing composite oxide is shown in Table 1. It was adjusted according to the molar proportion of perovskite type solid solution components. Then, each water-soluble metal salt aqueous solution is expressed as a volume ratio.
After mixing with 10 times the amount of KOH or NaOH aqueous solution medium and injecting the mixture of the above water-soluble metal salt aqueous solution and KOH or NaOH aqueous solution into a stainless steel autoclave (inner volume 3) equipped with a mantle heater, the mixture was heated to 200℃.
1 day of hydrothermal treatment and hydrothermal reaction to prepare 16 kinds of reaction product slurries of lead-containing complex oxide solid solutions of perovskite-type crystals with excellent filterability. The product Hissler thus obtained was then filtered, washed several times with ion-exchanged water, and finally collected as a cake, which was then washed at a temperature of 100°C for 2 hours.
After drying for more than an hour, 16 types of fine powders of perovskite-type microcrystalline lead-containing composite oxides were obtained. The crystal system and BET specific surface area of each of the obtained perovskite-type lead-containing oxide solid solution powders were measured, and the results are also shown in Table 1.
【表】
さらに、ここに得られたペロブスカイト型鉛含
有複合酸化物固溶体粉末の中から５種類を選び、
それぞれの粉末を1ton／cm2で円板状（10mmφ×１
mm）に加圧成形した後、950℃で１時間焼成した。
そして、この焼結体の密度、ビツカース硬度
（荷重500ｇ）を側定すると共に、この焼結体の両
面に電極を焼付け、誘電特性を調べたので、これ
らの結果を表２に示す。[Table] Furthermore, five types were selected from the perovskite-type lead-containing composite oxide solid solution powders obtained here.
Powder each powder at 1 ton/cm 2 into a disk shape (10 mmφ x 1
mm) and then baked at 950°C for 1 hour. Then, the density and Vickers hardness (load of 500 g) of this sintered body were determined, electrodes were baked on both sides of this sintered body, and the dielectric properties were investigated. The results are shown in Table 2.
【表】
この表から明らかなように、950℃という通常
の概念では低温である温度において、95％以上の
焼結度が得られていることが判る。このことは、
本発明によつて得た微粉末が焼結性に優れている
ことを示している。
又、ビツカース硬度からのデータから判るよう
に、本発明によつて得た微粉末を焼成した焼結体
は物理的安定性が高いものである。
さらには、誘電特性のデータから判るように、
クリテイカルな組成における誘電率の増加は大き
く、本発明によつて得た微粉末は誘電材料又は圧
電材料として好適なことが窺える。[Table] As is clear from this table, it can be seen that a degree of sintering of 95% or more is obtained at a temperature of 950°C, which is a low temperature according to the usual concept. This means that
This shows that the fine powder obtained by the present invention has excellent sinterability. Furthermore, as can be seen from the data on the Vickers hardness, the sintered body obtained by firing the fine powder obtained according to the present invention has high physical stability. Furthermore, as can be seen from the dielectric property data,
The increase in dielectric constant in critical compositions is large, and it can be seen that the fine powder obtained by the present invention is suitable as a dielectric material or a piezoelectric material.
第１図及び第２図は、Ｘ線回折像を示すもので
ある。
FIGS. 1 and 2 show X-ray diffraction images.
Claims (1)
コニウム塩を、アルカリ性水溶液媒体中で水熱反
応させることを特徴とするペロブスカイト型鉛含
有複合酸化物固溶体の製造方法。 ２ 特許請求の範囲第１項記載のペロブスカイト
型鉛含有複合酸化物固溶体の製造方法において、
アルカリ性水溶液媒体は、NaOH又はKOHの少
なくとも一つを約１〜18Nの濃度で含むもの。 ３ 特許請求の範囲第１項記載のペロブスカイト
型鉛含有複合酸化物固溶体の製造方法において、
水熱反応は、約100〜300℃の温度で、かつ、自生
圧力下で行なわれるもの。 ４ 特許請求の範囲第１項記載のペロブスカイト
型鉛含有複合酸化物固溶体の製造方法において、
水熱反応は、約50〜100℃の温度で、かつ、常圧
下で行なわれるもの。 ５ 特許請求の範囲第１項記載のペロブスカイト
型鉛含有複合酸化物固溶体の製造方法において、
水溶性鉛塩、水溶性チタン塩及び水溶性ジルコニ
ウム塩を、実質上Pb（ZrxTi1-x）O3（但し０＜ｘ
＜１）のモル比となるよう反応させるもの。[Scope of Claims] 1. A method for producing a perovskite-type lead-containing composite oxide solid solution, which comprises subjecting a water-soluble lead salt, a water-soluble titanium salt, and a water-soluble zirconium salt to a hydrothermal reaction in an alkaline aqueous medium. 2. In the method for producing a perovskite-type lead-containing composite oxide solid solution according to claim 1,
The alkaline aqueous medium includes at least one of NaOH or KOH at a concentration of about 1-18N. 3. In the method for producing a perovskite-type lead-containing composite oxide solid solution according to claim 1,
Hydrothermal reactions occur at temperatures of approximately 100 to 300°C and under autogenous pressure. 4. In the method for producing a perovskite-type lead-containing composite oxide solid solution according to claim 1,
Hydrothermal reactions are carried out at temperatures of approximately 50 to 100°C and under normal pressure. 5. In the method for producing a perovskite-type lead-containing composite oxide solid solution according to claim 1,
Water-soluble lead salts, water-soluble titanium salts, and water-soluble zirconium salts are substantially Pb(Zr x Ti 1-x ) O 3 (where 0<x
Something that is reacted so that the molar ratio is <1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226191A JPS6385014A (en) | 1986-09-26 | 1986-09-26 | Production of lead-containing compound oxide solid solution of perovskite type |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226191A JPS6385014A (en) | 1986-09-26 | 1986-09-26 | Production of lead-containing compound oxide solid solution of perovskite type |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6385014A JPS6385014A (en) | 1988-04-15 |
| JPH0262496B2 true JPH0262496B2 (en) | 1990-12-25 |
Family
ID=16841314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61226191A Granted JPS6385014A (en) | 1986-09-26 | 1986-09-26 | Production of lead-containing compound oxide solid solution of perovskite type |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6385014A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3727396A1 (en) * | 1987-08-17 | 1989-03-02 | Philips Patentverwaltung | METHOD FOR PRODUCING CERAMIC POWDERS WITH PEROWSKIT STRUCTURE |
| CA2005036A1 (en) * | 1988-12-08 | 1990-06-08 | Scott L. Swartz | Process for producing highly crystalline and homogeneous sub-micron doped and undoped piezoelectric ceramic powders with controlled stoichiometry and particle size |
| US5453262A (en) * | 1988-12-09 | 1995-09-26 | Battelle Memorial Institute | Continuous process for production of ceramic powders with controlled morphology |
| US5204031A (en) * | 1989-09-30 | 1993-04-20 | Osaka Titanium Co., Ltd. | Powder of oxide for dielectric ceramics and a process for producing dielectric ceramics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5969429A (en) * | 1982-10-07 | 1984-04-19 | Nippon Mining Co Ltd | Manufacture of ultrafine powder of zro2 |
-
1986
- 1986-09-26 JP JP61226191A patent/JPS6385014A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5969429A (en) * | 1982-10-07 | 1984-04-19 | Nippon Mining Co Ltd | Manufacture of ultrafine powder of zro2 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6385014A (en) | 1988-04-15 |
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