JPH0419165B2 - - Google Patents
Info
- Publication number
- JPH0419165B2 JPH0419165B2 JP62139998A JP13999887A JPH0419165B2 JP H0419165 B2 JPH0419165 B2 JP H0419165B2 JP 62139998 A JP62139998 A JP 62139998A JP 13999887 A JP13999887 A JP 13999887A JP H0419165 B2 JPH0419165 B2 JP H0419165B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- oxalic acid
- coprecipitant
- ceramic raw
- weight
- 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 116
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 46
- 239000000919 ceramic Substances 0.000 claims description 39
- 235000006408 oxalic acid Nutrition 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 150000002736 metal compounds Chemical class 0.000 claims description 22
- 238000000975 co-precipitation Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052788 barium Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052727 yttrium Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- -1 sensors Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003891 oxalate salts Chemical class 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- RYCFRVNAZOREPC-UHFFFAOYSA-N 1,1,2-triphenylguanidine Chemical compound C=1C=CC=CC=1N(C=1C=CC=CC=1)C(N)=NC1=CC=CC=C1 RYCFRVNAZOREPC-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical group OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MPYOKHFSBKUKPQ-UHFFFAOYSA-N n'-phenylbenzenecarboximidamide Chemical compound C=1C=CC=CC=1C(N)=NC1=CC=CC=C1 MPYOKHFSBKUKPQ-UHFFFAOYSA-N 0.000 description 1
- CLWIJUQLAFJNOF-UHFFFAOYSA-N n,n'-diphenylethanimidamide Chemical compound C=1C=CC=CC=1N=C(C)NC1=CC=CC=C1 CLWIJUQLAFJNOF-UHFFFAOYSA-N 0.000 description 1
- ZQUVDXMUKIVNOW-UHFFFAOYSA-N n,n'-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1NC=NC1=CC=CC=C1 ZQUVDXMUKIVNOW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
［産業上の利用分野］
この発明は、広い分野で利用されている種々の
セラミツクスを製造するための原料を均一に混合
する方法に関する。
［従来の技術］
近年、耐熱性が高い、電気的に絶縁性であ
つたり半導性のものが多く、磁気的、誘電的な性
質等の多機能性を有する、変形し難く、破壊す
るときには脆性破壊をする、靭性が低い、等の
性質を有するセラミツクスが種々の機能材料、機
械材料として着目され、パツケージ、基板、半導
体、センサー、光通信用フアイバー、超電導材料
等の電気、電子部品や、切削工具、バルブ、メカ
ニカルツール、プラスチツク強化用フアイバー、
半導体製造用治具、プラグ等の機械、自動車部品
や、人工歯根、人工間接、人工骨等の医療用機器
や、燃料棒、制御棒等の原子力関連機器等の分野
で広く利用されている。
そして、このようなセラミツクスを製造するに
は、その価値ある機能を発現させるために、高度
に精選された原料粉末を使用し、この原料粉末を
均一に配合してその化学組成が精密に調整された
セラミツクス原料を調製し、よく制御された成形
及び焼結を行うことが必要であるとされている。
そして、特に微構造制御を必要とし、あるい
は、材質の高度な均一性が要求される分野で使用
されるセラミツクスを製造するには、高度に精選
された原料粉末の選択も重要であるが、場合によ
つては微量添加される原料を高度に均一に混合
し、その化学組成を精密に調整したセラミツクス
原料の調製が極めて重要な課題になる。
このようなセラミツクス原料を調製する方法と
して、例えば、粉末混合法としては、原料粉末を
混合機で機械的に混合する乾式法や、原料粉末を
水やアルコールに懸濁し撹拌混合した後に固液分
離して乾燥する湿式法があり、また、原料が溶解
されている溶液から溶質を共沈させる共沈法とし
ては、蓚酸を使用し酸性領域で蓚酸塩として共沈
させる方法や、水酸化ナトリウム、水酸化カリウ
ム、アンモニア水等を使用して水酸化物として共
沈させる方法や、上記蓚酸とアルカリの混合系で
共沈させる方法等がある。
［発明が解決しようとする問題点］
しかしながら、上記原料粉末を機械的に混合す
る粉末混合法には、原料粉末の粒子の大きさを均
一にしたり、ある大きさ以下にする上で限界があ
り、このためセラミツクス原料の化学組成を高度
に均一に調整することが困難であるという問題が
あるほか、混合機からの汚染も避けられないとい
う問題がある。
また、共沈法では、溶液状態で原子レベルでの
混合が可能であるため、活性で焼結性に優れたセ
ラミツクス原料を調製することができるが、酸性
領域で蓚酸塩として共沈させる方法には定量的に
共沈させることができる元素の組合せが著しく制
限されるという問題があり、アルカリを使用して
共沈させる方法には例えばアルカリがアンモニア
であると銅のような金属はアンモニウム錯イオン
を形成して共沈せず、アルカリが水酸化ナトリウ
ム等であると沈澱物中にアルカリ金属が混入し、
微細粒子故に面倒な水洗工程が必要になるほか水
洗しても完全に除去するのが難しいという問題が
あり、いずれにしても共沈の操作中に必要な成分
が一定の割合で正しく析出しているかどうかが不
確実であり、特に微量添加する成分が溶媒中に残
存した場合には化学組成が大きく狂つてしまうと
いう問題がある。
従つて、本発明の目的は、共沈法によりその化
学組成が精密に調整され高度の均一性を有するセ
ラミツクス原料を調製することにある。また、本
発明の他の目的は、セラミツクス原料を蓚酸塩あ
るいは水酸化物の形で共沈させ、混合機等からの
汚染やアルカリ金属の混入等がなく、焼結した際
には高純度のセラミツクスを製造することができ
るセラミツクス原料を調製することにある。さら
に、本発明の目的は、セラミツクス原料として配
合した金属化合物の水系溶液からPH９以上に調製
された蓚酸系共沈剤を使用して金属蓚酸塩あるい
は金属水酸化物の形でほぼ定量的に共沈させる方
法を提供することにある。
［問題点を解決するための手段］
すなわち、本発明は、セラミツクス原料として
所定の割合で配合した金属化合物の水系溶液と有
機アミン系PH調整剤により塩基性に調整された蓚
酸系共沈剤とを混合し、金属をその蓚酸塩あるい
は水酸化物の形で共沈させて固液分離する共沈に
よるセラミツクス原料の調製法である。
本発明方法において、原料として使用される金
属化合物はそれが水溶性であつてPH９以上で蓚酸
塩あるいは水酸化物を形成し得るものであればよ
く、金属の種類としては、例えば、Cu等の族、
Ba、Zn、Ca、Mg、Sr等の族、Ｙ、In、Tb、
Eu、La、Dy等の族、Sn、Pb、Ti、Zr等の
族、Bi等の族、Cr等の族、Mn等の族、及
び、Fe、Co、Ni、Pb等の族の各金属、好まし
くは族のCu、族のBa、Zn、Ca、Mg、Sr、
族のＹ、In、希土類、族のPb、Ti、Zr、
族のCr、族のMn、族のFe、Co、Ni等を挙
げることができ、また、化合物の種類としては、
例えば上記各金属の酸化物や、塩酸塩、硝酸塩、
炭酸塩等の無機酸塩や、蓚酸塩、酢酸塩、蟻酸塩
等の有機酸塩等、好ましくは塩酸塩、硝酸塩、蓚
酸塩、酢酸塩等を挙げることができる。そして、
この金属化合物を溶解する水系溶媒については、
水以外に、例えば水−アルコール系溶媒、水−ピ
リジン系溶媒、水−ジオキサン系溶媒等の水と水
溶性有機溶媒との組合わせを使用することができ
る。
また、本発明で使用する蓚酸系共沈剤について
は、少なくとも上記金属化合物の水系溶液中に含
有される金属に対して当量以上、好ましくはこの
金属１当量に対して1.1当量以上、より好ましく
は1.2〜３当量の蓚酸イオンを含有する蓚酸の水
系溶液が使用される。そして、この蓚酸系共沈剤
を形成する水系溶媒としては、水以外に、例えば
水−アルコール系溶媒、水−ピリジン系溶媒、水
−ジオキサン系溶媒等の水と水溶性有機溶媒との
組合せが使用される。
さらに、上記蓚酸系共沈剤のPH調整剤として使
用される有機アミン系PH調整剤は、少なくとも上
記蓚酸系共沈剤を塩基性に調整し得るものであつ
て低温加熱で容易かつ可及的完全に除去可能であ
ることが必要であり、好ましくはこの蓚酸系共沈
剤のPHを８以上、より好ましくは９以上に調整し
得るものでる。このような有機アミン系PH調整剤
としては、例えば、下記一般式
（但し、式中R1、R2、R3及びR4はアルキル基又
は置換アルキル基示し、また、Ｘは水酸根、1/2
炭酸根又は重炭酸根を示す）で表されるテトラア
ルキルアンモニウム誘導体類や、トリメチルアミ
ン等のトリアルキルアミン類や、グアニジン、
１，３−ジフエニルグアニジン、１，１，３−ト
リフエニルグアニジン、ジオルソトリルグアニジ
ン等のグアニジン類や、アミジン、メチルアミジ
ン、１，８−ジアザビシクロ（５，４，０）ウン
デセン−７、ベンズアミジン、Ｎ−フエニルベン
ズアミジン、Ｎ，N′−ジフエニルホルムアミジ
ン、Ｎ，N′−ジフエニルアセトアミジン等のア
ミジン類を挙げることができ、これらはその１種
を適宜選択して使用できるほか、必要により組合
せ可能な２種以上の混合物としても使用できる。
本発明方法によりセラミツクス原料を調製する
には、先ず、所定の金属化合物を所定の割合に配
合してその水系溶液を調製し、一方、蓚酸系共沈
剤については、蓚酸と有機アミン系PH調製剤とを
所定の濃度及びPHとなるようにその使用量を調整
して蓚酸系共沈剤を調製し、これら金属化合物の
水系溶液と蓚酸系共沈剤とを混合し、所定時間放
置して生成した金属の蓚酸塩あるいは水酸化物を
共沈させればよい。このとき、上記金属化合物の
水系溶液と蓚酸系共沈剤とはそのいずれが一方を
他方に対して添加すればよいが、たとえ共沈操作
の途中であつても、金属化合物の水系溶液中にお
ける金属の組成と共沈によつて沈澱する沈澱物中
の金属の組成とが可及的に一致するように、蓚酸
系共沈剤中に金属化合物の水系溶液を撹拌下に添
加するのがよい。
そして、このように本発明方法でセラミツクス
原料を調製するに当つては、予め共沈させるべき
各金属について、それら各金属が溶液中に残留し
ている金属残留率と共沈剤のPHとの関係（PH−金
属残留率の関係）を調べておき、共沈させるべき
金属の配合割合を考慮して、例えば最もその配合
率の低い金属が最も効率良く沈澱するようなPHを
選定し、蓚酸系共沈剤のPHを有機アミン系PH調整
剤でそのPHに調整して使用するのがよい。また、
この共沈操作の際における溶液中への各金属の金
属残留率の許容量については、調製されるセラミ
ツクス原料の用途等によつて大幅に異なるが、一
般的には目標とする各金属の配合組成がその用途
で許容される範囲であることが必要であり、配合
される各金属についてその金属が１重量％以下、
好ましくは0.1重量％以下、より好ましくは0.05
重量％以下の範囲に納まるようにするのがよい。
本発明方法で共沈により沈澱した金属の蓚酸塩
あるいは水酸化物は、次に濾過、デカンテーシヨ
ン等の手段によつて固液分離され、場合により水
洗、乾燥、仮焼結、粉砕、本焼結等してセラミツ
クス原料とされる。
［作用］
本発明方法によれば、蓚酸系共沈剤を使用して
金属化合物の水系溶液から共沈させるに際し、有
機アミン系PH調整剤を使用して蓚酸系共沈剤のPH
を塩基性側に移行させるので、使用した金属をそ
の蓚酸塩あるいは水酸化物の形でほぼ完全に共沈
させることができ、始めに調製した金属化合物の
水系溶液における金属の組成を変えることなく原
子レベルで均一に混合したセラミツクス原料を調
製することができる。
また、共沈剤として使用する蓚酸や有機アミン
系PH調整剤は、いずれも低温加熱で容易かつ可及
的完全に除去できるので、共沈操作後に沈澱物の
水洗等の面倒な工程を必要としない。
［実施例］
以下、試験例、実施例及び比較例に基いて、本
発明方法を具体的に説明する。
試験例１：種々の金属についてのPH−金属残留
率の関係について
Mg、Ca、Sr、Ba、Ｙ、La、Eu、Tb、Ti、
Zr、Ｖ、Mn、Fe、Co、Cu、Cr、Ni、Zn、Al、
Sn、Pb、Biの各金属の塩酸塩、硝酸塩あるいは
酢酸塩の形の化合物について、その0.05〜1wt％
−水溶液を調製し、金属１当量に対して蓚酸1.5
当量を含有する蓚酸水溶液からなる蓚酸系共沈剤
に有機アミン系PH調整剤としてテトラメチルアン
モニウムハイドライドを添加してそのPH調製を行
い、この蓚酸系共沈剤中に上記各金属についての
水溶液を撹拌下に添加して各金属を蓚酸塩あるい
は水酸化物として沈澱させ、水溶液中に残留した
金属の濃度を測定して蓚酸系共沈剤のPHと金属残
留率との関係を調べた。結果を第１表に示す。
[Industrial Application Field] This invention relates to a method for uniformly mixing raw materials for manufacturing various ceramics, which is used in a wide range of fields. [Prior art] In recent years, there have been many materials that have high heat resistance, are electrically insulating or semiconductive, have multifunctional properties such as magnetic and dielectric properties, are difficult to deform, and are difficult to break. Ceramics, which have properties such as brittle fracture and low toughness, have attracted attention as various functional and mechanical materials, and are used in electrical and electronic parts such as packages, substrates, semiconductors, sensors, fibers for optical communication, superconducting materials, etc. Cutting tools, valves, mechanical tools, fibers for reinforcing plastics,
It is widely used in fields such as semiconductor manufacturing jigs, machines such as plugs, automobile parts, medical equipment such as artificial tooth roots, artificial joints, and artificial bones, and nuclear power related equipment such as fuel rods and control rods. In order to produce such ceramics, highly selected raw material powders are used, and the chemical composition is precisely adjusted by uniformly blending the raw material powders in order to bring out their valuable functions. There is a need to prepare ceramic raw materials and perform well-controlled shaping and sintering. In order to manufacture ceramics used in fields that particularly require microstructural control or a high degree of material uniformity, the selection of highly selected raw material powders is also important. In some cases, it is extremely important to prepare ceramic raw materials by mixing raw materials that are added in small amounts with a high degree of uniformity and precisely adjusting the chemical composition. Methods for preparing such ceramic raw materials include, for example, the powder mixing method, which includes a dry method in which the raw material powder is mechanically mixed in a mixer, and a solid-liquid separation method after suspending the raw material powder in water or alcohol and stirring and mixing. There is a wet method in which the raw materials are dissolved and then dried.Also, as a coprecipitation method in which the solute is coprecipitated from a solution in which raw materials are dissolved, there is a method in which oxalic acid is used to coprecipitate as oxalate in an acidic region, and a method in which sodium hydroxide, There are a method of coprecipitating as a hydroxide using potassium hydroxide, aqueous ammonia, etc., a method of coprecipitating with a mixed system of the above-mentioned oxalic acid and alkali, etc. [Problems to be Solved by the Invention] However, the powder mixing method of mechanically mixing the raw material powder has a limit in making the particle size of the raw material powder uniform or below a certain size. Therefore, there is a problem that it is difficult to adjust the chemical composition of the ceramic raw material to be highly uniform, and there is also a problem that contamination from the mixer is unavoidable. In addition, since the coprecipitation method allows mixing at the atomic level in a solution state, it is possible to prepare ceramic raw materials that are active and have excellent sinterability. There is a problem in that the combination of elements that can be quantitatively coprecipitated is severely limited, and the method of coprecipitating using an alkali has the problem that, for example, when the alkali is ammonia, the metal such as copper is mixed with an ammonium complex ion. If the alkali is sodium hydroxide etc., the alkali metal will be mixed into the precipitate,
Because of the fine particles, a troublesome water washing process is required and there is also the problem that it is difficult to completely remove them even with water washing. There is a problem in that it is uncertain whether the chemical composition is present or not, and the chemical composition will be greatly distorted, especially if a trace amount of the component added remains in the solvent. Therefore, an object of the present invention is to prepare a ceramic raw material whose chemical composition is precisely adjusted and has a high degree of uniformity by a coprecipitation method. Another object of the present invention is to co-precipitate ceramic raw materials in the form of oxalate or hydroxide, so that there is no contamination from mixers, no alkali metals, etc., and high purity is obtained when sintered. The purpose of this invention is to prepare ceramic raw materials from which ceramics can be manufactured. Furthermore, it is an object of the present invention to substantially quantitatively co-precipitate metal compounds in the form of metal oxalates or metal hydroxides by using an oxalic acid-based coprecipitant prepared to have a pH of 9 or higher from an aqueous solution of metal compounds blended as a raw material for ceramics. The purpose is to provide a method for sinking. [Means for Solving the Problems] That is, the present invention uses an aqueous solution of a metal compound mixed in a predetermined ratio as a ceramic raw material, an oxalic acid coprecipitant adjusted to basicity with an organic amine PH adjuster, and This is a method for preparing ceramic raw materials by coprecipitation, in which the metals are mixed together, the metals are co-precipitated in the form of their oxalates or hydroxides, and solid-liquid separation is performed. In the method of the present invention, the metal compound used as a raw material may be one that is water-soluble and capable of forming oxalate or hydroxide at a pH of 9 or higher. Examples of the metal compound include Cu, etc. family,
Groups such as Ba, Zn, Ca, Mg, Sr, Y, In, Tb,
Metals from groups such as Eu, La, and Dy, groups such as Sn, Pb, Ti, and Zr, groups such as Bi, groups such as Cr, groups such as Mn, and groups such as Fe, Co, Ni, and Pb. , preferably group Cu, group Ba, Zn, Ca, Mg, Sr,
Group Y, In, rare earth, Group Pb, Ti, Zr,
Examples include Cr of the group, Mn of the group, Fe, Co, Ni, etc. of the group, and types of compounds include:
For example, oxides, hydrochlorides, nitrates, etc. of each of the above metals,
Examples include inorganic acid salts such as carbonates, organic acid salts such as oxalates, acetates, and formates, and preferably hydrochlorides, nitrates, oxalates, and acetates. and,
Regarding the aqueous solvent that dissolves this metal compound,
In addition to water, a combination of water and a water-soluble organic solvent can be used, such as a water-alcohol solvent, a water-pyridine solvent, a water-dioxane solvent, and the like. Furthermore, the oxalic acid coprecipitant used in the present invention is at least equivalent to the metal contained in the aqueous solution of the metal compound, preferably 1.1 equivalent or more to 1 equivalent of this metal, and more preferably An aqueous solution of oxalic acid containing 1.2 to 3 equivalents of oxalate ions is used. In addition to water, the aqueous solvent that forms this oxalic acid coprecipitant may include combinations of water and water-soluble organic solvents, such as water-alcohol solvents, water-pyridine solvents, and water-dioxane solvents. used. Furthermore, the organic amine-based PH adjuster used as the PH adjuster for the oxalic acid-based coprecipitant is one that can at least adjust the oxalic acid-based coprecipitant to basicity, and that can be easily and as much as possible by heating at a low temperature. It is necessary to be completely removable, and preferably the pH of the oxalic acid coprecipitant can be adjusted to 8 or higher, more preferably 9 or higher. As such an organic amine-based PH adjuster, for example, the following general formula (However, in the formula, R 1 , R 2 , R 3 and R 4 represent an alkyl group or a substituted alkyl group, and X is a hydroxyl group, 1/2
(representing a carbonate or bicarbonate group), trialkylamines such as trimethylamine, guanidine,
Guanidines such as 1,3-diphenylguanidine, 1,1,3-triphenylguanidine, diorthotolylguanidine, amidine, methylamidine, 1,8-diazabicyclo(5,4,0)undecene-7, benzamidine , N-phenylbenzamidine, N,N'-diphenylformamidine, N,N'-diphenylacetamidine, etc., and one of these can be appropriately selected and used. It can also be used as a mixture of two or more types, which can be combined if necessary. To prepare ceramic raw materials by the method of the present invention, first, a predetermined metal compound is mixed in a predetermined ratio to prepare an aqueous solution thereof. An oxalic acid-based coprecipitant is prepared by adjusting the amount used to obtain a prescribed concentration and pH of the preparation, and the aqueous solution of these metal compounds and the oxalic acid-based coprecipitating agent are mixed and left for a prescribed period of time. The produced metal oxalate or hydroxide may be co-precipitated. At this time, either the aqueous solution of the metal compound or the oxalic acid-based coprecipitant may be added to the other, but even during the coprecipitation operation, it is possible to An aqueous solution of the metal compound is preferably added to the oxalic acid coprecipitant under stirring so that the composition of the metal matches the composition of the metal in the precipitate precipitated by coprecipitation as much as possible. In preparing ceramic raw materials using the method of the present invention, the ratio of each metal remaining in the solution and the pH of the coprecipitant is determined in advance for each metal to be coprecipitated. Investigate the relationship (relationship between PH and metal residual rate), consider the mixing ratio of metals to be co-precipitated, and select a pH that will allow the metal with the lowest mixing ratio to precipitate most efficiently. It is preferable to adjust the pH of the system coprecipitant to that level using an organic amine system PH adjuster before use. Also,
The allowable residual rate of each metal in the solution during this coprecipitation operation varies greatly depending on the intended use of the ceramic raw material to be prepared, but in general, the target combination of each metal is It is necessary for the composition to be within a range acceptable for the purpose, and for each metal to be blended, the content of that metal is 1% by weight or less,
Preferably 0.1% by weight or less, more preferably 0.05
It is preferable to keep it within a range of % by weight or less. The metal oxalate or hydroxide precipitated by coprecipitation in the method of the present invention is then separated into solid and liquid by means such as filtration and decantation. It is sintered and used as a raw material for ceramics. [Function] According to the method of the present invention, when co-precipitating an aqueous solution of a metal compound using an oxalic acid-based coprecipitant, an organic amine-based PH adjuster is used to adjust the pH of the oxalic acid-based coprecipitant.
Since the metal is transferred to the basic side, the metal used can be almost completely co-precipitated in the form of its oxalate or hydroxide, without changing the composition of the metal in the aqueous solution of the metal compound initially prepared. It is possible to prepare ceramic raw materials that are uniformly mixed at the atomic level. In addition, the oxalic acid and organic amine-based PH adjusters used as coprecipitants can be easily and completely removed by low-temperature heating, so there is no need for troublesome steps such as washing the precipitate with water after the coprecipitation operation. do not. [Example] Hereinafter, the method of the present invention will be specifically explained based on Test Examples, Examples, and Comparative Examples. Test example 1: Regarding the relationship between PH and metal residual rate for various metals Mg, Ca, Sr, Ba, Y, La, Eu, Tb, Ti,
Zr, V, Mn, Fe, Co, Cu, Cr, Ni, Zn, Al,
0.05-1wt% of compounds in the form of hydrochloride, nitrate or acetate of each metal Sn, Pb, Bi
- Prepare an aqueous solution with 1.5 oxalic acid per equivalent of metal.
Tetramethylammonium hydride is added as an organic amine-based PH adjuster to an oxalic acid-based coprecipitant consisting of an oxalic acid aqueous solution containing an equivalent amount to adjust the pH, and an aqueous solution of each of the above metals is added to the oxalic acid-based coprecipitant under stirring. The relationship between the pH of the oxalic acid-based coprecipitant and the metal residual rate was investigated by adding each metal to precipitate as oxalate or hydroxide, and measuring the concentration of the metal remaining in the aqueous solution. The results are shown in Table 1.
【表】
実施例 １
酢酸バリウム18.6ｇ、硝酸銅19.0ｇ及び硝酸イ
ツトリウム21.5ｇを純水２に溶解して金属化合
物の水溶液を調製した。
一方、25wt％−テトラメチルアンモニウムヒ
ドロキサイド水溶液250mlに蓚酸40ｇを溶解した
後、さらに25wt％−テトラメチルアンモニウム
ヒドロキサイド水溶液を添加し、PH13.0に調整さ
れた蓚酸系共沈剤を調製した。
このように調製された蓚酸系共沈剤中に、撹拌
しながら上記金属化合物の水溶液を添加し、１時
間放置してバリウム、銅及びイツトリウムについ
てそれぞれ蓚酸塩又は水酸化物の形で共沈させ
た。
共沈した沈澱物を濾過器で濾過して固液分離
し、乾燥機により120℃で乾燥し、セラミツクス
原料を調製した。このとき、濾液側に残留した各
金属について誘導結合プラズマ発光分光分析法及
びキレート滴定法によりその金属残留率を測定し
た結果、バリウムが0.53重量％、銅が0.02重量％
及びイツトリウムが0.01重量％であつた。
このようにして得られたセラミツクス原料を使
用し、これを900℃で焼結したところ、原料の金
属化合物から計算によつて求められる各金属の酸
化物の理論組成がBaO：46.99重量％、Y2O3：
26.67重量％及びCuO：26.34重量％に対し、得ら
れた焼結体の組成はBaO：46.8重量％、Y2O3：
26.7重量％及びCuO：26.4重量％であつた。
実施例 ２
10wt％−テトラプロピルアンモニウムヒドロ
キサイド水溶液600mlに蓚酸40ｇを溶解した後、
さらに10wt％−テトラプロピルアンモニウムヒ
ドロキサイド水溶液を添加し、PH12.8に調整した
蓚酸系共沈剤を使用した以外は、上記実施例１と
同様にしてセラミツクス原料23ｇを調製した。こ
のとき、瀘液側に残留した各金属についてその金
属残留率を測定した結果、バリウムが0.38重量
％、銅が0.01重量％及びイツトリウムが0.01重量
％であつた。
このセラミツクス原料を使用し、上記実施例１
と同様にして焼結したところ、組成がBaO：46.9
重量％、Y2O3：26.7重量％及びCuO：26.4重量％
の焼結体が得られた。
実施例 ３
酢酸バリウム２ｇと硝酸鉄33ｇとを純水１中
に溶解して金属化合物の水溶液を調製した。
一方、蓚酸25ｇを純水500ml中に溶解し、これ
にトリメチルアミンガスを吹込んでPHを9.1に調
製し蓚酸系共沈剤とした。
このようにして調製した蓚酸系共沈剤を撹拌下
に上記金属化合物の水溶液中に添加し、放置して
バリウムと鉄とをそれぞれ蓚酸塩又は水酸化物の
刑で共沈させ、上記実施例１と同様にしてセラミ
ツクス原料を得た。このとき、瀘液側に残留した
各金属についてその金属残留率を測定した結果、
バリウムが＜0.05重量％で、鉄が0.48重量％であ
つた。
このセラミツクス原料を使用し、上記実施例１
と同様にして焼結したところ、原料の金属化合物
から計算によつて求められる各金属酸化物の理論
組成がBaO：15.54重量％及びFe2O3：84.45重量
％であるのに対し、この実施例で得られた焼結体
の組成はBaO：15.6重量％及びFe2O3重量％であ
つた。
比較例 １
純水0.25中に蓚酸アンモニウム３ｇを溶解し
て調製した共沈剤を使用した以外は、上記実施例
１と同様にしてセラミツクス原料を得た。このと
き使用した共沈剤のPHは10であり、また、濾液側
に残留した各金属についてその金属残留率を測定
した結果、バリウムが0.36重量％、銅が95重量％
及びイツトリウムが0.1重量％であつた。
比較例 ２
純水0.25中に蓚酸９ｇを溶解して調製した共
沈剤を使用した以外は、上記実施例１と同様にし
てセラミツクス原料を得た。このとき使用した共
沈剤は酸性であり、また、濾液側に残留した各金
属についてその金属残率を測定した結果、バリウ
ムが75重量％、銅が0.55重量％及びイツトリウム
が0.05重量％であつた。
比較例 ３
純水0.4中にテトラメチルアンモニウムヒド
ロキサイド100ｇを溶解して調製した共沈剤を使
用した以外は、上記実施例１と同様にしてセラミ
ツクス原料を得た。このとき使用した共沈剤のPH
は12であり、また、濾液側に残留した各金属につ
いてその金属残留率を測定した結果、バリウムが
96重量％、銅が0.8重量％及びイツトリウムが
0.01重量％であつた。
［発明の効果］
本発明方法によれば、原料として使用した金属
をその蓚酸塩あるいは水酸化物の形でほぼ完全に
共沈させることができ、始めに調製した金属化合
物の水系溶液における金属の組成を変えることな
く原子レベルで均一に混合したセラミツクス原料
を調製することができ、これによつてその化学組
成が精密に調整され高度の均一性を有するセラミ
ツクス原料を調製することができ、価値ある機能
を有するセラミツクスを容易に製造することがで
きる。また、共沈剤として使用する蓚酸や有機ア
ミン系PH調整剤は、そのいずれも低温加熱で容易
かつ可及的完全に除去できるので、共沈操作後に
沈澱物の水洗等の面倒な工程を必要とせず、ま
た、高純度のセラミツクス原料を調製することが
できる。[Table] Example 1 An aqueous solution of a metal compound was prepared by dissolving 18.6 g of barium acetate, 19.0 g of copper nitrate, and 21.5 g of yttrium nitrate in pure water 2. On the other hand, 40 g of oxalic acid was dissolved in 250 ml of a 25 wt% tetramethylammonium hydroxide aqueous solution, and then a 25 wt% tetramethylammonium hydroxide aqueous solution was added to prepare an oxalic acid coprecipitant whose pH was adjusted to 13.0. An aqueous solution of the above metal compound was added to the oxalic acid coprecipitant thus prepared with stirring, and allowed to stand for 1 hour to coprecipitate barium, copper and yttrium in the form of oxalate or hydroxide, respectively. The co-precipitated precipitate was filtered using a filter to separate solid and liquid, and dried at 120°C using a drier to prepare a ceramic raw material. At this time, the metal residual rate of each metal remaining on the filtrate side was measured by inductively coupled plasma optical emission spectroscopy and chelate titration, and the results showed that barium was 0.53% by weight and copper was 0.02% by weight.
and 0.01% by weight of yttrium. Using the ceramic raw material obtained in this way and sintering it at 900°C, the theoretical composition of the oxides of each metal calculated from the raw metal compound was BaO: 46.99% by weight, Y 2O3 :
The composition of the obtained sintered body was BaO: 46.8% by weight, Y 2 O 3 : 26.67% by weight and CuO: 26.34% by weight.
26.7% by weight and CuO: 26.4% by weight. Example 2 After dissolving 40 g of oxalic acid in 600 ml of 10 wt% tetrapropylammonium hydroxide aqueous solution,
23 g of a ceramic raw material was prepared in the same manner as in Example 1, except that an oxalic acid coprecipitant whose pH was adjusted to 12.8 was further added with a 10 wt % aqueous solution of tetrapropylammonium hydroxide. At this time, the metal residual rates of each metal remaining on the filtrate side were measured, and as a result, barium was 0.38% by weight, copper was 0.01% by weight, and yttrium was 0.01% by weight. Using this ceramic raw material, the above Example 1
When sintered in the same manner as above, the composition was BaO: 46.9
Weight% , Y2O3 : 26.7% by weight and CuO: 26.4% by weight
A sintered body was obtained. Example 3 An aqueous solution of a metal compound was prepared by dissolving 2 g of barium acetate and 33 g of iron nitrate in 1 part of pure water. On the other hand, 25 g of oxalic acid was dissolved in 500 ml of pure water, and trimethylamine gas was blown into the solution to adjust the pH to 9.1 to obtain an oxalic acid coprecipitant. The oxalic acid-based coprecipitant thus prepared was added to the aqueous solution of the metal compound with stirring, and allowed to stand to coprecipitate barium and iron with oxalate or hydroxide, respectively. A ceramic raw material was obtained in the same manner as in 1. At this time, as a result of measuring the metal residual rate of each metal remaining on the filtrate side,
Barium was <0.05% by weight and iron was 0.48% by weight. Using this ceramic raw material, the above Example 1
When sintered in the same manner as above, the theoretical composition of each metal oxide determined by calculation from the raw metal compound was BaO: 15.54% by weight and Fe 2 O 3 : 84.45% by weight, but this method The composition of the sintered body obtained in the example was 15.6% by weight of BaO and 3 % by weight of Fe 2 O. Comparative Example 1 A ceramic raw material was obtained in the same manner as in Example 1, except that a coprecipitant prepared by dissolving 3 g of ammonium oxalate in 0.25% pure water was used. The pH of the coprecipitant used at this time was 10, and as a result of measuring the metal residual rate of each metal remaining on the filtrate side, barium was 0.36% by weight and copper was 95% by weight.
and 0.1% by weight of ythtrium. Comparative Example 2 A ceramic raw material was obtained in the same manner as in Example 1, except that a coprecipitant prepared by dissolving 9 g of oxalic acid in 0.25 g of pure water was used. The coprecipitant used at this time was acidic, and as a result of measuring the metal residual percentage of each metal remaining on the filtrate side, barium was 75% by weight, copper was 0.55% by weight, and yttrium was 0.05% by weight. Ta. Comparative Example 3 A ceramic raw material was obtained in the same manner as in Example 1, except that a coprecipitant prepared by dissolving 100 g of tetramethylammonium hydroxide in 0.4 g of pure water was used. PH of coprecipitant used at this time
is 12, and as a result of measuring the metal residual rate of each metal remaining on the filtrate side, it was found that barium
96% by weight, 0.8% by weight copper and yttrium
It was 0.01% by weight. [Effects of the Invention] According to the method of the present invention, the metal used as a raw material can be almost completely co-precipitated in the form of its oxalate or hydroxide, and the metal in the aqueous solution of the metal compound initially prepared can be co-precipitated. It is possible to prepare ceramic raw materials that are uniformly mixed at the atomic level without changing the composition, and this makes it possible to precisely adjust the chemical composition and prepare ceramic raw materials with a high degree of uniformity, making it valuable. Functional ceramics can be easily produced. In addition, oxalic acid and organic amine-based PH adjusters used as coprecipitants can be easily and completely removed by low-temperature heating, so there is no need for troublesome steps such as washing the precipitate with water after the coprecipitation operation. It is also possible to prepare high-purity ceramic raw materials.
Claims (1)
た金属化合物の水系溶液と有機アミン系PH調整剤
により塩基性に調整された蓚酸系共沈剤とを混合
し、金属をその蓚酸塩あるいは水酸化物の形で共
沈させて固液分離することを特徴とする共沈によ
るセラミツクス原料の調製法。 ２ 蓚酸系共沈剤がPH８以上である特許請求の範
囲第１項記載の共沈によるセラミツクス原料の調
製法。 ３ 有機アミン系PH調整剤が、テトラアルキルア
ンモニウム誘導体類、トリアルキルアミン類、グ
アニジン類又はアミジン類である特許請求の範囲
第１項記載の共沈によるセラミツクス原料の調製
法。 ４ 蓚酸系共沈剤中に金属化合物の水系溶液を撹
拌下に添加して混合する特許請求の範囲第１項な
いし第３項のいずれかに記載の共沈によるセラミ
ツクス原料の調製法。[Claims] 1. An aqueous solution of a metal compound blended in a predetermined ratio as a ceramic raw material and an oxalic acid coprecipitant adjusted to basicity with an organic amine PH adjuster are mixed, and the metal is converted into its oxalate. Alternatively, a method for preparing ceramic raw materials by coprecipitation, which is characterized by co-precipitation in the form of hydroxide and solid-liquid separation. 2. The method for preparing ceramic raw materials by coprecipitation according to claim 1, wherein the oxalic acid coprecipitant has a pH of 8 or higher. 3. The method for preparing ceramic raw materials by coprecipitation according to claim 1, wherein the organic amine-based PH regulator is a tetraalkylammonium derivative, a trialkylamine, a guanidine, or an amidine. 4. A method for preparing a ceramic raw material by coprecipitation according to any one of claims 1 to 3, wherein an aqueous solution of a metal compound is added to an oxalic acid coprecipitant under stirring and mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62139998A JPS63307102A (en) | 1987-06-05 | 1987-06-05 | Preparation of ceramics raw material by coprecipitation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62139998A JPS63307102A (en) | 1987-06-05 | 1987-06-05 | Preparation of ceramics raw material by coprecipitation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63307102A JPS63307102A (en) | 1988-12-14 |
| JPH0419165B2 true JPH0419165B2 (en) | 1992-03-30 |
Family
ID=15258552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62139998A Granted JPS63307102A (en) | 1987-06-05 | 1987-06-05 | Preparation of ceramics raw material by coprecipitation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63307102A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067833A (en) * | 2016-12-13 | 2018-06-21 | 대한민국(국방부 공군참모총장) | Radome Cover |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01286906A (en) * | 1988-05-11 | 1989-11-17 | Murata Mfg Co Ltd | Production of oxide powder for ceramic |
| US5252314A (en) * | 1990-11-30 | 1993-10-12 | Case Western Reserve University | Method for producing coprecipitated multicomponent oxide powder precursors using guanidine oxalate as precipitating agent |
| SG75850A1 (en) * | 1998-06-11 | 2000-10-24 | Univ Singapore | Method for producing sintered electroceramic materials from hydroxide and oxalate precursors |
| KR101551853B1 (en) | 2008-04-03 | 2015-09-08 | 사켐,인코포레이티드 | Process for preparing advanced ceramic powder using onium dicarboxylates |
| US10642073B2 (en) | 2014-06-04 | 2020-05-05 | Shin-Etsu Chemical Co., Ltd. | Method for producing transparent ceramic, transparent ceramic, magneto-optical device and rare earth oxide powder for sintering |
| CN110734292B (en) * | 2019-11-27 | 2022-03-11 | 宝鸡文理学院 | Method for uniformly mixing CuO and ceramic powder |
-
1987
- 1987-06-05 JP JP62139998A patent/JPS63307102A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067833A (en) * | 2016-12-13 | 2018-06-21 | 대한민국(국방부 공군참모총장) | Radome Cover |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63307102A (en) | 1988-12-14 |
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