JPH0782048A - Sintered titanium compound - Google Patents
Sintered titanium compoundInfo
- Publication number
- JPH0782048A JPH0782048A JP5161279A JP16127993A JPH0782048A JP H0782048 A JPH0782048 A JP H0782048A JP 5161279 A JP5161279 A JP 5161279A JP 16127993 A JP16127993 A JP 16127993A JP H0782048 A JPH0782048 A JP H0782048A
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- Prior art keywords
- titanium compound
- volume
- titanium
- whiskers
- oxides
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ウイスカー等の繊維状
物質を含有する繊維強化セラミックスに関し、詳細には
高靱性を有し、特に切削工具やその他耐摩耗性部品、装
飾材料に適したチタン化合物焼結体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fiber reinforced ceramics containing fibrous substances such as whiskers, and in particular titanium having high toughness and particularly suitable for cutting tools, other wear resistant parts and decorative materials. It relates to a compound sintered body.
【０００２】[0002]
【従来技術】従来、炭化チタン（ＴｉＣ）質焼結体は、
サーメット材料の主原料として各種の切削工具や産業機
械用部品に応用されている反面、靱性に劣るという欠点
を有するために利用分野の拡大が阻害されている。そこ
で従来はこれらにニッケル、コバルト等の金属を添加し
て靱性を改善することが行われている。2. Description of the Related Art Conventionally, titanium carbide (TiC) -based sintered bodies are
Although it is applied to various cutting tools and parts for industrial machines as a main raw material for cermet materials, it has a drawback of being poor in toughness, which hinders the expansion of fields of use. Therefore, conventionally, metals such as nickel and cobalt are added to these to improve toughness.
【０００３】[0003]
【発明が解決しようとする問題点】しかしながら、ニッ
ケル，コバルト等の金属は硬度が低いので、それらを含
まない材料に比較して摩耗量が多くなる傾向にある。ま
た、装飾品の分野では添加された金属により、皮膚にア
レルギーを生じる原因になる場合がある。However, since metals such as nickel and cobalt have low hardness, the amount of wear tends to increase as compared with materials that do not contain them. Also, in the field of ornaments, added metals may cause allergies to the skin.
【０００４】さらに、最近に至り、針状の結晶粒子（ウ
イスカー）によって靱性を向上することが試みられてい
る。その代表的なものはＳｉＣウイスカーであり多くの
研究が行われている。チタン化合物ウイスカーによる強
靱化も提案されているが、セラミックスの抗折強度，靱
性，硬度等の特性の点から未だ十分に検討されておら
ず、実用的なレベルに達していないのが現状であった。Furthermore, recently, attempts have been made to improve toughness by acicular crystal particles (whiskers). A typical one is SiC whiskers, and many studies have been conducted. Toughening with titanium compound whiskers has also been proposed, but it has not yet been fully examined from the viewpoint of characteristics such as bending strength, toughness, and hardness of ceramics, and at present it has not reached a practical level. It was
【０００５】[0005]
【問題点を解決するための手段】本発明者等は、上記チ
タン化合物ウイスカー系セラミックスに対して、詳細に
検討を重ねた結果、この材料と周期律表第４ａ，５ａ，
６ａ族元素の炭化物，窒化物，炭窒化物および酸化物の
少なくとも一種を複合化させることにより、破壊靱性を
はじめとする機械的特性を向上できることを知見し本発
明に至った。The inventors of the present invention have made detailed studies on the above-mentioned titanium compound whisker-based ceramics, and as a result, have found that this material and the periodic table 4a, 5a,
The present inventors have found that it is possible to improve mechanical properties such as fracture toughness by compounding at least one of carbides, nitrides, carbonitrides and oxides of 6a group elements, and arrived at the present invention.
【０００６】即ち、本発明のチタン化合物焼結体は、チ
タンの炭化物，窒化物，硼化物及び炭窒化物からなるチ
タン化合物のうち少なくとも一種を４５〜９５体積％含
有し、前記チタン化合物のうち少なくとも一種がチタン
化合物ウイスカーとして全量中５〜７０体積％の割合で
存在し、周期律表第４ａ，５ａ，６ａ族元素の炭化物，
窒化物，炭窒化物，酸化物のうち少なくとも一種を３体
積％以上含有するものである。以下、本発明を詳述す
る。That is, the titanium compound sintered body of the present invention contains 45 to 95% by volume of at least one titanium compound consisting of titanium carbide, nitride, boride and carbonitride. At least one is present as a titanium compound whisker in a proportion of 5 to 70% by volume in the total amount, and is a carbide of a group 4a, 5a, 6a element of the periodic table,
It contains at least 3% by volume of at least one of nitride, carbonitride, and oxide. Hereinafter, the present invention will be described in detail.
【０００７】本発明で用いられるチタン化合物ウイスカ
ーは、それ自体、単結晶あるいは多結晶質からなるもの
で、その平均直径は３μｍ以下、特に０．５乃至１μｍ
であることが好ましい。平均径が３μｍ以下では、高い
抗折強度を維持できるからであり、平均径が大きく成り
過ぎると均一に分散することも難しくなり、強度，靱性
ともバラツキが生じやすく、また切削工具として用いた
際に逃げ面の境界摩耗が大きくなるためである。尚、切
削工具として使用する場合には、チタン化合物焼結体の
表面に、厚さ０．１〜１５μｍの単層または２層以上の
周期律表第４ａ族元素およびＡｌの炭化物，窒化物，炭
窒化物，酸化物の少なくとも一種からなる表面被覆層を
形成しても良い。The titanium compound whiskers used in the present invention are composed of a single crystal or a polycrystal, and have an average diameter of 3 μm or less, particularly 0.5 to 1 μm.
Is preferred. This is because if the average diameter is 3 μm or less, high bending strength can be maintained. If the average diameter becomes too large, it becomes difficult to disperse uniformly, and variations in strength and toughness are likely to occur, and when used as a cutting tool. This is because the boundary wear of the flank becomes large. When used as a cutting tool, a titanium compound sintered body has a surface on the surface of which is a single layer or two or more layers of a periodic table group 4a element and Al carbide, nitride, and A surface coating layer made of at least one of carbonitride and oxide may be formed.
【０００８】一方、ウイスカーの長径／短径で表される
アスペクト比が小さすぎると繊維強化の効果が小さく高
い靱性が得られにくく、逆に大きすぎると原料としての
取扱が難しく、均一に分散することができないために高
い靱性を得ることが難しくなる。よって、アスペクト比
の平均は３乃至１００、特に１０乃至３０のものが好適
に使用される。On the other hand, if the aspect ratio represented by the major axis / minor axis of the whisker is too small, the effect of fiber reinforcement is small and high toughness is difficult to obtain, while if it is too large, it is difficult to handle as a raw material and uniformly dispersed. Therefore, it becomes difficult to obtain high toughness. Therefore, an average aspect ratio of 3 to 100, particularly 10 to 30, is preferably used.
【０００９】このようなチタン化合物ウイスカーは、例
えばＣＶＤ法により合成することができるが、どの様な
製法によって作られたものであっても使用できる。Such titanium compound whiskers can be synthesized, for example, by the CVD method, but any manufacturing method can be used.
【００１０】このチタン化合物ウイスカーは、周期律表
第４ａ，５ａ，６ａ族元素の炭化物、窒化物、炭窒化物
を主成分とする成分中に、全量中５〜７０体積％、特に
１０〜５０体積％、さらに好ましくは、２０〜４５体積
％分散含有させる。ウイスカーの量を上記の範囲に設定
したのは、ウイスカー量が５体積％未満では、ウイスカ
ー添加による靱性向上効果が小さく、７０体積％を越え
ると系全体の焼結性が低下するからである。尚、焼結を
容易にし、焼結に要するコストを削減するためには、Ｔ
ｉＣウイスカーの添加量は５乃至４５体積％が好まし
く、最適には１０乃至３０体積％が良い。チタン化合物
ウイスカーは、靱性向上のためには、４８〜７０体積％
含有させることが望ましい。This titanium compound whisker is 5 to 70% by volume, particularly 10 to 50% by volume in the total amount in the components containing carbides, nitrides and carbonitrides of elements of groups 4a, 5a and 6a of the periodic table. %, And more preferably 20 to 45% by volume. The amount of whiskers is set in the above range because if the amount of whiskers is less than 5% by volume, the effect of improving the toughness by adding whiskers is small, and if it exceeds 70% by volume, the sinterability of the entire system deteriorates. In order to facilitate the sintering and reduce the cost required for the sintering, T
The amount of iC whiskers added is preferably 5 to 45% by volume, and optimally 10 to 30% by volume. Titanium compound whiskers contain 48 to 70% by volume for improving toughness.
It is desirable to include it.
【００１１】本発明においては、チタン化合物ウイスカ
ーは、主としてＴｉＣウイスカーであり、ウイスカー以
外のチタン化合物としては、主としてＴｉＮであること
が望ましい。また、チタン化合物ウイスカーであるＴｉ
Ｃウイスカーを４０〜７０体積％、チタン化合物である
ＴｉＮを２〜１５体積％、炭化モリブデン，炭化ジルコ
ニウムのうち少なくとも一種を３〜１５体積％含有する
ことが望ましい。In the present invention, the titanium compound whiskers are mainly TiC whiskers, and the titanium compound other than the whiskers is preferably TiN. In addition, Ti which is a titanium compound whisker
It is desirable to contain 40 to 70% by volume of C whiskers, 2 to 15% by volume of titanium compound TiN, and 3 to 15% by volume of at least one of molybdenum carbide and zirconium carbide.
【００１２】本発明によれば、Ａｌ2 Ｏ3 を５０体積％
以下含有させても良い。これは、Ａｌ2 Ｏ3 はこの材料
を切削工具として用いた場合に耐摩耗性を向上させる効
果があるからである。即ち、Ａｌ2 Ｏ3 が５０体積％よ
りも多いと、焼結体の靱性が低下し、切削工具として用
いた場合にチッピングが生じ易いからである。Ａｌ2Ｏ
3 添加量は２０〜４５体積％、特に３５〜４５体積％含
有することが望ましい。アルミナを含有する場合には、
チタン化合物であるＴｉＮは、その一部がＡｌ2 Ｏ3 粒
子内部に存在することが望ましい。According to the invention, 50% by volume of Al 2 O 3 is used.
It may be contained below. This is because Al 2 O 3 has the effect of improving wear resistance when this material is used as a cutting tool. That is, when Al 2 O 3 is more than 50% by volume, the toughness of the sintered body is lowered and chipping easily occurs when it is used as a cutting tool. Al 2 O
3 The addition amount is preferably 20 to 45% by volume, and more preferably 35 to 45% by volume. When it contains alumina,
It is desirable that a part of TiN, which is a titanium compound, exists inside the Al 2 O 3 particles.
【００１３】また、本発明によれば、Ｎｉ，Ｃｏ及びそ
れらの酸化物，炭化物，窒化物のうち少なくとも一種を
５体積％以下含有させても良い。これは、Ｎｉ，Ｃｏ，
Ｃｒ及びそれらの酸化物，炭化物はＴｉＣウイスカーと
Ａｌ2 Ｏ3 を強固に結合させる効果があるからであり、
Ｃｒ及びそれらの酸化物，炭化物は焼結体の硬度を上げ
る効果があるからである。また、Ｎｉ，Ｃｏ，Ｃｒの添
加は材料の焼結性を改善する。Ｎｉ，Ｃｏ，Ｃｒおよび
それらの酸化物，炭化物，窒化物の添加量は、特に０．
５〜２体積％であることが望ましい。Further, according to the present invention, at least one of Ni, Co and their oxides, carbides, and nitrides may be contained in an amount of 5% by volume or less. This is Ni, Co,
This is because Cr and their oxides and carbides have the effect of firmly binding TiC whiskers and Al 2 O 3 .
This is because Cr and their oxides and carbides have the effect of increasing the hardness of the sintered body. Also, the addition of Ni, Co and Cr improves the sinterability of the material. The addition amount of Ni, Co, Cr and their oxides, carbides, and nitrides is especially 0.
It is preferably 5 to 2% by volume.
【００１４】本発明においては、周期律表第４ａ，５
ａ，６ａ族元素の炭化物、窒化物、炭窒化物，酸化物の
うち少なくとも一種を３体積％以上含有するが、特に炭
化モリブデン，炭化ジルコニウムのうち少なくとも１種
を３〜１５体積％含有することが硬度及び靱性の向上の
点から好ましい。３％未満では焼結体の破壊靱性および
硬度や強度が低下する傾向にある。In the present invention, the periodic table 4a, 5
Contain at least 3% by volume of at least one of carbides, nitrides, carbonitrides, and oxides of a and 6a group elements, and particularly contain at least one of molybdenum carbide and zirconium carbide at 3 to 15% by volume. Is preferable from the viewpoint of improving hardness and toughness. If it is less than 3%, the fracture toughness, hardness and strength of the sintered body tend to decrease.
【００１５】またウイスカーを分散するためのマトリッ
クスがＡｌ2 Ｏ3 を主体とする場合、窒化チタンを混合
するのがよい。窒化チタンは直径１μｍ以下の粒子であ
って、少なくとも一部がＡｌ2 Ｏ3 粒子内部に存在する
と、特に破壊靱性及び抗折強度向上という観点から添加
効果が大きい。窒化チタンをＡｌ2 Ｏ3 粒子内部に存在
させる為には焼結時の昇温速度と窒化チタンの粒子径を
コントロールすることが重要である。例えば、１０００
〜１８００℃までの昇温速度は窒化チタンの平均粒径が
１μｍ以下の場合、６℃／分以上、平均粒径が０．５μ
ｍ以下の場合３℃／分以上にすることが特に重要であ
る。When the matrix for dispersing the whiskers is mainly composed of Al 2 O 3 , it is preferable to mix titanium nitride. Titanium nitride is a particle having a diameter of 1 μm or less, and when at least a part thereof is present inside the Al 2 O 3 particle, the addition effect is large particularly from the viewpoint of improving fracture toughness and bending strength. In order to allow titanium nitride to exist inside Al 2 O 3 particles, it is important to control the temperature rising rate during sintering and the particle size of titanium nitride. For example, 1000
When the average particle diameter of titanium nitride is 1 μm or less, the temperature rising rate up to 1800 ° C. is 6 ° C./min or more, and the average particle diameter is 0.5 μm.
When it is m or less, it is particularly important to set it to 3 ° C./min or more.
【００１６】酸化アルミニウムを含有させる場合、焼結
助剤として公知の酸化物を添加してもよい。少量の酸化
物を添加することによりマトリックス成分としての焼結
性を高め、特性の向上を図ることができる。しかしこの
助剤量が多すぎると焼結体の靱性が低下する。よってこ
れらの焼結助剤は、全量中０．１乃至５重量％、特に
０．５乃至３重量％の割合で添加するのが良い。尚、こ
こで用いられる酸化物としてはＹｂ，Ｎｄ，Ｅｒ，Ｃ
ｅ，Ｓｍ，Ｇｄ，Ｄｙ等の酸化物が挙げられる。When aluminum oxide is contained, a known oxide as a sintering aid may be added. By adding a small amount of oxide, the sinterability as a matrix component can be improved and the characteristics can be improved. However, if the amount of this auxiliary agent is too large, the toughness of the sintered body decreases. Therefore, these sintering aids are preferably added in a proportion of 0.1 to 5% by weight, particularly 0.5 to 3% by weight, based on the total amount. The oxides used here are Yb, Nd, Er, C.
Examples thereof include oxides such as e, Sm, Gd and Dy.
【００１７】本発明のチタン化合物焼結体を製造するに
は、まずチタンの炭化物、窒化物及び炭窒化物のチタン
化合物、同じくチタン化合物ウイスカー、周期律表第４
ａ，５ａ，６ａ族元素の炭化物，窒化物，炭窒化物，酸
化物、酸化アルミニウム、Ｎｉ，Ｃｏ，Ｃｒの酸化物，
炭化物、必要に応じて焼結助剤を前述した割合で混合、
粉砕後に所望の成形手段、金型プレス、押し出し成形、
射出成形、冷間静水圧成形等によって成形後、焼成す
る。In order to manufacture the titanium compound sintered body of the present invention, first, titanium compounds of titanium carbides, nitrides and carbonitrides, titanium compound whiskers, and periodic table No. 4 are used.
Carbides, nitrides, carbonitrides, oxides, aluminum oxides, Ni, Co, Cr oxides of a, 5a, and 6a group elements,
Carbide, optionally mixed with a sintering aid in the proportions described above,
After crushing, desired molding means, mold press, extrusion molding,
After molding by injection molding, cold isostatic molding, etc., firing is performed.
【００１８】焼成は、普通焼成、ホットプレス法、熱間
静水圧焼成法等が適用され、１６５０℃〜１８５０℃の
温度でＡｒやＨｅ等の不活性ガスもしくはカーボン等の
存在する還元性雰囲気およびそれらの加圧もしくは減圧
雰囲気中で０．５〜６時間行う。特に高密度の焼結体を
得るためには、普通焼成あるはホットプレス法によって
対理論密度比９６％以上の焼結体を作成し、この焼結体
をさらに熱間静水圧焼成すればよい。As the firing, a normal firing, a hot pressing method, a hot isostatic firing method or the like is applied, and a reducing atmosphere in which an inert gas such as Ar or He or carbon is present at a temperature of 1650 ° C. to 1850 ° C. It is performed for 0.5 to 6 hours in the pressurized or reduced pressure atmosphere. In order to obtain a particularly high density sintered body, a sintered body having a theoretical density ratio of 96% or more may be prepared by ordinary firing or hot pressing, and this sintered body may be further subjected to hot isostatic firing. .
【００１９】[0019]
【作用】本発明においては、チタン化合物ウイスカーの
引き抜き効果を顕著に発揮させるこにより焼結体の靱性
を向上することができる。また、チタン化合物やチタン
化合物ウイスカーを用いることにより、切削工具として
の耐摩耗性や装飾材料としての色調を改善することがで
きる。In the present invention, the toughness of the sintered body can be improved by remarkably exerting the pulling-out effect of the titanium compound whiskers. Further, by using a titanium compound or a titanium compound whisker, it is possible to improve wear resistance as a cutting tool and color tone as a decorative material.
【００２０】以下、本発明を次の例で説明する。The present invention will be described below with reference to the following examples.
【００２１】[0021]
【実施例】先ず、出発原料として、チタン化合物粉末
と、周期律表第４ａ，５ａ，６ａ族元素粉末と、平均粒
径１μｍ以下、純度９９．９％以上のＡｌ2 Ｏ3 粉末
と、その他の粉末を用意し、表１，２に示す割合で秤量
後、回転ミルにて１２時間混合粉砕した。この混合粉末
に平均粒径１μｍ、アスペクト比が１０〜３０のチタン
化合物ウイスカーを所定量添加し、回転ミルで１２時間
混合した。混合後のスラリーを乾燥してホットプレス用
原料とした。EXAMPLES First, as starting materials, titanium compound powder, periodic table group 4a, 5a, and 6a element powders, Al 2 O 3 powder having an average particle size of 1 μm or less and a purity of 99.9% or more, and others. The powder was prepared, weighed at the ratios shown in Tables 1 and 2, and mixed and pulverized for 12 hours on a rotary mill. A predetermined amount of titanium compound whiskers having an average particle size of 1 μm and an aspect ratio of 10 to 30 was added to this mixed powder and mixed for 12 hours in a rotary mill. The mixed slurry was dried to obtain a raw material for hot pressing.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】この原料をカーボン型に充填し、１７５０
℃の温度，５００ｋｇ／ｃｍ2 の圧力でホットプレス焼
成してＪＩＳ規格に基づく抗折試験片を作成した。A carbon mold was filled with this raw material, and 1750
Hot-press firing was performed at a temperature of 500 ° C. and a pressure of 500 kg / cm 2 to prepare a bending test piece based on JIS standard.
【００２５】得られた各試料を研磨して、荷重２０ｋｇ
によるビッカース硬度、また鏡面にポリッシング加工し
ＩＭ法で靱性（Ｋ1C) を測定した。また、顕微鏡写真か
ら組織観察し焼結性について評価した。結果を表３，４
に示す。Each of the obtained samples was ground to give a load of 20 kg.
Vickers hardness according to the above, and toughness (K 1C ) was measured by IM method after polishing the mirror surface. Further, the structure was observed from the micrograph and the sinterability was evaluated. The results are shown in Tables 3 and 4.
Shown in.
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【表４】 [Table 4]
【００２８】表３，４によれば、ウイスカー添加量が多
い場合（試料Ｎo.１，７，２３）では硬度が低く、ま
た、密度が低いため鏡面仕上げが不可能であるという理
由から靱性が測定できず、ボイドも発生した。また、ウ
イスカーを添加しない場合（試料Ｎo.３０）では靱性が
極端に小さかった。周期律表第４ａ，５ａ，６ａ族元素
化合物を添加しなかった場合（資料Ｎo.７，１６，２
４）では硬度が低いことが判る。According to Tables 3 and 4, when the amount of whiskers added is large (Samples No. 1, 7, and 23), the hardness is low and the toughness is low because the mirror finish is impossible because of the low density. It could not be measured and a void was generated. Further, the toughness was extremely low when no whiskers were added (Sample No. 30). When no group 4a, 5a, 6a group element compound is added to the periodic table (Data No. 7, 16, 2)
It can be seen that in 4) the hardness is low.
【００２９】これに対して、本発明に基づき作成した試
料は、いずれも優れた靱性および硬度を有することが判
る。On the other hand, it can be seen that the samples prepared according to the present invention all have excellent toughness and hardness.
【００３０】[0030]
【発明の効果】以上詳述した通り、本発明のチタン化合
物焼結体は、チタン化合物と、チタン化合物ウイスカー
と、周期律表第４ａ，５ａ，６ａ族元素の炭化物，窒化
物，炭窒化物，酸化物のうち少なくとも１種を含有する
ので、チタン化合物イウスカーのいわゆる引き抜き効果
を顕著に発揮させることができ、焼結体の靱性および硬
度を向上することができる。また、チタン化合物やチタ
ン化合物ウイスカーを用いることにより、切削工具とし
ての耐摩耗性や装飾材料としての色調を改善することが
できる。これにより、切削工具やその他耐摩耗性部品，
装飾材料に適したチタン化合物焼結体を得ることができ
る。As described in detail above, the titanium compound sintered body of the present invention comprises a titanium compound, a titanium compound whisker, and carbides, nitrides and carbonitrides of elements of groups 4a, 5a and 6a of the periodic table. Since at least one of the oxides is contained, the so-called extraction effect of the titanium compound Iusker can be remarkably exhibited, and the toughness and hardness of the sintered body can be improved. Further, by using a titanium compound or a titanium compound whisker, it is possible to improve wear resistance as a cutting tool and color tone as a decorative material. This allows cutting tools and other wear resistant parts,
A titanium compound sintered body suitable for a decorative material can be obtained.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/58 １０１ Ｇ １０５ Ｋ Ｃ０４Ｂ 35/56 Ｔ Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C04B 35/58 101 G 105 K C04B 35/56 T
Claims (1)
化物からなるチタン化合物のうち少なくとも一種を４５
〜９７体積％含有し、前記チタン化合物のうち少なくと
も一種がチタン化合物ウイスカーとして全量中５〜７０
体積％の割合で存在し、さらに、周期律表第４ａ，５
ａ，６ａ族元素の炭化物，窒化物，炭窒化物，酸化物の
うち少なくとも一種を３体積％以上含有することを特徴
とするチタン化合物焼結体。1. At least one of titanium compounds consisting of titanium carbide, nitride, boride and carbonitride is used.
To 97% by volume, and at least one of the titanium compounds as a titanium compound whisker in the total amount of 5 to 70
It exists in a volume% ratio, and further, the periodic table 4a, 5
A titanium compound sintered body containing at least 3% by volume of at least one of carbides, nitrides, carbonitrides and oxides of a and 6a group elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5161279A JP3051603B2 (en) | 1993-06-30 | 1993-06-30 | Titanium compound sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5161279A JP3051603B2 (en) | 1993-06-30 | 1993-06-30 | Titanium compound sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0782048A true JPH0782048A (en) | 1995-03-28 |
| JP3051603B2 JP3051603B2 (en) | 2000-06-12 |
Family
ID=15732093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5161279A Expired - Fee Related JP3051603B2 (en) | 1993-06-30 | 1993-06-30 | Titanium compound sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3051603B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020114725A1 (en) * | 2018-12-07 | 2020-06-11 | The Swatch Group Research And Development Ltd | Decorative ceramic article |
| EP3974405A1 (en) * | 2020-09-25 | 2022-03-30 | The Swatch Group Research and Development Ltd | Ceramic decorative item |
| JP2024017328A (en) * | 2022-07-27 | 2024-02-08 | 黒崎播磨株式会社 | Alumina sintered body and electrostatic chuck |
-
1993
- 1993-06-30 JP JP5161279A patent/JP3051603B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020114725A1 (en) * | 2018-12-07 | 2020-06-11 | The Swatch Group Research And Development Ltd | Decorative ceramic article |
| CN113165983A (en) * | 2018-12-07 | 2021-07-23 | 斯沃奇集团研究和开发有限公司 | Decorative ceramic article |
| JP2022509119A (en) * | 2018-12-07 | 2022-01-20 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Decorative ceramics |
| EP3974405A1 (en) * | 2020-09-25 | 2022-03-30 | The Swatch Group Research and Development Ltd | Ceramic decorative item |
| JP2024017328A (en) * | 2022-07-27 | 2024-02-08 | 黒崎播磨株式会社 | Alumina sintered body and electrostatic chuck |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3051603B2 (en) | 2000-06-12 |
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