JPH01298064A - Production of plzt - Google Patents
Production of plztInfo
- Publication number
- JPH01298064A JPH01298064A JP63128620A JP12862088A JPH01298064A JP H01298064 A JPH01298064 A JP H01298064A JP 63128620 A JP63128620 A JP 63128620A JP 12862088 A JP12862088 A JP 12862088A JP H01298064 A JPH01298064 A JP H01298064A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- plzt
- precipitate
- components
- calcined
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000002244 precipitate Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 238000007580 dry-mixing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 11
- UKDYPJBSLOCNRU-UHFFFAOYSA-J ethanol tetrachlorotitanium Chemical compound CCO.Cl[Ti](Cl)(Cl)Cl UKDYPJBSLOCNRU-UHFFFAOYSA-J 0.000 description 9
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000004679 hydroxides Chemical class 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 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 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids 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
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 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
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 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
- -1 oxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ＰＬＺＴの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing PLZT.
ＰＬＺＴは、偏光素子、光シャッタ、画像記↑９素子な
どのオプトエレクトロニクス材料として広範囲の応用が
期待されている。PLZT is expected to have a wide range of applications as an optoelectronic material such as polarizing elements, optical shutters, and image recording elements.
ＰＬＺＴは、工業的には構成原料粉末を混合、仮焼し、
得られた粉末を成形後焼結するいわゆる乾式法によって
製造される。PLZT is produced industrially by mixing and calcining constituent raw material powders,
It is manufactured by a so-called dry method in which the obtained powder is molded and then sintered.
しかし、これら原料粉末の特性が十分でない場合には、
粉末特性の良いＰＬＺＴ粉末を得ることは難しい。However, if the characteristics of these raw material powders are not sufficient,
It is difficult to obtain PLZT powder with good powder properties.
例えばＺｒ（ジルコニウム）原料粉末は特に凝集し易い
ことが知られており、単分散したサブミクロン級の粉末
特性の良いものを得ることは難しい。このような凝集し
た原料粉末を使用して乾式法でＰＬＺＴ粉末を作成して
も、その平均粒径はせいぜい２μｍ程度で、これを焼結
しても高密度かつ透光性に優れ、光学的に均一なＰＬＺ
Ｔを得ることは難しい。For example, it is known that Zr (zirconium) raw material powder is particularly prone to agglomeration, and it is difficult to obtain a monodispersed submicron powder with good properties. Even if PLZT powder is made by a dry method using such agglomerated raw material powder, the average particle size is about 2 μm at most, and even if it is sintered, it has high density, excellent translucency, and optical properties. Uniform PLZ
It's difficult to get T.
一方、アルコキシド法、共沈法などの湿式法で粉末を作
成すれば、サブミクロン級の易焼結性粉末が得られる場
合があるが、乾式法によるものに比べて高価になり、ま
た操作も面倒である欠点がある。On the other hand, if powder is prepared using a wet method such as an alkoxide method or a coprecipitation method, submicron-level easily sinterable powder may be obtained, but it is more expensive than a dry method and is more difficult to operate. It has the disadvantage of being troublesome.
〔発明が解決しようとする課題］
本発明はＺｒ（ジルコニウム）のような粉末特性の悪い
原料粉末を用いてＰＬＺＴの乾式法による合成における
欠点を解消すべくなされたもので、その目的は原料粉末
の一部を多段湿式法によって分散性の優れたサブミクロ
ン級の変成酸化物粉末となし、残部原料を単なる乾式法
によって、変成酸化物粉末に添加することによって、サ
ラ゛ミクロン級の易焼結性で均一なＰＬＺＴ粉末とし、
更にこれを焼結して高密度でかつ透光性に優れ光学的に
均一なＰＬＺＴを製造する方法を提供することにある。[Problems to be Solved by the Invention] The present invention was made in order to solve the drawbacks in the dry synthesis of PLZT using a raw material powder with poor powder properties such as Zr (zirconium). A part of the raw material is made into a submicron-grade modified oxide powder with excellent dispersibility using a multi-stage wet method, and the remaining raw material is added to the modified oxide powder using a simple dry method to easily sinter the submicron-class powder. PLZT powder with uniform properties,
Furthermore, it is an object of the present invention to provide a method for producing optically uniform PLZT with high density and excellent translucency by sintering the same.
〔課題を解決するための手段及び作用〕本発明者等は前
記目的を達成すべく鋭意研究の結果、一般式
％式％
示されるＰＬＺＴの製造方法において、ＰＬＺＴを構成
する少な（ともジルコニウムを含む溶液（被変成成分溶
液）及びＰｂ、Ｌａ、Ｔｉのうち少なくとも一種の成分
の溶液（変成成分溶液）を作成する。[Means and Effects for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have developed a method for manufacturing PLZT shown by the general formula %. A solution (solution of component to be modified) and a solution of at least one component among Pb, La, and Ti (solution of component to be modified) are prepared.
次いで、これらいずれかの二種の溶液を二つの段階に分
けて沈殿形成液と順次混合して均密沈殿を作るか、ある
いは二種の溶液から別個に沈殿形成液を混合して沈殿を
形成後混合することにより均密沈殿を作り、均密沈殿を
洗浄、乾燥後、４００〜１４００℃で仮焼すると、凝集
の極めて少ないサブミクロン級の変成酸化物粉末が得ら
れることをｌＩＮ認した。Next, either of these two types of solutions are divided into two stages and mixed with a precipitate forming liquid in order to form a homogeneous precipitate, or a precipitate is formed by separately mixing the precipitate forming liquid from the two types of solutions. It has been confirmed that by post-mixing to form a homogeneous precipitate, washing and drying the homogeneous precipitate, and calcining at 400 to 1400°C, a submicron-grade modified oxide powder with extremely little agglomeration can be obtained.
これを原料とし、目的とするＰＬＺＴ組成を得るため、
残りの化合物粉末を乾式法によって混合し、仮焼すると
サブミクロン級の粉末特性（易焼結性、高嵩密度）の優
れたＰＬＺＴ粉末が得られ、これを成形、焼結すると、
ホットプレスやＨＩＰなどの操作を省略しても高密度で
透光性に優れ、光学的に均一なＰＬＺＴが容易に得られ
ることを究明した。In order to obtain the desired PLZT composition using this as a raw material,
The remaining compound powder is mixed by a dry method and calcined to obtain a PLZT powder with excellent submicron powder properties (easy sinterability, high bulk density), which is then molded and sintered.
It has been found that optically uniform PLZT with high density and excellent translucency can be easily obtained even if operations such as hot pressing and HIP are omitted.
〔第１実施例〕
四塩化チタンエタノール溶液（１，０ｍｏｆｆｉ／ｌ濃
度）４０．０Ｏｃｃ、及びオキシ硝酸ジルコニウム水溶
液（１，０ｍｏＥ／ｌ濃度）２６０．０ｃｃを用意した
。[First Example] 40.0 cc of a titanium tetrachloride ethanol solution (1.0 moffi/l concentration) and 260.0 cc of a zirconium oxynitrate aqueous solution (1.0 moE/l concentration) were prepared.
ここで、四塩化チタンエタノール溶液は、、ＰＬＺＴを
構成するＴｉ成分の必要全量でなく、適量を含んでおり
、一方オキシ硝酸ジルコニウム水溶液はＰＬＺＴを構成
するＺｒ成分の必要全量を含んでいる。四塩化チタン水
溶液を撹拌している６Ｎ−アンモニア水（沈殿形成液）
１ρ中に徐々に添加してＴｉ”の水酸化物沈殿を形成後
、撹拌を続行しつつオキシ硝酸ジルコニウム水溶液を添
加してＴｉ”とＺｒ”の水酸化物の均密沈殿を生成させ
た。これを洗浄、乾燥後、１１２０℃で仮焼して（Ｔ
ｉｏ、ｚ Ｚ ｒｏ、、ｅ） ０２組成の変成酸化物粉
末を作成した。この粉末の一次粒子の平均径は０．２μ
ｍで殆ど単分散状態であった。Here, the titanium tetrachloride ethanol solution contains not the entire required amount of the Ti component constituting PLZT, but an appropriate amount, while the zirconium oxynitrate aqueous solution contains the necessary total amount of the Zr component constituting PLZT. 6N-ammonia water (precipitation forming liquid) stirring titanium tetrachloride aqueous solution
After hydroxide precipitates of Ti'' were formed by gradually adding the hydroxides into 1ρ, an aqueous solution of zirconium oxynitrate was added while stirring to form a homogeneous precipitate of hydroxides of Ti'' and Zr''. After washing and drying, this was calcined at 1120°C (T
io, z Z ro,, e) A modified oxide powder having a composition of 02 was created. The average diameter of the primary particles of this powder is 0.2μ
It was almost monodispersed at m.
変成酸化物粉末９．０９８３ ｇと市販のＴｉＯ□微粒
子（Ｔｉ成分の残りを含む）１．４６４４ｇ。9.0983 g of modified oxide powder and 1.4644 g of commercially available TiO□ fine particles (including the remainder of the Ti component).
ＰｂＯ粉末（平均粒径１．５ ｕｍ） ２１．７６６
ｇ。PbO powder (average particle size 1.5 um) 21.766
g.
Ｌａ、０３微粒子１．４６６２ ｇをボールミルで一昼
夜混合粉砕した後、７４０℃で１時間仮焼して（Ｐ ｂ
ｏ、ｑ＋ Ｌ ａ ０．０９）（Ｚ ｒ ｏ、ｂｓ
Ｔ ｉ ｏ、５ｓ）ｏ、ｑｔ７ｓ０３粉末を得た。その
平均粒径は０．２５μｍの単分散粒子であった。After mixing and pulverizing 1.4662 g of La, 03 fine particles overnight in a ball mill, the mixture was calcined at 740°C for 1 hour (Pb
o, q+ L a 0.09) (Z r o, bs
Tio, 5s)o, qt7s03 powder was obtained. The average particle size was monodisperse particles of 0.25 μm.
得られた粉末を１ ｔｏｎ ／ ｃｒＭの圧力で成形後
、鉛蒸気、酸素ガス共存雰囲気下、１２００℃で１０時
間焼結した結果、その密度は７．８１に達し、理論密度
（７，８４）に極めて近い値であった。また光透過率は
波長６００ｎｍの光を用い、サンプル厚み５００μｍで
約６０％で理論透過率に極めて近い値であった。The obtained powder was molded at a pressure of 1 ton/crM and then sintered at 1200°C for 10 hours in an atmosphere coexisting with lead vapor and oxygen gas, resulting in a density of 7.81, which is the theoretical density (7,84). The value was extremely close to . Further, the light transmittance was approximately 60% using light with a wavelength of 600 nm and a sample thickness of 500 μm, which was a value extremely close to the theoretical transmittance.
〔第２実施例〕
硝酸鉛水溶液（１ｍｏｊｌ！／ｆ濃度）９１．０ｃｃ、
硝酸ランタン水溶液（０，２５ｍｏｆｆ ／ ｌ′ａ度
）３６．０ＣＣ，オキシ硝酸ジルコニウム水溶液（１ｍ
ｏｌ／Ａ濃度）６３．５３８ｃｃ、四塩化チタンエタノ
ール溶液（０，５ｍｏρ／ｌ濃度）２９．３２５ｃｃを
作成した。[Second Example] Lead nitrate aqueous solution (1 mojl!/f concentration) 91.0 cc,
Lanthanum nitrate aqueous solution (0.25 moff / l'a degree) 36.0CC, zirconium oxynitrate aqueous solution (1 m
ol/A concentration) and 29.325 cc of titanium tetrachloride ethanol solution (0.5 moρ/l concentration) were prepared.
ここで、硝酸鉛水溶液は、ＰＬＺＴを構成するために必
要全量のＰｂ成分を含み、同様に硝酸ランタン水溶液は
必要全量のＬａ成分を含み、硝酸ジルコニウム水溶液は
必要全量のＺｒ成分を含む。Here, the lead nitrate aqueous solution contains the entire necessary amount of Pb component to constitute PLZT, similarly, the lanthanum nitrate aqueous solution contains the necessary total amount of La component, and the zirconium nitrate aqueous solution contains the necessary total amount of Zr component.
四塩化チタンエタノール溶液は必要全量でなく、適量の
Ｔｉ成分を含む。硝酸鉛水溶液と硝酸ランタン水溶液を
混合し、オキシ硝酸ジルコニウム水溶液と四塩化チタン
エタノール溶液を混合した。The titanium tetrachloride ethanol solution contains an appropriate amount of Ti component, not the entire required amount. A lead nitrate aqueous solution and a lanthanum nitrate aqueous solution were mixed, and a zirconium oxynitrate aqueous solution and a titanium tetrachloride ethanol solution were mixed.
硝酸鉛、硝酸ランタン混合水溶液を撹拌した６Ｎ−アン
モニア水沈殿形成液ｌｌ中に徐々に添加して、ｐｂ”と
Ｌａ”の水酸化物の均密沈殿を形成後、撹拌を続行しつ
つ、オキシ硝酸ジルコニウム水溶液と、四塩化チタンエ
タノール溶液の混合溶液を添加して、Ｐｂ”、Ｌａ３°
、Ｚｒ’°、Ｔｉ”の水酸化物の均密沈殿を生成させた
。これを洗浄、乾燥後、９５０℃で仮焼して、（Ｐ ｂ
ｏ、ｑ＋ Ｌ ａｏ、ｏＪ（Ｚ ｒ ｏ、ｂ、Ｔ ！
ｏ、＋ｓ）ｏ、ｑｑｙｓ Ｏｚ、ｂＭｉ成の変成酸化
物粉末を作成した。この粉末の一次粒子の平均粒径は、
０．２３μｍで殆ど単分散状態であった。A mixed aqueous solution of lead nitrate and lanthanum nitrate was gradually added to the stirred 6N ammonia water precipitation forming solution to form a homogeneous precipitate of pb" and La" hydroxides. By adding a mixed solution of zirconium nitrate aqueous solution and titanium tetrachloride ethanol solution, Pb'', La3°
A homogeneous precipitate of hydroxides of , Zr'°, Ti'' was formed. After washing and drying, this was calcined at 950°C to form (P b
o, q+ L ao, oJ (Z r o, b, T!
o, +s) o, qqys Oz, bMi modified oxide powder was created. The average particle size of the primary particles of this powder is
It was 0.23 μm and almost monodispersed.
変成酸化物粉末３０．７６３ ｇと市販のＴｉｅ。30.763 g of modified oxide powder and commercially available Tie.
微粒子１．５６２ ｇをボールミルで一昼夜混合粉砕し
た後、７４０℃で１時間仮焼して、（Ｐｂ−、ｑ＋Ｌ
ａ Ｏ，０９）（Ｚ ｒ ｏ、ｂｓ Ｔ ｉ ｏ、５ｓ
）ｏ、ｑｔｑｓ Ｃ）＋粉末を得た。このＰＬＺＴ粉末
の平均粒子径は０．２７μｍで、単分散粒子であった。After mixing and pulverizing 1.562 g of fine particles in a ball mill overnight, they were calcined at 740°C for 1 hour to obtain (Pb-, q+L
a O, 09) (Z r o, bs T io, 5s
) o, qtqs C) + powder was obtained. The average particle diameter of this PLZT powder was 0.27 μm, and it was a monodisperse particle.
得られたＰＬＺＴ粉末を、１ｔｏｎ／ｃ＋ｆｌで成形後
、鉛蒸気酸素ガス共存雰囲気下、１２００℃で１０時間
焼結した。得られた焼結体の密度は７．８０で、これは
、理論密度に極めて近い値であった。また透光率は、波
長６００ｎｍの光を用い、サンプル厚み５００μｍで約
６０％であり、理論透過率に極めて近い値であった。The obtained PLZT powder was molded at 1 ton/c+fl, and then sintered at 1200° C. for 10 hours in an atmosphere containing lead vapor and oxygen gas. The density of the obtained sintered body was 7.80, which was very close to the theoretical density. Further, the light transmittance was about 60% using light with a wavelength of 600 nm and a sample thickness of 500 μm, which was a value extremely close to the theoretical transmittance.
〔比較例〕
市販のＰｂＯ，ＬａｚＯｉ、Ｚｒ０ｚ、Ｔ ｉｏｚの各
粉末を、（Ｐ ｂ Ｏ（１，９１Ｌ ａ Ｏ，０９）（
Ｚ ｒ ｏ、ｂｓＴ ｉ ａ、 ３ｓ） ｏ、ｑｑｌ、
０３の組成になるように配合し、ボールミルで一昼夜混
合、粉砕した後８５０℃で２時間仮焼した。仮焼時の粉
末の平均粒径は２．８μｍであった。該粉末をｌ ｔ
ｏｎ／ｃｆｆｌで成形し、第１実施例と同じ条件下で焼
結した。得られた焼結体の密度は、７．６程度であった
。また、透光性は得られなかった。[Comparative example] Commercially available powders of PbO, LazOi, ZrOz, and Tioz were mixed into (PbO(1,91L aO,09)(
Z r o, bsT i a, 3s) o, qql,
The mixture was blended to have a composition of 03, mixed overnight in a ball mill, pulverized, and then calcined at 850° C. for 2 hours. The average particle size of the powder during calcination was 2.8 μm. The powder is
on/cffl and sintered under the same conditions as the first example. The density of the obtained sintered body was about 7.6. Moreover, translucency was not obtained.
〔第３実施例〕
第１実施例と同様に四塩化チタンエタノール溶液とオキ
シ硝酸ジルコニウム水溶液を作成し、用意した。[Third Example] A titanium tetrachloride ethanol solution and a zirconium oxynitrate aqueous solution were prepared in the same manner as in the first example.
次に四塩化チタンエタノール溶液を攪拌している６Ｎ−
アンモニア水ｌｌ中に徐々に添加して、Ｔｉ”の水酸化
物沈殿を形成した。また、別の容器を用いてオキシ硝酸
ジルコニウム水溶液を攪拌している６Ｎ−アンモニア水
１１中に徐々に添加してＺｒ”の水酸化物沈殿を形成し
た。Next, the titanium tetrachloride ethanol solution is stirred with 6N-
Aqueous zirconium oxynitrate was gradually added to 1 liter of ammonia water to form a Ti'' hydroxide precipitate. Using another container, an aqueous solution of zirconium oxynitrate was gradually added to 11 liters of 6N ammonia water while stirring. A hydroxide precipitate of Zr was formed.
ついで、両方の水酸化物沈殿を含む溶液を攪拌しながら
混合し、Ｔｉ４°とＺｒ”の水酸化物の均密沈殿を生成
させた。これを洗浄、乾燥後、１１２０℃で仮焼して（
Ｔ ｉｏ、ｚ Ｚ ｒｏ、ｓ） Ｏｚ組成の変成酸化物
粉末を作成した。この粉末の平均粒径は、０．２μｍで
ほとんど単分散状態であった。以下第１実施例と同様に
ＰＬＺＴ粉末を作成し、これを用いてＰＬＺＴを作成し
た。Next, the solutions containing both hydroxide precipitates were mixed with stirring to form a homogeneous precipitate of Ti4° and Zr'' hydroxides. After washing and drying, this was calcined at 1120°C. (
A modified oxide powder having a composition of T io, z Z ro, s) Oz was created. This powder had an average particle size of 0.2 μm and was almost monodispersed. Thereafter, PLZT powder was prepared in the same manner as in the first example, and PLZT was prepared using this powder.
得られた磁器の密度は７．８４で、理論密度に近い値で
あった。The density of the obtained porcelain was 7.84, which was close to the theoretical density.
第３実施例では、Ｔｉを用いてＺｒの変成酸化物粉末を
作成したが、四塩化チタンエタノール溶液の代わりに硝
酸鉛水溶液を用い、Ｐｂを用いて変成酸化物粉末を作成
してもよい。In the third embodiment, a Zr modified oxide powder was created using Ti, but a lead nitrate aqueous solution may be used instead of the titanium tetrachloride ethanol solution, and a modified oxide powder may be created using Pb.
なお、ＰＺＬＴにおいては、その焼結性や特性を改善す
るために、微量の助剤を添加する場合がある。これらの
助剤は湿式部分の工程で溶液の形として、または乾式的
に適宜添加すればよい。ＰＬＺＴ構成部分、Ｐｂ、Ｌａ
、Ｚｒ、Ｔｉの化合物の水またはアルコール溶液を作成
するための化合物としては、それらの硫酸塩、硝酸塩、
塩化物、オキシ硝酸塩、オキシ塩化物、水酸化物、酸化
物、ギ酸塩、しゅう酸塩、炭酸塩及び金属などが挙げら
れる。これらが水またはアルコールに可溶でないときは
適宜鉱酸等を加えて可溶とすることができる。Note that a small amount of auxiliary agent may be added to PZLT in order to improve its sinterability and properties. These auxiliary agents may be added as appropriate in the form of a solution in the wet part process or in a dry process. PLZT component, Pb, La
, Zr, Ti compounds for preparing water or alcohol solutions include their sulfates, nitrates,
Examples include chlorides, oxynitrates, oxychlorides, hydroxides, oxides, formates, oxalates, carbonates and metals. If these are not soluble in water or alcohol, they can be made soluble by appropriately adding mineral acids or the like.
湿式部分の工程は原則として水溶液またはアルコール溶
液で行うが、アルコキシド溶液で行ってもよい。In principle, the wet part process is carried out using an aqueous solution or an alcohol solution, but it may also be carried out using an alkoxide solution.
沈殿形成液の試薬としては、例えば、アンモニヤ、炭酸
アンモニウム、苛性アルカリ、しゅう酸、しゅう酸アン
モニウムなどの他、アミン酸、水酸化テトラメチルアン
モン、尿素などの有機試薬が挙げられる。しかし、これ
に限定されるものではない。Examples of reagents for the precipitation forming solution include ammonia, ammonium carbonate, caustic alkali, oxalic acid, ammonium oxalate, and organic reagents such as amino acid, tetramethylammonium hydroxide, and urea. However, it is not limited to this.
湿式部分の工程の沈殿形成に用いる沈殿形成液の種類は
一つのプロセスにおいても一種に限定されるものではな
い。The type of precipitate forming liquid used for precipitate formation in the wet part process is not limited to one type even in one process.
また沈殿形成を沈殿形成液を用いない方法、例えば加水
分解法、噴霧分解法等によって行ってもよい。Precipitate formation may also be carried out by a method that does not use a precipitate-forming liquid, such as a hydrolysis method or a spray decomposition method.
変成酸化物粉末を作成するために添加される変成成分の
種類と量は、該変成成分の添加によって得られる変成酸
化物粉末の凝集を抑制して得られるものであることが必
要である。The type and amount of the metamorphic component added to create the metamorphic oxide powder must be such that it can suppress agglomeration of the metamorphic oxide powder obtained by adding the metamorphic component.
変成酸化物粉未作成のための仮焼塩度は４００〜１４０
０ ℃であることが好ましい。４００℃より低いと凝集
が起こり易くなり、１４００℃を越えると粒子が粗大化
する傾向がある。このようにして得られた変成酸化物粉
末に、目的とするＰＬＺＴ組成を達成するために必要な
成分の全量に相当する化合物粉末を混合する。The calcining salinity is 400 to 140 for not creating modified oxide powder.
Preferably it is 0°C. If the temperature is lower than 400°C, aggregation tends to occur, and if it exceeds 1400°C, the particles tend to become coarse. The thus obtained modified oxide powder is mixed with a compound powder corresponding to the total amount of the components necessary to achieve the desired PLZT composition.
この場合、添加混合する化合物粉末は、市販されている
サブミクロン級のものであることが好ましい。In this case, the compound powder to be added and mixed is preferably a commercially available submicron grade powder.
ただし、酸化鉛はある程度粗大なものであっても、得ら
れるＰＬＺＴ粉末の特性には悪い影響を与えない。However, even if lead oxide is coarse to some extent, it does not have a negative effect on the properties of the obtained PLZT powder.
仮焼温度は、各構成成分の組成比により４００〜１４０
０℃の範囲で大幅に変化する。要は固相反応が完了する
最低温度以上で、顕著な粒子成長が生じない温度の範囲
で仮焼すればよい。The calcination temperature ranges from 400 to 140 depending on the composition ratio of each component.
It changes significantly in the 0°C range. In short, calcination may be carried out at a temperature not lower than the minimum temperature at which the solid phase reaction is completed and at which no significant particle growth occurs.
焼結温度は仮焼温度の場合と同様に各構成成分の組成比
によって異なる。−船釣に７００〜１５００℃である。As with the calcination temperature, the sintering temperature varies depending on the composition ratio of each component. - 700-1500°C for boat fishing.
７００″Ｃより低いと焼結が不十分であり、１５００℃
を越えると粒子が粗大化したり、成分の揮発が起こる。If the temperature is lower than 700"C, sintering is insufficient, and if the temperature is lower than 1500"C.
If it exceeds this, the particles will become coarse and the components will volatilize.
本発明の方法によると、ＰＬＺＴの構成成分の二種以上
を含む変成酸化物粉末（例えばチタンで変成したジルコ
ニウム粉末）は、はぼ単分散したサブミクロン級の均一
粒子として得られる。それは多段に沈殿を形成させるの
で、この沈殿は多相の高度に相互に分散した状態となり
、その結果、乾燥工程、仮焼工程で凝集しにく（なるた
めである。この粉末を使用することによって、以後単な
る乾式法によって容易にサブミクロン級の易焼結性、高
嵩密度のＰＬＺＴ粉末が得られる。従来、乾式法によっ
てはせいぜい２μｍ程度の粉末しか得られなかった現状
において、このことは画期的なことである。更にこのよ
うなサブミクロン級の単分散Ｐ Ｌ Ｚ Ｔ粉末を成形
・焼結することによってほぼ理論密度に近い高密度で透
光性に優れ、光学的に均一なＰＬＺＴが得られる。According to the method of the present invention, a modified oxide powder (for example, zirconium powder modified with titanium) containing two or more of the constituent components of PLZT is obtained as substantially monodispersed submicron-level uniform particles. Since it forms a precipitate in multiple stages, this precipitate becomes a multi-phase, highly interdispersed state, and as a result, it is difficult to agglomerate during the drying and calcination steps. Therefore, PLZT powder with submicron level easy sinterability and high bulk density can be easily obtained by a simple dry method.In the current situation where dry methods could only obtain powders of about 2 μm at most, this is This is groundbreaking.Furthermore, by molding and sintering such submicron-level monodisperse PLZT powder, it is possible to create a material with high density close to the theoretical density, excellent translucency, and optically uniform properties. PLZT is obtained.
このような効果のほか、次のよ・うな効果も得られる。In addition to these effects, you can also obtain the following effects.
（１）仮焼によって得られたままの変成酸化物粉末は、
多少の凝集が認められる場合があるが、その妨集力は極
めて弱いので、これを成分化合物とボールミル等での混
合粉砕過程で容易に単分散状態となし得る。従って、変
成酸化物を仮焼したままで市場に供給し得られ、それだ
けＰＬＺＴ粉末の低コスト化が達成される。(1) The modified oxide powder as obtained by calcination is
Although some agglomeration may be observed, since its blocking force is extremely weak, it can be easily made into a monodisperse state by mixing and pulverizing the component compounds in a ball mill or the like. Therefore, the modified oxide can be supplied to the market in its calcined state, and the cost of PLZT powder can be reduced accordingly.
（２）本発明の方法で得られるＰＬＺＴ粉末は仮焼によ
って単分散状態で得られるもので、粉砕工程を省略して
も十分易焼結性で且つ高嵩密度のものとなし得る。(2) The PLZT powder obtained by the method of the present invention is obtained in a monodisperse state by calcination, and can be made to have sufficient sinterability and high bulk density even if the pulverization step is omitted.
（３）極めて高密度、高透光率、光学的均一性が要求さ
れるＰ Ｌ Ｚ Ｔにおいて、ＨＴＰやホットプレスな
どの操作を必要とせず、単なる常圧焼結によって理論密
度に近いセラミックスを得ることができる。(3) In PLZT, which requires extremely high density, high light transmittance, and optical uniformity, ceramics with a density close to the theoretical density can be produced by simple pressureless sintering without the need for operations such as HTP or hot pressing. Obtainable.
（４）本発明で得られる変成酸化物粉末は十分な均一性
を有し、これに乾式法で混合、仮焼して得られるＰＬＺ
Ｔ粉末は従来の共沈法やアルコキシド法由来のものに匹
敵する均一性を存する。(4) The modified oxide powder obtained in the present invention has sufficient uniformity, and the PLZ obtained by mixing and calcining it by a dry method
The T powder has a uniformity comparable to that derived from conventional coprecipitation and alkoxide methods.
代理人弁理士 岡 部 隆Representative Patent Attorney Takashi Okabe
Claims (2)
Ｔｉのうち、少なくとも一種の成分の必要全量でない適
量を含む溶液を作成し、 前記溶液の一方から沈殿を形成し、次いで前記溶液の他
方を混合して少なくとも二種の成分を含む均密沈殿を形
成し、 得られた均密沈殿を洗浄、乾燥後、４００〜１４００℃
で仮焼し、変成酸化物粉末を作成し、この変成酸化物粉
末と、ＰＬＺＴ組成の残りの構成成分の化合物を乾式混
合して４００〜１４００℃で仮焼し、 得られた仮焼粉末を成形し７００〜１５００℃で焼成す
ることを特徴とするＰＬＺＴの製造方法。(1) A solution containing the required total amount of Zr components and Pb, La,
Prepare a solution containing an appropriate amount, but not the entire amount, of at least one component of Ti, form a precipitate from one of the solutions, and then mix the other solution to form a homogeneous precipitate containing at least two components. After washing and drying the resulting homogeneous precipitate, heat at 400 to 1400°C.
The modified oxide powder is dry-mixed with the compounds of the remaining components of the PLZT composition, and the resulting calcined powder is calcined at 400 to 1400°C. A method for manufacturing PLZT, which comprises molding and firing at 700 to 1500°C.
Ｔｉのうち少なくとも一種の成分の必要全量でない適量
を含む溶液を作成し、 前記溶液の一方から沈殿を形成し、前記溶液の他方と沈
殿形成液とから沈殿を形成し、これらを混合して少なく
とも二種の成分を含む均密沈殿を形成し、得られた均密
沈殿を洗浄、乾燥後、４００〜１４００℃で仮焼し、変
成酸化物粉末を作成し、 この変成酸化物粉末と、ＰＬＺＴ組成の残りの構成成分
の化合物を乾式混合して４００〜１４００℃で仮焼し、 得られた仮焼物を成形し７００〜１５００℃で焼成する
ことを特徴とするＰＬＺＴの製造方法。(2) A solution containing the required total amount of Zr components and Pb, La,
A solution containing an appropriate amount other than the total amount of at least one component of Ti is prepared, a precipitate is formed from one side of the solution, a precipitate is formed from the other side of the solution and a precipitate forming liquid, and these are mixed to form at least one of the components. A homogeneous precipitate containing two types of components is formed, and the resulting homogeneous precipitate is washed, dried, and then calcined at 400 to 1400°C to create a modified oxide powder. This modified oxide powder and PLZT A method for producing PLZT, which comprises dry mixing the remaining components of the composition, calcining the mixture at 400 to 1400°C, shaping the resulting calcined product, and firing at 700 to 1500°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128620A JPH01298064A (en) | 1988-05-26 | 1988-05-26 | Production of plzt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63128620A JPH01298064A (en) | 1988-05-26 | 1988-05-26 | Production of plzt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01298064A true JPH01298064A (en) | 1989-12-01 |
Family
ID=14989296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63128620A Pending JPH01298064A (en) | 1988-05-26 | 1988-05-26 | Production of plzt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01298064A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6287460A (en) * | 1985-10-11 | 1987-04-21 | 住友精化株式会社 | Manufacture of plzt light transparent ceramics |
| JPS62105927A (en) * | 1985-10-14 | 1987-05-16 | Natl Inst For Res In Inorg Mater | Production of ceramic powder having electro-optical properties |
| JPS63156057A (en) * | 1986-12-19 | 1988-06-29 | 科学技術庁無機材質研究所長 | Manufacture of high density perovskite ceramics |
-
1988
- 1988-05-26 JP JP63128620A patent/JPH01298064A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6287460A (en) * | 1985-10-11 | 1987-04-21 | 住友精化株式会社 | Manufacture of plzt light transparent ceramics |
| JPS62105927A (en) * | 1985-10-14 | 1987-05-16 | Natl Inst For Res In Inorg Mater | Production of ceramic powder having electro-optical properties |
| JPS63156057A (en) * | 1986-12-19 | 1988-06-29 | 科学技術庁無機材質研究所長 | Manufacture of high density perovskite ceramics |
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