JPS6363512B2 - - Google Patents
Info
- Publication number
- JPS6363512B2 JPS6363512B2 JP59228760A JP22876084A JPS6363512B2 JP S6363512 B2 JPS6363512 B2 JP S6363512B2 JP 59228760 A JP59228760 A JP 59228760A JP 22876084 A JP22876084 A JP 22876084A JP S6363512 B2 JPS6363512 B2 JP S6363512B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- lead
- precipitate
- plzt
- titanium
- 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
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- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000001272 pressureless sintering Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- 150000004703 alkoxides Chemical class 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- -1 zirconium alkoxide Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UMZXEKFNURNTSQ-UHFFFAOYSA-M C(C(=O)[O-])(=O)[O-].[Zr+].[NH4+] Chemical compound C(C(=O)[O-])(=O)[O-].[Zr+].[NH4+] UMZXEKFNURNTSQ-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 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PLZT透光性セラミツクスの製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing PLZT translucent ceramics.
PLZT透光性セラミツクスは、オプトエレクト
ロニクスにおける光シヤツタ、光バルブ、画像蓄
積装置、ゴーグル、透明発音体、表示装置、光変
調素子などとして期待されている。 PLZT translucent ceramics are expected to be used in optoelectronics such as optical shutters, light valves, image storage devices, goggles, transparent sounding bodies, display devices, and light modulation elements.
本発明におけるPLZTとは、ペロブスカイト構
造を有する一般式、（Pb1-xLax）〔（Zry・Ti1-y）1-
ｘ／４□ｘ／４〕O3、もしくは（Pb1-3x/2□x/2Lax）
（Zry・Ti1-y）O3（ただし、ｘ＝0.01〜0.3、ｙ＝
0.05〜0.95、□は陽イオン空孔を表わす）で示さ
れるセラミツクス及び両者の中間組成体を言う。 PLZT in the present invention has a general formula (Pb 1-x La x ) [( Zry・Ti 1-y ) 1- having a perovskite structure.
x/4 □ x/4 〕O 3 , or (Pb 1-3x/2 □ x/2 La x )
(Zr y・Ti 1-y ) O 3 (x=0.01~0.3, y=
0.05 to 0.95 (□ represents a cationic vacancy) and intermediate compositions between the two.
従来技術
PLZT透光性セラミツクスは原料粉末を作り、
成型後、空気中もしくは酸素雰囲気中でホツトプ
レスするか、鉛を過剰に加えて酸素と鉛雰囲気下
で液相焼結する方法によつて製造されている。こ
の場合、原料粉末が均一且つ、低コスト、易焼結
性であることが極めて重要である。Conventional technology PLZT translucent ceramics is made from raw material powder,
After molding, it is manufactured by hot pressing in air or an oxygen atmosphere, or by adding an excessive amount of lead and performing liquid phase sintering in an oxygen and lead atmosphere. In this case, it is extremely important that the raw material powder be uniform, low cost, and easily sinterable.
従来のPLZT透光性セラミツクスの原料粉末の
製造方法としては、乾式法、アルコキシド法、蓚
酸塩法などが知られている。 Conventional methods for producing raw material powder for PLZT translucent ceramics include the dry method, alkoxide method, and oxalate method.
乾式法は構成成分の化合物を混合し、これを仮
焼する方法であるが、この方法では均一組成を達
成することが困難であり、またPLZTの固相反応
を完遂させるために仮焼温度を高くすることが必
要であるので、これにより粒子が粗大化して易焼
結性になりにくい欠点があつた。 The dry method is a method in which the constituent compounds are mixed and calcined, but it is difficult to achieve a uniform composition with this method, and the calcining temperature must be adjusted to complete the solid phase reaction of PLZT. Since it is necessary to increase the particle size, this has the disadvantage that the particles become coarse and easily sinterable.
アルコキシド法は酸化鉛粉末、ジルコニウムア
ルコキシド溶液、チタンアルコキシド溶液、ラン
タン酢酸塩溶液をブレンドした後、乾燥、粉砕す
るなどの方法である。この方法によると高価なア
ルコキシド、酢酸塩などを必要とするため、高コ
ストとなるばかりでなく、99.9％以上の高純度の
試薬を用いること、またアルコキシド、酢酸塩の
製造工程が繁雑で作業性も悪いなどの欠点があ
る。 The alkoxide method involves blending lead oxide powder, zirconium alkoxide solution, titanium alkoxide solution, and lanthanum acetate solution, followed by drying and pulverizing. This method requires expensive alkoxides, acetates, etc., which not only results in high costs, but also requires the use of reagents with a purity of 99.9% or higher, and the process for producing alkoxides and acetates is complicated and difficult to work with. There are some drawbacks as well.
蓚酸塩法はチタンアルコキシドと硝酸とからオ
キシ硝酸チタン溶液を作り、これと硝酸ジルコニ
ヤ溶液及び蓚酸アンモニウム粉末を混合して、蓚
酸チタニルアンモニウムと蓚酸ジルコニウムアン
モニウム混合液となし、次いでこれに硝酸鉛溶液
と硝酸ランタン溶液を混合して複合蓚酸塩共沈物
を生成し、蒸発乾固、熱分解・粉砕・仮焼するな
どの方法である。この方法によると高価な薬品を
多数必要とし、かつ99.9％以上の高純度の試薬を
必要とするので高コストになるばかりでなく、工
程も繁雑で作業性も悪い欠点がある。 In the oxalate method, a titanium oxynitrate solution is made from titanium alkoxide and nitric acid, and this is mixed with a zirconia nitrate solution and ammonium oxalate powder to form a mixed solution of titanylammonium oxalate and zirconium ammonium oxalate, which is then mixed with a lead nitrate solution. The method involves mixing a lanthanum nitrate solution to produce a composite oxalate coprecipitate, followed by evaporation to dryness, thermal decomposition, crushing, and calcining. This method requires a large number of expensive chemicals and reagents with a purity of 99.9% or higher, which not only results in high costs, but also has the drawback of complicated steps and poor workability.
このような高価なアルコキシドやオキシ硝酸チ
タンを使用する湿式法が考えられた背景には、安
価な四塩化チタンをチタン原料として使用した場
合、四塩化チタンを共沈法に使用すると、四塩化
チタンの塩素が鉛と反応して白色沈殿が生じ、乾
式共沈法を行うことができないことが挙げられ
る。 The reason behind the idea of such a wet method that uses expensive alkoxides and titanium oxynitrate is that when cheap titanium tetrachloride is used as a titanium raw material, when titanium tetrachloride is used in the coprecipitation method, titanium tetrachloride The chlorine reacts with lead to form a white precipitate, making dry coprecipitation impossible.
発明の目的
本発明は従来法の欠点を解消するためになされ
たもので、その目的は、原料として安価な四塩化
チタンを使用することができ、かつ、高価な試薬
を必要としないで湿式法によつて均一でかつ易焼
結性の原料を作り、これを焼結することにより、
透光性及び特性の優れたPLZTセラミツクスを製
造する方法を提供するにある。Purpose of the Invention The present invention was made in order to overcome the drawbacks of the conventional method.The purpose of the present invention is to use a wet method that can use inexpensive titanium tetrachloride as a raw material and does not require expensive reagents. By creating a uniform and easily sinterable raw material and sintering it,
The object of the present invention is to provide a method for manufacturing PLZT ceramics with excellent translucency and properties.
発明の構成
本発明者は前記の目的を達成するため鋭意研究
の結果、構成成分の全部を同時に共沈させること
なく、二重に沈殿を形成させると従来の共沈法の
欠点を解決し、従来の共沈法では使用し得なかつ
た安価な四塩化チタンをチタン原料として使用し
得られ、また二次粒子の生成もなく、組成成分が
均一に分散された易焼結性、高嵩密度の原料粉末
が容易に得られる。また二重沈殿方式にすると、
各段階で各組成成分に適した沈殿形成液の種類及
び濃度を選ぶことができ、目的組成をもつた原料
粉末が容易に得られることを究明し得た。これを
原料として使用すると、透光性の優れたセラミツ
クスが得られることが分つた。これらの知見に基
いて本発明を完成した。Structure of the Invention In order to achieve the above object, the present inventor has conducted intensive research and found that the drawbacks of the conventional coprecipitation method are solved by forming double precipitates without co-precipitating all the constituent components at the same time. It can be obtained by using inexpensive titanium tetrachloride, which could not be used with the conventional coprecipitation method, as a titanium raw material, and there is no generation of secondary particles, and the composition is uniformly dispersed, making it easy to sinter, and has a high bulk density. raw material powder can be easily obtained. Also, if you use the double precipitation method,
It has been found that the type and concentration of the precipitate forming liquid suitable for each component can be selected at each stage, and a raw material powder having the desired composition can be easily obtained. It has been found that ceramics with excellent translucency can be obtained by using this as a raw material. The present invention was completed based on these findings.
本発明の要旨は、ペロブスカイト構造を有する
一般式（Pb1-xLax）〔（Zry・Ti1-y）1-x/4□x/4〕O3、
（Pb1-3x/2□x/2Lax）（Zry・Ti1-y）O3（ただし、ｘ
＝0.01〜0.3、ｙ＝0.05〜0.95、□は陽イオン空孔
を表わす）または両者の中間組成体、もしくはこ
れらの組成に10wt％以下の鉛を過剰に添加した
粉末成型体の焼結による透光性PLZTセラミツク
スの製造において、
(1) 鉛、ランタン、ジルコニウム、チタン四成分
の水溶液を作り、ランタン水溶液とジルコニウ
ム水溶液を鉛水溶液もしくはチタン水溶液のい
ずれか一方に混合して二種類の水溶液とし、そ
の内一種の水溶液に過剰の沈殿形成液を混合し
て沈殿を形成させた後、この沈殿の分散した水
溶液に残つた他の水溶液を均一に混合して全成
分の均密沈殿を作り、これを500〜1100℃で仮
焼し、
(2) 次いで、仮焼物を成形後、1000〜1280℃で空
気中もしくは酸素雰囲気中でホツトプレスする
か、あるいは酸素と鉛蒸気の混合雰囲気下で常
圧焼結することを特徴とする透光性セラミツク
スの製造法にある。 The gist of the present invention is that the general formula (Pb 1-x La x ) [( Zry・Ti 1-y ) 1-x/4 □ x/4 ]O 3 having a perovskite structure,
(Pb 1-3x/2 □ x/2 La x ) (Zr y・Ti 1-y ) O 3 (However, x
= 0.01 to 0.3, y = 0.05 to 0.95, □ represents a cation vacancy) or an intermediate composition between the two, or a transparent powder formed by sintering a powder molded product with an excess of 10 wt% or less of lead added to these compositions. In the production of photosensitive PLZT ceramics, (1) Create an aqueous solution of four components: lead, lanthanum, zirconium, and titanium, mix the lanthanum aqueous solution and the zirconium aqueous solution with either the lead aqueous solution or the titanium aqueous solution to form two types of aqueous solutions, One of these aqueous solutions is mixed with an excess of the precipitate forming liquid to form a precipitate, and then the remaining aqueous solution is uniformly mixed with the aqueous solution in which this precipitate has been dispersed to form a homogeneous precipitate of all the components. (2) Then, after forming the calcined product, it is hot-pressed at 1000-1280°C in air or an oxygen atmosphere, or it is sintered under normal pressure in a mixed atmosphere of oxygen and lead vapor. The present invention relates to a method for producing translucent ceramics characterized by bonding.
PLZT系の構成成分の水溶液を調製するための
成分化合物としては、オキシ硝酸塩、硫酸塩、硝
酸塩、酢酸塩、ぎ酸塩、しゆう酸塩、オキシ塩化
物、塩化物、酸化物、金属などがある。これらが
水で可溶でない場合は鉱酸などを添加して可溶と
することができる。 Component compounds for preparing an aqueous solution of PLZT system components include oxynitrates, sulfates, nitrates, acetates, formates, oxalates, oxychlorides, chlorides, oxides, metals, etc. be. If these are not soluble in water, mineral acids or the like can be added to make them soluble.
沈殿形成液としては、例えばアンモニヤ、炭酸
アンモニウム、苛性アルカリ、炭酸ソーダ、しゆ
う酸、しゆう酸アンモニウム及びオキシンやアミ
ンなどの有機試薬などが挙げられる。これらの中
から適当なものを選べばよい。 Examples of the precipitation forming liquid include ammonia, ammonium carbonate, caustic alkali, soda carbonate, oxalic acid, ammonium oxalate, and organic reagents such as oxine and amines. You can choose an appropriate one from these.
構成成分の沈殿を生成するには、液を撹拌しな
がら行うことが好ましい。 In order to generate precipitation of the constituent components, it is preferable to perform the precipitation while stirring the liquid.
また、ある沈殿の生成後、ろ液を除き、沈殿形
成液の種類や濃度を残り成分に適したものに変え
て沈殿させてもよい。 Further, after the formation of a certain precipitate, the filtrate may be removed, and the type and concentration of the precipitate forming liquid may be changed to those suitable for the remaining components, and the precipitate may be precipitated.
沈殿物の洗浄に際して、エタノールなどのアル
コール類を用いると、以後の乾燥、仮焼工程で沈
殿の凝結が抑制されて好結果が得られる。 If an alcohol such as ethanol is used to wash the precipitate, good results can be obtained since coagulation of the precipitate is suppressed in the subsequent drying and calcination steps.
得られた沈殿物を乾燥し、500〜1100℃で仮焼
する。仮焼温度が500℃未満ではPLZTの生成反
応や脱ガスが完結せず、また得られるPLZT粉末
の嵩密度が低くなる。1100℃を超えるとPLZT粉
末粒子が粗大化して焼結性が悪くなる。従つて仮
焼温度は500〜1100℃であることが適当である。
これにより、均一、高嵩密度で、かつ易焼結性の
PLZT系粉末が得られる。 The obtained precipitate is dried and calcined at 500-1100°C. If the calcination temperature is less than 500°C, the PLZT production reaction and degassing will not be completed, and the bulk density of the obtained PLZT powder will be low. When the temperature exceeds 1100°C, the PLZT powder particles become coarse and the sinterability deteriorates. Therefore, it is appropriate that the calcination temperature is 500 to 1100°C.
This results in uniform, high bulk density, and easy sinterability.
PLZT powder is obtained.
次に、成形・焼結する。焼結は空気中でホツト
プレスを行うことが安価で有利であるが、これを
酸素雰囲気中で行うと焼結性を増大させることが
できる。また、酸素や空気が通過可能にした閉鎖
中に、鉛を含んだ例えばペロブスカイト化合物な
どを共存させて鉛蒸気を雰囲気中に含ませて常圧
焼結を行うことにより、焼結の際鉛の飛散を抑制
することができる。 Next, it is molded and sintered. For sintering, hot pressing in air is inexpensive and advantageous, but sinterability can be increased by performing this in an oxygen atmosphere. In addition, by performing atmospheric pressure sintering with a perovskite compound containing lead coexisting in the atmosphere while it is closed to allow oxygen and air to pass through, lead can be removed during sintering. Scattering can be suppressed.
焼結温度は850℃より低いと焼結が不十分であ
り、1280℃を超えると鉛の飛散が顕著となり多孔
質化するので、850〜1280℃であることが必要で
ある。 If the sintering temperature is lower than 850°C, the sintering will be insufficient, and if it exceeds 1280°C, the scattering of lead will be noticeable and the material will become porous, so it is necessary to be in the range of 850 to 1280°C.
実施例
硝酸鉛30.140ｇ、硝殿ランタン2.925ｇ、オキ
シ硝酸ジルコニウム11.303ｇを含有する水溶液
300c.c.を調製し、これを撹拌した4Nアンモニヤ水
１中に滴下して水酸化物の共沈物を作つた。こ
の共沈物の懸濁した水溶液を撹拌しつつ、これに
四塩化チタン8.344ｇを溶解した水溶液100c.c.中に
滴下し、鉛、チタン、ジルコニウム、ランタンの
水酸化物の均密沈殿物を得た。水洗後、800℃で
１時間仮焼してPb0.91La0.09（Zr0.55・Ti0.45）0.97
75O3の組成のPLZT原料粉末を得た。該粉末を電
子顕微鏡により観察したところ、平均粒径約0.2μ
ｍの均一粒子からなつていた。またＸ線回折法に
よる組成変動の測定を行つた結果、組成変動は殆
んど観察されなかつた。鉛を過剰に含まない該粉
末を1.5t／cm2の圧力下で直径12mm、厚さ２mmに成
型し、酸素ガスと鉛蒸気の混合雰囲気下、常圧
1200℃で24時間焼結した。得られた焼結体は透過
度72％で理論透過度にほぼ等しいPLZTセラミツ
クスであつた。Example Aqueous solution containing 30.140 g of lead nitrate, 2.925 g of lanthanum nitrate, and 11.303 g of zirconium oxynitrate
300 c.c. was prepared and added dropwise to 1 part of stirred 4N ammonia water to form a coprecipitate of hydroxide. While stirring the aqueous solution in which this coprecipitate was suspended, 8.344 g of titanium tetrachloride was added dropwise to 100 c.c. of the aqueous solution, resulting in a homogeneous precipitate of hydroxides of lead, titanium, zirconium, and lanthanum. I got it. After washing with water, calcining at 800℃ for 1 hour to obtain Pb 0.91 La 0.09 (Zr 0.55・Ti 0.45 ) 0.97
A PLZT raw powder with a composition of 75 O 3 was obtained. When the powder was observed using an electron microscope, the average particle size was approximately 0.2μ.
It consisted of uniform particles of m. Furthermore, as a result of measuring compositional fluctuations by X-ray diffraction, almost no compositional fluctuations were observed. The powder, which does not contain excessive lead, is molded under a pressure of 1.5 t/cm 2 to a diameter of 12 mm and a thickness of 2 mm, and then molded under a mixed atmosphere of oxygen gas and lead vapor at normal pressure.
Sintered at 1200℃ for 24 hours. The obtained sintered body was PLZT ceramic with a transmittance of 72%, which was almost equal to the theoretical transmittance.
比較例
市販のPbO、TiO2、La2O3、ZrO2各粉末を
（Pb0.91La0.09）（Zr0.55Ti0.45）0.9775O3の組成にな
る
ように配合し、ボールミルで混合後、800℃で約
２時間仮焼し、再びボールミルで粉砕した。該粉
末を電子顕微鏡で観察したところ、二次粒子を含
んだ平均粒径約1.0μｍの不揃いの粒子から構成さ
れていた。またＸ線回折法による組成変動の測定
を行つた結果、かなりの変動が確認された。この
粉末を実施例と同一条件で常圧焼結した結果、殆
んど透光性は認められなかつた。Comparative Example Commercially available PbO, TiO 2 , La 2 O 3 , and ZrO 2 powders were blended to have a composition of (Pb 0.91 La 0.09 ) (Zr 0.55 Ti 0.45 ) 0.9775 O 3 , mixed in a ball mill, and then heated at 800°C. The mixture was calcined for about 2 hours and ground again using a ball mill. When the powder was observed under an electron microscope, it was found to be composed of irregular particles with an average particle diameter of about 1.0 μm, including secondary particles. Furthermore, as a result of measuring compositional fluctuations using X-ray diffraction, considerable fluctuations were confirmed. As a result of pressureless sintering of this powder under the same conditions as in the example, almost no translucency was observed.
発明の効果
本発明の方法によると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 excellent effects.
(1) PLZTの原料成分の内、鉛とTiを共沈させな
いので、チタン原料として安価な四塩化チタン
を使用することができる。(1) Among the raw material components of PLZT, lead and Ti are not co-precipitated, so cheap titanium tetrachloride can be used as a titanium raw material.
(2) PLZTの構成成分の全部を共沈させないで、
二重沈殿を生成させるため、これらの沈殿は相
互分散された状態となり、従来の全成分の共沈
におけるような乾燥、仮焼時に二次粒子の形成
が少ない。従つて高嵩密度の易焼結性のものが
得られる。(2) Without co-precipitating all of the constituent components of PLZT,
Since double precipitates are formed, these precipitates are in a mutually dispersed state, and there is less formation of secondary particles during drying and calcining as in conventional co-precipitation of all components. Therefore, a material with high bulk density and easy sinterability can be obtained.
(3) 二重沈殿生成を行うため、各段階で各成分に
適した沈殿剤の種類及び濃度を選択し得られ、
目的組成のPLZTが容易に得られる。(3) In order to perform double precipitation, the type and concentration of precipitant suitable for each component can be selected and obtained at each stage.
PLZT with the desired composition can be easily obtained.
(4) 従来の乾式法におけるような組成成分の不均
一のない高密度のPLZTの透光性セラミツクス
が容易に得られる。(4) High-density translucent PLZT ceramics can be easily obtained without the non-uniform composition of conventional dry methods.
(5) プロセスが簡単なこと、使用する薬品が安価
なこと、高純度薬品を使用しなくても良いこ
と、単なる固相常圧焼結法でも透光性が達成で
きることなどの理由により、高性能透光性
PLZTセラミツクスを極めて安価に製造でき
る。(5) The process is simple, the chemicals used are inexpensive, there is no need to use high-purity chemicals, and translucency can be achieved even with a simple solid-state pressureless sintering method. Performance translucency
PLZT ceramics can be manufactured at extremely low cost.
Claims (1)
Lax）〔（Zry・Ti1-y）1-x/4□x/4〕O3、（Pb1-3x/2□x
/2
Lax）（Zry・Ti1-y）O3（ただし、ｘ＝0.01〜0.3、
ｙ＝0.05〜0.95、□は陽イオン空孔を表わす）ま
たは両者の中間組成体、もしくはこれらの組成に
10wt％以下の鉛を過剰に添加した粉末を焼結す
ることによる透光性PLZTセラミツクスの製造に
おいて、 (1) 鉛、ランタン、ジルコニウム、チタン四成分
の水溶液を作り、ランタン水溶液とジルコニウ
ム水溶液を鉛水溶液もしくはチタン水溶液のい
ずれか一方に混合して二種類の水溶液とし、そ
の内一種の水溶液に過剰の沈殿形成液を混合し
て沈殿を形成させた後、この沈殿の分散した水
溶液に残つた他の水溶液を均一に混合して全成
分の均密沈殿を作り、これを500〜1100℃で仮
焼し、 (2) 次いで、仮焼物を成形後、1000〜1280℃で空
気中か酸素雰囲気中でホツトプレスするか、あ
るいは酸素と鉛蒸気の混合雰囲気下で常圧焼結
することを特徴とする透光性セラミツクスの製
造法。[Claims] 1 General formula (Pb 1-x
La x ) [(Zr y・Ti 1-y ) 1-x/4 □ x/4 ] O 3 , (Pb 1-3x/2 □ x
/2
La x ) (Zr y・Ti 1-y ) O 3 (where x=0.01~0.3,
y = 0.05 to 0.95, □ represents a cation vacancy) or an intermediate composition of both, or a composition of these
In the production of translucent PLZT ceramics by sintering powder to which lead is added in excess of 10 wt% or less, (1) an aqueous solution of four components of lead, lanthanum, zirconium, and titanium is made, and a lanthanum aqueous solution and a zirconium aqueous solution are mixed with lead. After mixing with either an aqueous solution or a titanium aqueous solution to form two types of aqueous solutions, and forming a precipitate by mixing an excess precipitate-forming liquid with one of the aqueous solutions, the remaining aqueous solution in which this precipitate is dispersed. (2) After the calcined product is molded, it is heated at 1000 to 1280°C in air or in an oxygen atmosphere. A method for producing translucent ceramics, which is characterized by hot-pressing or pressureless sintering in a mixed atmosphere of oxygen and lead vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59228760A JPS61106457A (en) | 1984-10-30 | 1984-10-30 | Manufacture of plzt light permeable ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59228760A JPS61106457A (en) | 1984-10-30 | 1984-10-30 | Manufacture of plzt light permeable ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61106457A JPS61106457A (en) | 1986-05-24 |
| JPS6363512B2 true JPS6363512B2 (en) | 1988-12-07 |
Family
ID=16881395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59228760A Granted JPS61106457A (en) | 1984-10-30 | 1984-10-30 | Manufacture of plzt light permeable ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61106457A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62105927A (en) * | 1985-10-14 | 1987-05-16 | Natl Inst For Res In Inorg Mater | Production of ceramic powder having electro-optical properties |
| JPS6330365A (en) * | 1986-07-23 | 1988-02-09 | 新日本製鐵株式会社 | Manufacture of plzt light-transmitting ceramics |
| JP2647436B2 (en) * | 1988-05-25 | 1997-08-27 | 住友大阪セメント株式会社 | PLZT synthesis method |
-
1984
- 1984-10-30 JP JP59228760A patent/JPS61106457A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61106457A (en) | 1986-05-24 |
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