JPH042658A - High-strength colored zirconia sintered material and production thereof - Google Patents
High-strength colored zirconia sintered material and production thereofInfo
- Publication number
- JPH042658A JPH042658A JP2099289A JP9928990A JPH042658A JP H042658 A JPH042658 A JP H042658A JP 2099289 A JP2099289 A JP 2099289A JP 9928990 A JP9928990 A JP 9928990A JP H042658 A JPH042658 A JP H042658A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- mol
- stabilizer
- burning
- powder
- 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.)
- Granted
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 8
- 239000011787 zinc oxide Substances 0.000 claims 4
- 150000002123 erbium compounds Chemical class 0.000 claims 2
- 238000007493 shaping process Methods 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 18
- 239000003086 colorant Substances 0.000 abstract description 11
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002706 hydrostatic effect Effects 0.000 abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910009523 YCl3 Inorganic materials 0.000 abstract 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 abstract 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 abstract 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカラージルコニア焼結体に関し、特に、ピンク
色で低温焼結性のジルコニア焼結体に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a colored zirconia sintered body, and particularly to a pink zirconia sintered body that is sinterable at low temperatures.
〔従来の技術と発明が解決しようとする課題〕ジルコニ
ア焼結体、特に正方品ジルコニア焼結体はその高い強度
と鏡面研磨後の表面光沢の美しさから刃物等の家庭用品
やゴルフシューズスパイク等のスポーツ用品への応用が
進んでいるが、時計ケースやアクセサリ−等の装飾部材
への応用も広がりをみせている。こうした広がる用途に
対応するためには、各種のカラーを持ったカラージルコ
ニアが要望されている。特に女性用の製品の場合、赤や
ピンク色のカラーが好まれるがこう、したカラーのジル
コニアは余り報告されていない。通常、カラージルコニ
アの製造方法としては、安定化したジルコニアに顔料（
主に酸化物）を添加混合して焼結する方法（特開昭５９
−１０５０５５）や、安定化剤とともに少量の着色剤（
主に稀土類）を共沈法等で固溶させる方法（特開昭６２
５９５７１）等が粉末の製造方法として知られている。[Prior art and problems to be solved by the invention] Zirconia sintered bodies, especially square zirconia sintered bodies, are used for household items such as knives, golf shoe spikes, etc. due to their high strength and beautiful surface gloss after mirror polishing. Although its application to sporting goods is progressing, its application to decorative parts such as watch cases and accessories is also expanding. In order to meet these expanding uses, colored zirconia with various colors is required. Particularly in the case of products for women, red and pink colors are preferred, but zirconia in these colors has not been reported much. Normally, the manufacturing method for colored zirconia involves adding pigments to stabilized zirconia.
A method of adding and mixing (mainly oxides) and sintering (Japanese Patent Application Laid-open No. 59
-105055) or a small amount of coloring agent (
A method of dissolving mainly rare earths) by co-precipitation method etc.
59571) etc. are known as powder manufacturing methods.
しかし、上記の着色顔料を混合する方法には、添加量が
比較的釜いため焼結しにくく焼結体の特性、特に機械的
強度が低下するという大きな問題や、アルミナに較べて
顔料が固溶しにくいため鮮明な色が出にくいといった問
題が残っていた。また、少量の着色剤を共沈法で固溶さ
せる方法には、色の濃度が薄くカラージルコニアとして
は色が不鮮明で用途が限定されるという欠点があった。However, the above method of mixing color pigments has the major problem that the amount added is relatively large, making it difficult to sinter and reducing the properties of the sintered body, especially the mechanical strength. There remained the problem that it was difficult to produce clear colors because it was difficult to apply. In addition, the method of dissolving a small amount of coloring agent into solid solution by coprecipitation has the disadvantage that the color density is low and the color is unclear as colored zirconia, which limits its uses.
また、これら両方法は焼結性の面では特に改良された点
はなく、顔料添加法にいたってはむしろ焼結性が低下し
強度も低下するという大きな問題点があった。従って、
顔料添加法では高温高圧焼結（ＨＩ Ｐ処理）が常用さ
れるなど焼結が容易ではなかった。In addition, both of these methods have no particular improvement in terms of sinterability, and the pigment addition method has the major problem of decreasing sinterability and strength. Therefore,
Sintering was not easy in the pigment addition method, as high-temperature, high-pressure sintering (HIP treatment) was commonly used.
本発明の目的はかかる従来の着色ジルコニアの欠点を解
消するもので、特にピンク色のカラージルコニアを高強
度で、かつ明瞭なカラーで得ることにある。The object of the present invention is to eliminate the drawbacks of conventional colored zirconia, and in particular to obtain pink colored zirconia with high strength and clear color.
本発明に係わるカラージルコニア焼結体は、安定化剤と
少量の着色剤並びに焼結助剤とを含むＺｒＯ７から成る
もので、焼結温度が低く、色調が明瞭で機械的強度の低
下のないピンク色ジルコニア焼結体である。The colored zirconia sintered body according to the present invention is made of ZrO7 containing a stabilizer, a small amount of coloring agent, and a sintering aid, and has a low sintering temperature, a clear color tone, and no decrease in mechanical strength. It is a pink zirconia sintered body.
着色剤としてはエルビウム（Ｅｒ）化合物を用いるが、
ジルコニア中に安定化剤と共に共沈法、蓚酸塩法、蒸発
乾固法、加水分解法等で添加・固溶する場合には水溶性
化合物、具体的には塩化物、硝酸塩等が使用でき、また
安定化剤を既に含むＺｒＯ２粉に添加する場合には前記
の水溶性化合物の他に酸化物、酢酸塩、炭酸塩なども使
用でき、焼結体中における酸化物としての量が、安定化
剤を含むＺｒＯ２に対して０．５〜２，０モル％になる
ように添加する。Erbium (Er) compound is used as a coloring agent,
Water-soluble compounds, specifically chlorides, nitrates, etc., can be used when adding or dissolving in zirconia together with a stabilizer by a coprecipitation method, oxalate method, evaporation drying method, hydrolysis method, etc. In addition, when adding to ZrO2 powder that already contains a stabilizer, oxides, acetates, carbonates, etc. can be used in addition to the above-mentioned water-soluble compounds, and the amount of oxide in the sintered body stabilizes. It is added in an amount of 0.5 to 2.0 mol % based on ZrO2 containing the agent.
焼結助剤としてはＺｎ化合物を用いるが、酸化物や炭酸
塩等の不溶性化合物をはじめ酢酸塩、塩化物等の可溶性
化合物等、焼成後に酸化物となる化合物であれば特に種
類を限定する必要はなく、焼結体中における酸化物とし
ての量か、安定化剤を含むＺｒＯ２に対して０，１〜０
．６モル％になるよう添加する。A Zn compound is used as a sintering aid, but the type must be particularly limited if it is a compound that becomes an oxide after sintering, such as insoluble compounds such as oxides and carbonates, as well as soluble compounds such as acetates and chlorides. 0.1 to 0 relative to the amount of oxide in the sintered body or ZrO2 containing the stabilizer.
．． Add so that the amount becomes 6 mol%.
安定化剤としては、得られるピンク色ジルコニア焼結体
が高強度を必要とする場合には、焼成後Ｙ２０．となる
Ｙ化合物が最も好ましく （添加量としては１．０モル
％〜７．０モル％）、次いでＣｅＣＬ （１０モル％
〜１６モル％）が好ましいが、高強度を余り必要としな
い場合にはＣａ化合物（焼成後ＣａＯとなるもの二８〜
１２モル％）やＭｇ化合物（焼成後ＭｇＯとなるもの：
１６〜２６モル％）も安定化剤として使用できる。As a stabilizer, if the resulting pink zirconia sintered body requires high strength, Y20. The most preferable Y compound is (the amount added is 1.0 mol% to 7.0 mol%), followed by CeCL (10 mol%
~16 mol%) is preferred, but if high strength is not required, Ca compounds (which become CaO after sintering) are preferred.
12 mol%) and Mg compounds (things that become MgO after firing:
16-26 mol %) can also be used as a stabilizer.
本発明において着色剤の含有量を、安定化剤を含むＺｒ
Ｏ２に対して０．５〜２．０モル％に限定した理由は、
着色剤が０．５モル％未満では着色の効果が得難く、ま
た、２．０モル％を超えると焼結体特性に悪影響がでる
ためである。In the present invention, the content of the colorant is changed to Zr containing a stabilizer.
The reason for limiting it to 0.5 to 2.0 mol% with respect to O2 is
This is because if the colorant content is less than 0.5 mol%, it is difficult to obtain a coloring effect, and if it exceeds 2.0 mol%, the properties of the sintered body are adversely affected.
本発明において焼結助剤の添加量を、安定化剤を含むＺ
ｒ Ｏ２に対して０．１〜０．６モル％に限定した理
由は、焼結助剤が０．１モル％未満では助剤の効果が出
難く、また、０．６モル％を超えると焼結体特性に悪影
響がでるためである。In the present invention, the amount of the sintering aid added is changed to Z containing the stabilizer.
The reason why the content of the sintering aid is limited to 0.1 to 0.6 mol% relative to O2 is that if the sintering aid is less than 0.1 mol%, it is difficult to obtain the effect of the sintering aid, and if it exceeds 0.6 mol%, This is because the properties of the sintered body are adversely affected.
本発明に於ける仮焼温度は８００〜１１００℃であるが
、得られる仮焼粉の比表面積は低温仮焼はど大きく、ま
た高温仮焼はど低くなるので、好ましい仮焼温度は目的
とする粉末の比表面積により選へばよい。従って、比表
面積１５〜２０Ｍの粉末を得たい場合は９００℃前後、
６〜１０耐の粉末を得たい場合は１０００〜１０５０℃
ぐらいの仮焼温度が好ましい。The calcination temperature in the present invention is 800 to 1,100°C, but the specific surface area of the resulting calcined powder is large in low-temperature calcinations and low in high-temperature calcinations, so the preferred calcination temperature depends on the objective. The powder may be selected depending on the specific surface area of the powder. Therefore, if you want to obtain powder with a specific surface area of 15 to 20M, the temperature should be around 900℃.
If you want to obtain powder with a resistance of 6 to 10, use 1000 to 1050℃.
A calcination temperature of about
本発明に於けるピンク色ジルコニアの焼結温度は、粉末
の比表面積や成形圧力により異なるが、通常比表面積６
ｍの粉末では成形圧が静水圧２ｔ／ｃｒｊの場合で１３
００〜１４００℃で、比表面積１５Ｍの粉末で１２００
〜１３００°Ｃの焼結温度で理論密度の９８％以上の焼
結体が得られる。この焼結温度は通常市販されているジ
ルコニア粉末（比表面積ｌＯ〜１５イ）の焼結温度（１
４５０〜１５００°Ｃ）に比べて２００〜３００℃低い
温度である。また、得られるピンク色ジルコニア焼結体
の曲げ強度は、ＪＩＳ規格の３点曲げ法で比較した場合
、市販されているジルコニア焼結体（Ｙ２Ｏ３含量３モ
ル％品）と同等かそれ以上の強度を示す。The sintering temperature of pink zirconia in the present invention varies depending on the specific surface area of the powder and the compacting pressure, but usually the specific surface area is 6.
m powder, when the molding pressure is hydrostatic pressure 2t/crj, it is 13
00-1400℃, powder with specific surface area 15M
A sintered body having a theoretical density of 98% or more can be obtained at a sintering temperature of ~1300°C. This sintering temperature is the sintering temperature (1
The temperature is 200 to 300°C lower than that of 450 to 1500°C. In addition, the bending strength of the pink zirconia sintered body obtained is equivalent to or higher than that of a commercially available zirconia sintered body (Y2O3 content 3 mol% product) when compared using the JIS standard three-point bending method. shows.
以下に実施例を挙げて本発明をさらに具体的に説明する
。The present invention will be explained in more detail with reference to Examples below.
実施例１
高強度ピンク色ジルコニア焼結体を製造するに際し、オ
キシ塩化ジルコニウムＺ ｒ ＯＣ１２２００ｇ （１
，１２３モル） 、ＹＣｌ ｈ ６．９２４ ｇ （０
，０３５５モル）及びＥ ｒ Ｃｌ ３ ６．４５７ｇ
（０，０２３６モル）を溶解した酸性水溶液をアンモ
ニア水に滴下して生成した共沈物をろ過、水洗、アルコ
ール洗浄した後１１０℃で減圧乾燥した。得られた乾燥
粉を１０００℃で３時間仮焼して、比表面積約６−の粉
末を得た。この仮焼粉末１００ｇ （０，８１２モル）
に酢酸亜鉛・２水和物０．５３６ ｇ （０，００２４
４モル）とエタノール２５０−を加え、ジルコニアボー
ルで約２４時間ボールミルをおこなった後、スラリーを
蒸発乾固して原料粉末を得た。Example 1 When producing a high-strength pink zirconia sintered body, 12200 g of zirconium oxychloride Z r OC (1
, 123 mol), YCl h 6.924 g (0
,0355 mol) and E r Cl 3 6.457 g
An acidic aqueous solution in which (0,0236 mol) was dissolved was added dropwise to aqueous ammonia, and the resulting coprecipitate was filtered, washed with water, washed with alcohol, and then dried under reduced pressure at 110°C. The obtained dry powder was calcined at 1000°C for 3 hours to obtain a powder with a specific surface area of about 6. 100g (0,812 mol) of this calcined powder
Zinc acetate dihydrate 0.536 g (0,0024
After adding 4 moles of ethanol and 250 moles of ethanol and performing ball milling with zirconia balls for about 24 hours, the slurry was evaporated to dryness to obtain a raw material powder.
この粉末を静水圧２ｔ／ｃｎｆでプレス成形して得た成
形体を１３００℃で３時間焼成してピンク色ジルコニア
焼結体を得た。得られた焼結体の密度と曲げ強度（ＪＩ
Ｓ規格３点曲げ試験）、Ｋｔｃ値（ビッカースインデン
テーション法）は表１に示したように高い値が得られた
。This powder was press-molded under a hydrostatic pressure of 2 t/cnf, and the resulting compact was fired at 1300°C for 3 hours to obtain a pink zirconia sintered body. Density and bending strength (JI) of the obtained sintered body
S standard 3-point bending test) and Ktc value (Vickers indentation method) as shown in Table 1, high values were obtained.
実施例２
オキシ塩化ジルコニウムＺｒ０Ｃ］２２００ｇ（１，１
２３モル） 、ＹＣ１，９，２３１ｇ （０，４７３モ
ル） 、Ｅ ｒ Ｃ１ｇ ３．２３１ ｇ （０，０１
１８モル）を溶解した酸性水溶液にこれら化合物の倍モ
ル量以上の蓚酸を溶解した水溶液を滴下撹拌し、得られ
た蓚酸塩沈澱物をろ過、水洗、エタノール洗浄後減圧乾
燥し、ついで９００℃で３時間仮焼して比表面積１５ｍ
′の粉末を得た。この仮焼粉末１００ ｇ （０，８１
２モル）に炭酸亜鉛０．３０６ ｇ （０，００２４４
モル）とエタノール２５０−を加えジルコニアボールを
用いて約２４時間ボールミルした後スラリーを蒸発乾固
して原料粉末を得た。Example 2 Zirconium oxychloride Zr0C] 2200 g (1,1
23 mol), YC1,9,231g (0,473 mol), E r C1g 3.231 g (0,01
An aqueous solution containing oxalic acid in an amount equal to or more than double the mole of these compounds was added dropwise to an acidic aqueous solution containing 18 moles of oxalic acid dissolved therein, and the resulting oxalate precipitate was filtered, washed with water, washed with ethanol, dried under reduced pressure, and then dried at 900°C. Calcinate for 3 hours to obtain a specific surface area of 15m
’ powder was obtained. This calcined powder 100 g (0,81
2 mol) of zinc carbonate (0.306 g (0,00244
After adding 250 moles of ethanol and ball milling using zirconia balls for about 24 hours, the slurry was evaporated to dryness to obtain a raw material powder.
この粉末を実施例１と同様に静水圧でプレス成形し１２
００°Ｃ−３時間焼成してピンク色ジルコニア焼結体を
得た。得られた焼結体の密度と機械的特性を表１に示し
た。This powder was press-molded using hydrostatic pressure in the same manner as in Example 1.
A pink zirconia sintered body was obtained by firing at 00°C for 3 hours. Table 1 shows the density and mechanical properties of the obtained sintered body.
実施例３
Ｙ２Ｏ，を２モル％含有する比表面積１５Ｍのジルコニ
ア粉末１００ｇ （０，８１２モル）をＥｒ２０ ｓ
２．４３５ ｇ （０，００８９０モル）を含む酸性水
溶液２５０−にボールミル等でよく分散させた後Ｅｒ化
合物の倍モル量以上の蓚酸を含む水溶液２５〇−を滴下
して得られるＥｒ蓚酸塩とジルコニア粉末の混合沈澱を
ろ過水法、エタノール洗浄減圧乾燥し、ついで１０００
℃で３時間仮焼して比表面積６ｄの粉末を得た。この仮
焼粉末１００ｇに酢酸亜鉛・２水和物０．５３６ ｇ
（０，００，２４４モル）とエタノール２５０−を加え
ジルコニアボールで２４時間ボールミルした後、スラリ
ーを蒸発乾固しで原料粉末を得た。得られた粉末を実施
例１と同様に成形し、１３００°Ｃで３時間焼成してピ
ンク色ジルコニア焼結体を得た。得られた焼結体の特性
を表１に示した。Example 3 100 g (0,812 mol) of zirconia powder containing 2 mol % of Y2O and a specific surface area of 15 M was added to Er20 s.
Er oxalate obtained by dispersing well in an acidic aqueous solution 250- containing 2.435 g (0,00890 mol) using a ball mill etc. and then dropping an aqueous solution 250- containing oxalic acid in an amount more than double the molar amount of the Er compound. The mixed precipitate of zirconia powder was washed with ethanol and dried under reduced pressure using the filtered water method, and then
The powder was calcined at ℃ for 3 hours to obtain a powder having a specific surface area of 6d. 0.536 g of zinc acetate dihydrate to 100 g of this calcined powder
(0,00,244 mol) and 250 mol of ethanol were added and ball milled for 24 hours using zirconia balls, and the slurry was evaporated to dryness to obtain a raw material powder. The obtained powder was molded in the same manner as in Example 1 and fired at 1300°C for 3 hours to obtain a pink zirconia sintered body. Table 1 shows the properties of the obtained sintered body.
比較例ｌ
Ｙ２Ｏ，を３モル％含有する市販のジルコニア粉末（比
表面積１５イ） １００ｇ（０，８１１６モル）に色
材として酸化エンビウムＥ ｒ２０．３．１３６ｇ （
０，００８２０モル）を加えジルコニアボールで２４時
間ボールミルした後、スラリーを蒸発乾固して原料粉末
を得た。得られた粉末を実施例１と同様の方法で成形し
１２００℃で焼成した。Comparative Example 1 100 g (0,8116 mol) of commercially available zirconia powder (specific surface area 15) containing 3 mol% of Y2O, and 20.3.136 g of enbium oxide E as a coloring material (
After adding 0,00820 mol) and ball milling with zirconia balls for 24 hours, the slurry was evaporated to dryness to obtain a raw material powder. The obtained powder was molded in the same manner as in Example 1 and fired at 1200°C.
得られた焼結体の結果を表１に示した。Table 1 shows the results of the obtained sintered body.
比較例２
オキシ塩化ジルコニウムＺｒ０Ｃ１□２００ｇ（１，１
２３モル） 、ＭＣＩ 、 ６．９２４ｇ （０，０
３５５モル）及びＥ ｒ Ｃｌ 、 ６．４５７ ｇ
（０，０２３６モル）を溶解した酸性水溶液をアンモニ
ア水に滴下して生成した共沈物をろ過、水洗、アルコー
ル洗浄した後、１１０℃で減圧乾燥した。得られた乾燥
粉を１０００℃で３時間仮焼して、比表面積６ｒ＋（の
粉末を得た。この仮焼粉末をエタノールとともにジルコ
ニアボールを用いて約２４時間ボールミル、得られたス
ラリーを蒸発乾固して原料粉末を得た。得られた粉末を
実施例１と同様に成形し、１３００℃で３時間焼成した
。Comparative Example 2 Zirconium oxychloride Zr0C1□200g (1,1
23 mol), MCI, 6.924g (0,0
355 mol) and E r Cl , 6.457 g
An acidic aqueous solution in which (0,0236 mol) was dissolved was added dropwise to aqueous ammonia, and the resulting coprecipitate was filtered, washed with water, washed with alcohol, and then dried under reduced pressure at 110°C. The obtained dry powder was calcined at 1000°C for 3 hours to obtain a powder with a specific surface area of 6r+. This calcined powder was ball milled with ethanol using a zirconia ball for about 24 hours, and the resulting slurry was evaporated to dryness. The powder was solidified to obtain a raw material powder.The obtained powder was molded in the same manner as in Example 1 and fired at 1300°C for 3 hours.
得られた焼結体の特性を表１に示した。Table 1 shows the properties of the obtained sintered body.
上記の実施例には安定化剤にＹ２Ｏ３を使用した場合を
示したが、他の安定化剤（ＣｅＣＬ、Ｃａｂ、Ｍｇ０）
を使用した場合でも、同様の低温焼結特性を示し比較例
に比へて低温で高密度・高強度の焼結体が得られる。The above example shows the case where Y2O3 was used as the stabilizer, but other stabilizers (CeCL, Cab, Mg0)
Even when used, the same low-temperature sintering properties are obtained, and a sintered body with higher density and higher strength can be obtained at a lower temperature than in the comparative example.
焼結温度が低く、色調が鮮明で、機械的強度の高いピン
ク色ジルコニア焼結体が得られる。A pink zirconia sintered body with a low sintering temperature, clear color, and high mechanical strength can be obtained.
出願人 （４３０）日本曹達株式会社
代理人 （７１２５）横 山 吉 美（９６４８
）東 海 裕 作Applicant (430) Nippon Soda Co., Ltd. Agent (7125) Yoshimi Yokoyama (9648)
) Written by Hiroshi Tokai
Claims (3)
を０．５〜２．０モル％、ＺｎＯを０．１〜０．６モル
％含有することを特徴とするピンク色ジルコニア焼結体
。1. For ZrO_2 containing stabilizer, Er_2O_3
A pink zirconia sintered body characterized by containing 0.5 to 2.0 mol% of ZnO and 0.1 to 0.6 mol% of ZnO.
合物、並びに焼成後Ｅｒ＿２Ｏ＿３となるエルビウム化
合物を含む溶液から得た混合物を仮焼した後、焼成によ
り酸化亜鉛を生成する化合物を均一に添加混合して、成
形・焼成することを特徴とするピンク色ジルコニア焼結
体の製造方法。2. After calcining a mixture obtained from a solution containing a stabilizer, a zirconium compound that becomes ZrO_2 after firing, and an erbium compound that becomes Er_2O_3 after firing, a compound that produces zinc oxide upon firing is uniformly added and mixed, and molded. - A method for producing a pink zirconia sintered body characterized by firing.
を添加後仮焼し、さらに焼成により酸化亜鉛を生成する
亜鉛化合物を添加混合して、成形後焼成することを特徴
とするピンク色ジルコニア焼結体の製造方法。3. Production of a pink zirconia sintered body characterized by adding an erbium compound to zirconia powder containing a stabilizer, then calcining it, adding and mixing a zinc compound that produces zinc oxide upon firing, and firing after shaping. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099289A JP2946343B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099289A JP2946343B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH042658A true JPH042658A (en) | 1992-01-07 |
| JP2946343B2 JP2946343B2 (en) | 1999-09-06 |
Family
ID=14243489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2099289A Expired - Lifetime JP2946343B2 (en) | 1990-04-17 | 1990-04-17 | High strength color zirconia sintered body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2946343B2 (en) |
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|---|---|---|---|---|
| JP2005306678A (en) * | 2004-04-22 | 2005-11-04 | Matsushita Electric Works Ltd | Zirconia-alumina colored composite ceramic material, and method for manufacturing the same |
| WO2009157508A1 (en) | 2008-06-26 | 2009-12-30 | 京セラ株式会社 | Pinkish to purplish ceramic and decorative part |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306678A (en) * | 2004-04-22 | 2005-11-04 | Matsushita Electric Works Ltd | Zirconia-alumina colored composite ceramic material, and method for manufacturing the same |
| WO2009157508A1 (en) | 2008-06-26 | 2009-12-30 | 京セラ株式会社 | Pinkish to purplish ceramic and decorative part |
| JP5511661B2 (en) * | 2008-06-26 | 2014-06-04 | 京セラ株式会社 | Pink to purple ceramics and decorative parts |
| CN102766154A (en) * | 2012-07-28 | 2012-11-07 | 山东大学 | Method for preparing organic poly-zirconium precursor or silk-thrawn liquor thereof for zirconia fiber production by one-step solvent method |
| WO2014104236A1 (en) | 2012-12-28 | 2014-07-03 | 東ソー株式会社 | Colored light-transmitting zirconia sintered body and use thereof |
| JP2014141388A (en) * | 2012-12-28 | 2014-08-07 | Tosoh Corp | Colored light-transmitting zirconia sintered compact and use thereof |
| US9428422B2 (en) | 2012-12-28 | 2016-08-30 | Tosoh Corporation | Colored translucent zirconia sintered body and its use |
| JP2018002590A (en) * | 2012-12-28 | 2018-01-11 | 東ソー株式会社 | Colored light transmissive zirconia sintered body and application therefor |
| EP3838248A1 (en) | 2012-12-28 | 2021-06-23 | Tosoh Corporation | Colored translucent zirconia sintered body and its use |
| JP2017145158A (en) * | 2016-02-16 | 2017-08-24 | 東ソー株式会社 | Colored zirconia sintered body |
| CN114644520A (en) * | 2022-04-22 | 2022-06-21 | 烟台核晶陶瓷新材料有限公司 | Pink nano zirconia ceramic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2946343B2 (en) | 1999-09-06 |
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