JPH08310860A - Black zirconia ceramics sintered body and method for producing the same - Google Patents
Black zirconia ceramics sintered body and method for producing the sameInfo
- Publication number
- JPH08310860A JPH08310860A JP7138674A JP13867495A JPH08310860A JP H08310860 A JPH08310860 A JP H08310860A JP 7138674 A JP7138674 A JP 7138674A JP 13867495 A JP13867495 A JP 13867495A JP H08310860 A JPH08310860 A JP H08310860A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- component
- weight
- black zirconia
- zirconia ceramics
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000005452 bending Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 230000001953 sensory effect Effects 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000004040 coloring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003086 colorant Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
(57)【要約】
【目的】 時計枠、ネクタイピンなどの黒色装飾部材と
して用いられる黒色ジルコニアセラミックスにおいて、
ジルコニアセラミックスの高強度性を損なう事なく、よ
り滑らかで深みのある均一に着色された黒色ジルコニア
セラミックスを提供する。
【構成】 部分安定化ＺｒＯ2粉末を９５〜９９．５重
量％と、黒色化剤として、炭化物と酸化物の各々少なく
とも１種を０．１〜２．０重量％、合計にして０．５〜
５．０重量％添加し、これらを混合した粉末を１０Ｔｏ
ｒｒ以下の真空中において１３００〜１６００℃の範囲
で焼結して相対密度９３％以上とすることにより、ＪＩ
ＳＺ８７２９に基づく感覚色でＬ*＜４８、−２＜ａ*＜
２、−２＜ｂ*＜２の範囲の黒色で、曲げ強度が１００
ｋｇ／ｍｍ2以上の黒色ジルコニアセラミック焼結体を
得る。(57) [Summary] [Purpose] In black zirconia ceramics used as black decorative members such as watch frames and tie pins,
Provided is a black zirconia ceramic that is smoother, has a deeper color, and is uniformly colored, without impairing the high strength of the zirconia ceramics. [Structure] 95 to 99.5% by weight of partially stabilized ZrO 2 powder and 0.1 to 2.0% by weight of at least one of each of a carbide and an oxide as a blackening agent, 0.5 in total. ~
5.0 wt% was added and the powder obtained by mixing them was mixed with 10 To
By sintering in a vacuum of rr or less in the range of 1300 to 1600 ° C. to obtain a relative density of 93% or more, JI
L * <48, -2 <a * <with a sense color based on SZ8729.
2, black in the range of -2 <b * <2, with a bending strength of 100
A black zirconia ceramic sintered body having a kg / mm 2 or more is obtained.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、黒色ジルコニア焼結体
を用いた部材、例えば、スパイク、時計枠、時計バン
ド、ネクタイピン、ボタンなどの黒色装飾部材に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a member using a black zirconia sintered body, for example, a black decorative member such as a spike, a watch frame, a watch band, a tie pin and a button.
【０００２】[0002]
【従来の技術】ジルコニア焼結体は、靭性、曲げ強度な
どの機械特性が優れている為に、広範囲な分野の用途が
期待されている。特に、色調を黒色化させたジルコニア
焼結体は、例えば、時計枠、時計バンド、ネクタイピ
ン、ボタンなどの装飾用として用いられている。2. Description of the Related Art Zirconia sintered bodies are expected to be used in a wide range of fields because they have excellent mechanical properties such as toughness and bending strength. In particular, a zirconia sintered body having a black color tone is used for decoration of, for example, a watch frame, a watch band, a tie pin, a button and the like.
【０００３】高強度ＺｒＯ2の着色技術については種々
の試みがなされている。その手段としてはＺｒＯ2に着
色成分を加える方法が主体である。Various attempts have been made to color the high-strength ZrO 2 . As a means for this, a method of adding a coloring component to ZrO 2 is mainly used.
【０００４】例えば（１）特開昭６０−９０８７２号公
報には安定化したＺｒＯ2に少量の炭素を加えた還元性
雰囲気中で焼結し炭素および炭化ジルコニウムを生成さ
せた黒色ＺｒＯ2が開示されている。又、（２）炭素を
ＺｒＯ2成形体の周囲に配置して非酸化性雰囲気中で焼
成して炭素を含浸させ前記公報（１）と同様炭素および
炭化ジルコニウムを生成させ黒色化したＺｒＯ2が特開
昭６３−１０００５９号公報に、さらに（３）類似の方
法でさらに周期律表IVａ，Ｖａ，VIａ，VIIａ，VIIIａ
族元素の金属配化物着色成分を加えた事例が特公平７−
１２９７８号公報に記載されている。又、（４）類似の
酸化物からなる着色剤を炭素とともに添加するものが特
公平３−９０６２号公報に開示されている。For example, (1) Japanese Patent Laid-Open No. 60-90872 discloses black ZrO 2 obtained by sintering stabilized ZrO 2 in a reducing atmosphere containing a small amount of carbon to produce carbon and zirconium carbide. Has been done. In addition, (2) carbon is placed around the ZrO 2 compact and fired in a non-oxidizing atmosphere to impregnate the carbon to produce carbon and zirconium carbide, and blackened ZrO 2 is obtained. In Japanese Patent Application Laid-Open No. 63-100059, the periodic table IVa, Va, VIa, VIIa, VIIIa is further prepared by a method similar to (3).
Special case is 7-
No. 12978. Further, (4) Japanese Patent Publication No. 3-9062 discloses that a colorant composed of a similar oxide is added together with carbon.
【０００５】さらに（５）Ｙ2Ｏ3等の安定化剤を加えた
ＺｒＯ2焼結体を還元性雰囲気中で処理すると１２００
℃以上で黒色化したＺｒＯ2のえられることが特公平３
−６７９８３号に記載されている。Further, (5) a ZrO 2 sintered body to which a stabilizer such as Y 2 O 3 was added was treated in a reducing atmosphere to produce 1200
It is especially fair that ZrO 2 that turns black above ℃ can be obtained 3
-67983.
【０００６】[0006]
【発明が解決しようとする課題】以上述べた従来の技術
の中で（１）〜（４）については焼結体中に炭素が単体
で残留し、特に表面に比べ内部に多くなるため黒色化の
程度に差が生じ易い。又（５）についても焼結体の表面
と内部での還元状況に差が生じ易いため着色の均一化に
問題が残る。Among the conventional techniques described above, regarding (1) to (4), carbon alone remains in the sintered body, and in particular, the amount of carbon remains inside the sintered body, so that blackening occurs. Is likely to vary. Further, with respect to (5), there is still a problem in uniform coloring because a difference easily occurs between the reduction state on the surface of the sintered body and the reduction state on the inside.
【０００７】本発明は、上記問題点を鑑みて鋭意研究の
末、なされたものであり、ジルコニアセラミックスの高
強度性を損なう事なく、より滑らかで深みのある均一に
着色した黒色ジルコニアセラミックス、及びその製造方
法を提供するものである。The present invention has been made as a result of intensive studies in view of the above-mentioned problems, and it is a uniformly colored black zirconia ceramic having a smoother and deeper color, without impairing the high strength of the zirconia ceramics, and The manufacturing method is provided.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するた
め、この発明は、部分安定化ジルコニアを主成分とし、
黒色化剤として、炭化物と酸化物の各々を少なくとも１
種含有する焼結体において、ＪＩＳＺ８７２９に基づく
感覚色でＬ*＜４８、−２＜ａ*＜２、−２＜ｂ*＜２の
範囲の黒色を呈し、曲げ強度が１００ｋｇ／ｍｍ2以上
の黒色ジルコニアセラミックス焼結体としたものであ
る。In order to solve the above-mentioned problems, the present invention comprises partially stabilized zirconia as a main component,
At least one of each of carbide and oxide is used as a blackening agent.
The seed-containing sintered body exhibits a black color in the range of L * <48, -2 <a * <2, -2 <b * <2 as a sensory color based on JIS Z8729, and a bending strength of 100 kg / mm 2 or more. It is a black zirconia ceramics sintered body.
【０００９】また、本発明の黒色ジルコニアセラミック
ス焼結体の製造方法としては、部分安定化ＺｒＯ2粉末
を９５〜９９．５重量％と、黒色化剤として、炭化物と
酸化物の各々少なくとも１種を０．１〜２．０重量％、
合計にして０．５〜５．０重量％添加し、これらを混合
した粉末を１０Ｔｏｒｒ以下の真空中において１３００
〜１６００℃の範囲で焼結し、相対密度９３％以上の黒
色ジルコニアセラミックス焼結体を得るものである。Further, as a method for producing a black zirconia ceramics sintered body of the present invention, 95 to 99.5% by weight of partially stabilized ZrO 2 powder and at least one of a carbide and an oxide are used as a blackening agent. 0.1 to 2.0% by weight,
A total of 0.5 to 5.0% by weight was added, and a powder obtained by mixing them was added to a powder of 1300 in a vacuum of 10 Torr or less.
Sintering is performed in the range of 1600 ° C. to obtain a black zirconia ceramics sintered body having a relative density of 93% or more.
【００１０】なお、本発明で用いる前記黒色化剤として
は、第１成分に第IVａ族の炭化物、第２成分に第Ｖａ
族、第VIａ族の酸化物、第３成分に第IIａ族、第VIII族
の酸化物の少なくとも１種を各々０．１〜２．０重量
％、合計にして０．５〜５．０重量％含むのが好まし
い。As the blackening agent used in the present invention, the first component is a Group IVa carbide and the second component is a Va group.
0.1 to 2.0% by weight of at least one of Group IIa and Group VIII oxides as a third component, Group VIa oxide, and a total of 0.5 to 5.0% by weight. % Is preferable.
【００１１】更に、上記第１成分にはＴｉＣ，ＨｆＣの
少なくとも１種、第２成分にはＣｒ，Ｍｏ，Ｗ，Ｖ，Ｔ
ａの内の少なくとも１種の酸化物、第３成分にはＦｅ，
Ｃｏ，Ｎｉ，Ｍｇの内の少なくとも１種以上の酸化物を
用いるのが好ましく、第４成分としてＡｌ2Ｏ3を０．１
〜２．０重量％混合するようにすることもできる。Further, the first component is at least one of TiC and HfC, and the second component is Cr, Mo, W, V, T.
at least one oxide of a, Fe as the third component,
Co, Ni, it is preferable to use at least one or more oxides of the Mg, the for Al 2 O 3 fourth component 0.1
It is also possible to mix up to 2.0% by weight.
【００１２】又、前記黒色ジルコニアセラミックス焼結
体の製造方法において、焼結の後に２００ｋｇ／ｍｍ2
以上の加圧下、１３００〜１６００℃にて熱間静水圧プ
レスする焼結工程を含ませることもできる。In the method for producing a black zirconia ceramics sintered body, after sintering, 200 kg / mm 2
A sintering process of hot isostatic pressing at 1300 to 1600 ° C under the above pressure can be included.
【００１３】[0013]
【作用】本発明による黒色ジルコニアセラミックス焼結
体は、安定化剤として公知の材質を用いたセラミックス
であり、安定化剤としては例えばＹ2Ｏ3，ＣｅＯ2が適
切である。The black zirconia ceramics sintered body according to the present invention is a ceramic using a known material as a stabilizer, and Y 2 O 3 and CeO 2 are suitable as the stabilizer.
【００１４】ジルコニアセラミックスは固相焼結する
が、安定化剤以外に黒色化剤を添加する場合、ジルコニ
ア粉末の割合が９５重量％未満であれば、優れた機械特
性の焼結体が得られず、９９．５重量％を越えると、着
色効果が不十分となる。Zirconia ceramics is solid-phase sintered, but when a blackening agent is added in addition to the stabilizer, if the proportion of zirconia powder is less than 95% by weight, a sintered body having excellent mechanical properties can be obtained. If it exceeds 99.5% by weight, the coloring effect becomes insufficient.
【００１５】ジルコニアセラミックスを黒色化させる為
に黒色化剤として、金属酸化物、あるいは金属炭化物等
を単独添加すると、一般的に多量の黒色化剤を加える必
要があり、その為に焼結性が悪くなり、機械特性が劣化
する傾向にある。この為に、できるだけ少量の添加剤で
ジルコニアセラミックスを効果的に黒色化させる必要が
ある。When a metal oxide, a metal carbide or the like is solely added as a blackening agent for blackening the zirconia ceramics, it is generally necessary to add a large amount of the blackening agent, and therefore the sinterability is improved. The mechanical properties tend to deteriorate and the mechanical properties deteriorate. For this reason, it is necessary to effectively blacken the zirconia ceramics with as little additive as possible.
【００１６】本発明によれば、金属炭化物および金属酸
化物を同時に加える事が重要である。両者を添加する事
により、少ない添加剤で効果的にジルコニアセラミック
スを均一に黒色化させる事が可能である。According to the invention, it is important to add the metal carbide and the metal oxide simultaneously. By adding both, it is possible to effectively blacken the zirconia ceramics uniformly with a small amount of additives.
【００１７】この場合、第１成分としての炭化物は、第
IVａ族のものがよく含有量は０．１〜２．０重量％とす
る。第IVａ族の中でも、特にＴｉ，Ｈｆが好適である。In this case, the carbide as the first component is
Group IVa is preferable, and the content is 0.1 to 2.0% by weight. Among the Group IVa, Ti and Hf are particularly preferable.
【００１８】また、酸化物としては含有量は０．１〜
２．０重量％とし、第Ｖａ族、第VIａ族の酸化物を第２
成分として、さらに第IIａ族、第VIII族の元素の酸化物
を第３成分として選びそれぞれの成分の少なくとも１種
を選定する必要がある。特に、第２成分としてはＣｒ，
Ｍｏ，Ｗ，Ｖ，Ｔａが、第３成分としてはＦｅ，Ｃｏ，
Ｎｉ，Ｍｇが好適である。The content of the oxide is 0.1-0.1%.
2.0 wt.% And the oxides of Group Va and VIa are secondarily added.
As the component, it is necessary to further select an oxide of a Group IIa or Group VIII element as the third component and select at least one of the respective components. In particular, as the second component, Cr,
Mo, W, V, Ta are Fe, Co,
Ni and Mg are preferable.
【００１９】以上の第１〜第３成分の量は合計にして
０．５〜５．０重量％添加する。各成分とも０．１重量
％未満であると、添加の効果がなく、２．０重量％を越
えると、他の添加剤との分散状態が悪くなり着色の滑ら
かさが低下する。また、これらの黒色化剤が合計で０．
５重量％未満であれば均一な黒色調にはなるが本発明の
意図する深く滑らかな着色の効果が現れにくくなり、
５．０重量％を越えるとそれ以上の着色の効果がえられ
ず、逆に焼結性が低下し、その為に機械的特性が劣化す
る。更に、場合によっては黒色系以外の色を示す事もあ
り、本発明で開示した感覚色の範囲を逸脱する場合があ
る。The above-mentioned first to third components are added in a total amount of 0.5 to 5.0% by weight. If the content of each component is less than 0.1% by weight, the effect of addition is not obtained, and if it exceeds 2.0% by weight, the state of dispersion with other additives is deteriorated and the smoothness of coloring is deteriorated. The total amount of these blackening agents is 0.
If it is less than 5% by weight, a uniform black tone is obtained, but the effect of deep and smooth coloring intended by the present invention is difficult to appear,
If it exceeds 5.0% by weight, no further coloring effect can be obtained, and conversely, the sinterability is lowered, and therefore the mechanical properties are deteriorated. Furthermore, in some cases, colors other than black may be displayed, which may deviate from the range of sensory colors disclosed in the present invention.
【００２０】また、Ａｌ2Ｏ3を添加するのは、黒色化剤
を多く添加すると、それだけでは場合によっては粒成長
が著しくなる為に、その抑制剤として使用するのであ
る。Further, Al 2 O 3 is used as an inhibitor because if a large amount of a blackening agent is added, grain growth becomes remarkable depending on the case.
【００２１】本発明による黒色ジルコニアセラミックス
焼結体は、以上の酸化物と炭化物を含むが、炭化物と酸
化物との化合物、あるいは酸化物同志の反応による複合
化合物が形成されていても構わない。The black zirconia ceramics sintered body according to the present invention contains the above oxides and carbides, but a compound of carbides and oxides or a complex compound formed by the reaction of oxides may be formed.
【００２２】次に本発明による焼結とＨＩＰの効果を説
明する。Next, the effects of sintering and HIP according to the present invention will be described.
【００２３】本発明の場合、１００ｋｇ／ｍｍ2以上の
抗折力を持った黒色ジルコニアを作成する為には、１０
Ｔｏｒｒ以下の真空度で焼結しなければならない。１０
Ｔｏｒｒよりも低い真空度で焼結を行なうと、焼結体の
表面が酸化されて白色を呈する傾向がある。In the case of the present invention, in order to prepare a black zirconia having a bending strength of 100 kg / mm 2 or more, 10
Sintering must be done at a vacuum below Torr. 10
When sintering is performed at a vacuum degree lower than Torr, the surface of the sintered body tends to be oxidized and white.
【００２４】焼結の温度条件としては、１３００〜１６
００℃が好ましい。これは、１３００℃未満では緻密化
が不十分であり、また１６００℃を越えると焼結体の粒
成長が著しく、かつ強度の低下が大きい為である。The sintering temperature conditions are 1300 to 16
00 ° C is preferred. This is because if the temperature is lower than 1300 ° C, the densification is insufficient, and if the temperature exceeds 1600 ° C, the grain growth of the sintered body is remarkable and the strength is largely reduced.
【００２５】更に、抗折力１００ｋｇ／ｍｍ2以上の焼
結体を得る為には、相対密度が９３％以上になるように
焼結する必要がある。Further, in order to obtain a sintered body having a transverse rupture strength of 100 kg / mm 2 or more, it is necessary to sinter so that the relative density is 93% or more.
【００２６】又、焼結後さらにＨＩＰをする場合の条件
についても、同様の理由により温度は１３００〜１６０
０℃の範囲内で行ない、２００ｋｇ／ｃｍ2以上の加圧
下で行なう必要がある。これは、２００ｋｇ／ｃｍ2未
満の圧力下であると、焼結時に残った焼結体中の気孔を
効果的に除去できずに、緻密化できないからである。Also, for the condition when HIP is further performed after sintering, the temperature is 1300 to 160 for the same reason.
It is necessary to perform the treatment within the range of 0 ° C. and under the pressure of 200 kg / cm 2 or more. This is because if the pressure is less than 200 kg / cm 2 , the pores in the sintered body remaining during sintering cannot be effectively removed and the densification cannot be performed.
【００２７】本発明の黒色化したジルコニアセラミック
ス焼結体の黒色化の程度を感覚色で定義すると、ＪＩＳ
Ｚ８７２９によって規定されているＬ*ａ*ｂ*表色系に
よれば、Ｌ*＜４８、−２＜ａ*＜２、−２＜ｂ*＜２の
範囲を満たす色でなければならない。When the degree of blackening of the blackened zirconia ceramics sintered body of the present invention is defined by the sensory color, JIS
According to the L * a * b * color system defined by Z8729, the colors must satisfy the ranges of L * <48, -2 <a * <2, -2 <b * <2.
【００２８】ここで、Ｌ*は明度、ａ*、ｂ*は色度を表
わすもので、Ｌ*の値が高くなれば白くなり、ａ*が高く
なれば赤、低くなれば緑色を帯び、ｂ*が高くなれば黄
色、低くなれば青色を帯びる。Here, L * represents lightness, and a * and b * represent chromaticity . When the value of L * is high, the color is white, when the value of a * is high, the color is red, and when the value is low, the color is green. When b * is high, it is yellow, and when it is low, it is blue.
【００２９】被測定物の感覚色は、被測定物の表面粗さ
に依存する。この為、本発明で開示している値は、被測
定物の表面粗さが、Ｒａ＜０．０２μｍの条件を満たす
場合の感覚色を示している。The sensory color of the object to be measured depends on the surface roughness of the object to be measured. Therefore, the values disclosed in the present invention indicate the sensory color when the surface roughness of the measured object satisfies the condition Ra <0.02 μm.
【００３０】被測定物の表面粗さが粗くなると、感覚
色、特に明度Ｌ*が低下する。例えば、本発明で開示し
ている黒色ジルコニアセラミックス焼結体をＲａ＜０．
０２μｍの面粗さに加工して感覚色を測定すると、Ｌ*
＜４８、−２＜ａ*＜２、−２＜ｂ*＜２となるが、同じ
焼結体を、Ｒａ＝０．５μｍの面粗さになるように加工
すると、その感覚色は、Ｌ*は約１６ほど値が低下す
る。When the surface roughness of the object to be measured becomes rough, the sensory color, particularly the lightness L * , decreases. For example, when the black zirconia ceramics sintered body disclosed in the present invention is Ra <0.
When processed with a surface roughness of 02 μm and measuring the sensory color, L *
<48, -2 <a * <2, -2 <b * <2, but when the same sintered body was processed to have a surface roughness of Ra = 0.5 μm, the sense color was L * Decreases about 16 values.
【００３１】また、Ｒａ＜０．０２μｍの条件下で、よ
り深みのある滑らかな黒色の度合いは、Ｌ*＜４６、−
０．３＜ａ*＜０．３、−０．３＜ｂ*＜０．３である。Under the condition of Ra <0.02 μm, the degree of deep and smooth black is L * <46, −
0.3 <a * <0.3 and −0.3 <b * <0.3.
【００３２】[0032]
（実施例１）Ｙ2Ｏ3を含有した部分安定化ＺｒＯ2粉末
（平均粒径０．４μｍ）と表１に示す組合せの黒色化剤
粉末（いずれも平均粒径０．６μｍ）をそれぞれ混合し
混合粉末を５００ｋｇ／ｃｍ2の圧力で成形して、５ｍ
ｍ（幅）×４５ｍｍ（長さ）×４ｍｍ（厚み）の型押体
を得た。(Example 1) Partially stabilized ZrO 2 powder containing Y 2 O 3 (average particle size 0.4 μm) and a combination of blackening agent powders shown in Table 1 (all average particle size 0.6 μm) were mixed. Then, the mixed powder is molded at a pressure of 500 kg / cm 2 and
An embossed body of m (width) × 45 mm (length) × 4 mm (thickness) was obtained.
【００３３】この型押体を１０-2Ｔｏｒｒの真空炉で温
度１５００℃×３時間焼結した。又、一部の試料は更に
アルゴンガス中１０００ｋｇ／ｃｍ2の圧力下で１４０
０℃×１時間ＨＩＰを行なった。The embossed body was sintered in a vacuum furnace of 10 -2 Torr at a temperature of 1500 ° C for 3 hours. In addition, some of the samples were further subjected to 140 kg in argon gas under a pressure of 1000 kg / cm 2.
HIP was performed at 0 ° C. for 1 hour.
【００３４】このようにして得られた焼結体を４ｍｍ
（幅）×３６ｍｍ（長さ）×３ｍｍ（厚み）の試験片に
研磨加工し、曲げ強度、相対密度および電気伝導度を測
定した。又、試験片の表面粗さをＲａ＜０．０２μｍに
なるよう加工して感覚色を測定した。その結果を表２に
示す。4 mm of the thus obtained sintered body
A test piece of (width) × 36 mm (length) × 3 mm (thickness) was polished, and bending strength, relative density and electric conductivity were measured. The sensory color was measured by processing the surface roughness of the test piece to Ra <0.02 μm. The results are shown in Table 2.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】尚、これらの焼結体のＸ線回析パターンを
確認した結果、正方晶系及び単斜晶系のＺｒＯ2のピー
クと各黒色化剤のピークが検出された。As a result of confirming the X-ray diffraction pattern of these sintered bodies, peaks of tetragonal and monoclinic ZrO 2 and peaks of each blackening agent were detected.
【００３８】以上の結果より、黒色化剤として炭化物の
みを加えたＮｏ．１については、黒色化の程度が十分で
なく、また表面の一部に色むらが認めら、また曲げ強度
も低い。又、酸化物のみを加えたＮｏ．２についても、
黒色化の程度が十分でないだけでなく、曲げ強度も低
い。From the above results, No. 1 containing only carbide as a blackening agent was added. Regarding No. 1, the degree of blackening was not sufficient, color unevenness was observed on a part of the surface, and the bending strength was low. In addition, No. Also for 2,
Not only is the degree of blackening not sufficient, but the bending strength is also low.
【００３９】更に、☆３、☆４のように、焼結体にさら
にＨＩＰ処理を行なったものはそれぞれ対応するＮｏ．
３、Ｎｏ．４の焼結体に比べ、相対密度が向上してお
り、より緻密化している。この為、曲げ強度及びシャル
ピー衝撃値はより向上している。又、電気伝導度は試料
Ｎｏ．１以外は１０-7Ω-1／ｃｍ以下であった。Further, as shown by * 3 and * 4, those obtained by subjecting the sintered body to the HIP treatment further correspond to No.
3, No. Compared with the sintered body of No. 4, the relative density is improved and it is more densified. Therefore, the bending strength and the Charpy impact value are further improved. In addition, the electrical conductivity of the sample No. Other than 1 was 10 -7 Ω -1 / cm or less.
【００４０】（実施例２）実施例１と同様の部分安定化
ＺｒＯ2粉末と表３に示す組合せの黒色化剤粉末（いず
れも平均粒径０．６μｍ）をそれぞれ混合した混合粉末
を実施例１同様の条件で成形、焼結した。又、一部の試
料については更に実施例１と同様の条件でＨＩＰを行な
った。Example 2 A mixed powder obtained by mixing the partially stabilized ZrO 2 powder similar to that of Example 1 and the blackening agent powder of the combinations shown in Table 3 (each having an average particle size of 0.6 μm) was used as an example. 1. Molded and sintered under the same conditions. Further, some of the samples were further subjected to HIP under the same conditions as in Example 1.
【００４１】このようにして得られた焼結体を実施例１
と同様の試験片とし、実施例１と同様の特性確認を行な
った。その結果を表４に示す。The sintered body thus obtained was used in Example 1.
The same test piece as in Example 1 was used, and the same characteristics as in Example 1 were confirmed. The results are shown in Table 4.
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【表４】 [Table 4]
【００４４】これらの焼結体のＸ線回析より、ＺｒＯ2
相は正方晶系及び単斜晶系からなり、各黒色化剤のピー
クが検出された。From X-ray diffraction of these sintered bodies, ZrO 2
The phases consisted of tetragonal system and monoclinic system, and peaks of each blackening agent were detected.
【００４５】以上の結果より黒色化剤の合計量が０．５
重量％に満たない場合には、曲げ強度は１００ｋｇ／ｃ
ｍ2以上を示すが、黒色化の度合いが不十分で、Ｌ*＜４
８、−２＜ａ*＜２、−２＜ｂ*＜２を満たさず、又、５
重量％を越えると、感覚色は５重量％以下の場合と殆ど
差異がないにもかかわらず焼結性が劣化する為に、相対
密度、曲げ強度、シャルピー衝撃値のような機械特性が
低下していることがわかる（試料Ｎｏ．１１および１
５）。From the above results, the total amount of the blackening agent is 0.5.
If the weight is less than 100%, the bending strength is 100 kg / c.
m 2 or more, but the degree of blackening is insufficient and L * <4
8, -2 <a * <2, -2 <b * <2 are not satisfied, and 5
When the content exceeds 5% by weight, the sensual color is almost the same as that when the content is 5% by weight or less, but the sinterability deteriorates, so that the mechanical properties such as relative density, bending strength and Charpy impact value deteriorate. (Sample Nos. 11 and 1)
5).
【００４６】又、黒色化剤各成分の量が１成分でも０．
１重量％に満たないと、その成分の着色効果が現れにく
く、本発明で開示した感覚色の範囲の条件を満たさず、
２．０重量％を越えても、同じように所定の範囲の感覚
色が得られず、又、分散性が悪くなる為に一部色むらが
存在していることがわかる（試料Ｎｏ．１６〜２１）。Even if the amount of each component of the blackening agent is one,
If it is less than 1% by weight, the coloring effect of the component is difficult to appear, and the condition of the sensory color range disclosed in the present invention is not satisfied,
Even if the amount exceeds 2.0% by weight, it is found that the sensory color in the predetermined range cannot be obtained in the same manner, and the dispersibility is deteriorated, so that some color unevenness exists (Sample No. 16). 21).
【００４７】（実施例３）実施例１と同じ部分安定化Ｚ
ｒＯ2粉末と黒色化剤各成分からなる表５に示す組合せ
の粉末をそれぞれ混合し、実施例１と同じ条件で成形・
焼結し、同様の試験片を作り結晶粒径及び実施例１と同
様の評価を行なった。(Embodiment 3) The same partially stabilized Z as in Embodiment 1
The powders of the combinations shown in Table 5 consisting of rO 2 powder and each component of the blackening agent were mixed and molded under the same conditions as in Example 1.
Sintering was performed to prepare the same test piece, and the same evaluation as the crystal grain size and Example 1 was performed.
【００４８】又、一部のものについては更に実施例１と
同様のＨＩＰ処理を行なった。これについても同様の評
価を行なった。その結果を表６に示す。Further, some of them were further subjected to the same HIP treatment as in Example 1. The same evaluation was performed for this. Table 6 shows the results.
【００４９】Ｘ線で確認したところ正方晶系と単斜晶系
のＺｒＯ2相及び各黒色化剤相が共存しており、複合物
相として試料Ｎｏ．２８〜３０ではＮｉＡｌ2Ｏ4が観察
された。When confirmed by X-ray, the tetragonal and monoclinic ZrO 2 phases and the respective blackening agent phases coexist, and as a composite phase, the sample No. NiAl 2 O 4 was observed at 28 to 30.
【００５０】[0050]
【表５】 [Table 5]
【００５１】[0051]
【表６】 [Table 6]
【００５２】このうち第４成分としてＡｌ2Ｏ3を加えた
試料Ｎｏ．２９，３０については、加えないものに比べ
てＺｒＯ2の結晶粒径は小さくなっており、それにより
曲げ強度、シャルピー衝撃値も高くなっている。Of these, sample No. 4 containing Al 2 O 3 as the fourth component was added. Regarding Nos. 29 and 30, the crystal grain size of ZrO 2 is smaller than that of the ones not added, so that the bending strength and the Charpy impact value are also higher.
【００５３】但しＡｌ2Ｏ3量が０．１重量％未満のＮ
ｏ．２８では結晶粒径は添加しないＮｏ．２２とほとん
ど変わりなく、曲げ強度、シャルピー衝撃値もほとんど
変わらない。However, N containing Al 2 O 3 in an amount of less than 0.1% by weight.
o. In No. 28, the crystal grain size is not added. The bending strength and the Charpy impact value are almost the same as those of No. 22.
【００５４】更に、Ａｌ2Ｏ3量が２重量％を越えたＮ
ｏ．３１では粒径は小さいものの、実施例２と同様に、
分散性が悪くなり、表面の一部には色むらが観察され
た。Further, N containing Al 2 O 3 in an amount of more than 2% by weight.
o. In No. 31, although the particle size is small, as in Example 2,
Dispersibility deteriorated, and color unevenness was observed on a part of the surface.
【００５５】（実施例４）実施例１のＮｏ．３とＮｏ．
４の組成及び形状の成形体を表７の各種焼結条件で焼結
し、実施例１と同形状の試験片を準備した。その評価結
果を同じ表７に示す。(Embodiment 4) No. 1 of the first embodiment. 3 and No.
A molded product having the composition and shape of 4 was sintered under various sintering conditions shown in Table 7 to prepare a test piece having the same shape as that of Example 1. The evaluation results are shown in the same Table 7.
【００５６】[0056]
【表７】 [Table 7]
【００５７】この結果より、真空度は１０Ｔｏｒｒ以
下、温度は１３００〜１６００℃の場合、曲げ強度、シ
ャルピー衝撃値ともにそれぞれ１２０ｋｇ／ｍｍ2以
上、０．２６０ｋｇｆ／ｍｍ2以上の値が得られ、又、
黒色化の色調についても滑らかでかつ均一な黒色のもの
が得られることがわかる。From these results, when the degree of vacuum is 10 Torr or less and the temperature is 1300 to 1600 ° C., the bending strength and the Charpy impact value are 120 kg / mm 2 or more and 0.260 kgf / mm 2 or more, respectively. ,
It can be seen that a smooth and uniform black color tone can be obtained.
【００５８】（実施例５）実施例４のＮｏ．３４、Ｎ
ｏ．３８の焼結体を更に表８に示す各種条件でＨＩＰ処
理し、実施例１と同じ形状の試験片とし実施例４と同様
の評価を行なった。その結果を表８に示す。(Fifth Embodiment) No. 4 of the fourth embodiment. 34, N
o. The sintered body of No. 38 was subjected to HIP treatment under various conditions shown in Table 8 to obtain a test piece having the same shape as that of Example 1, and the same evaluation as that of Example 4 was performed. Table 8 shows the results.
【００５９】[0059]
【表８】 [Table 8]
【００６０】この結果より真空度１０Ｔｏｒｒ以下、温
度１３００〜１６００℃、圧力２００ｋｇ／ｃｍ2以上
の条件でＨＩＰを行なうことによってより緻密なものが
得られ、曲げ強度、シャルピー衝撃値ともに焼結時点よ
り顕著に改善されることがわかる。From this result, it is possible to obtain a denser product by performing HIP under the conditions of a vacuum degree of 10 Torr or less, a temperature of 1300 to 1600 ° C., and a pressure of 200 kg / cm 2 or more. It can be seen that it is remarkably improved.
【００６１】[0061]
【発明の効果】以上のように、本発明により、ジルコニ
アセラミックスの緻密で高強度という特性を損なう事な
く、より滑らかで深みのある均一に着色された黒色ジル
コニアセラミックス焼結体を提供する事ができる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide a smoother, deeper and uniformly colored black zirconia ceramics sintered body without impairing the dense and high strength characteristics of the zirconia ceramics. it can.
Claims (9)
色化剤として、炭化物と酸化物の各々を少なくとも１種
含有する焼結体において、ＪＩＳＺ８７２９に基づく感
覚色でＬ*＜４８、−２＜ａ*＜２、−２＜ｂ*＜２の範
囲の黒色を呈し、曲げ強度が１００ｋｇ／ｍｍ2以上の
黒色ジルコニアセラミックス焼結体。1. A sintered body containing partially stabilized zirconia as a main component and containing at least one of a carbide and an oxide as a blackening agent, and having a sensory color according to JIS Z8729, L * <48, -2 <. A black zirconia ceramics sintered body exhibiting a black color in the range of a * <2, −2 <b * <2 and having a bending strength of 100 kg / mm 2 or more.
族の炭化物、第２成分に第Ｖａ族、第VIａ族の酸化物、
第３成分に第IIａ族、第VIII族の酸化物を各々少なくと
も１種を各々０．１〜２．０重量％、合計にして０．５
〜５．０重量％含む事を特徴とする請求項１に記載の黒
色ジルコニアセラミックス焼結体。2. The first component as the blackening agent is IVa
Group III carbides, second component Va, VIa oxides,
The third component is at least one oxide of Group IIa and Group VIII, and each is 0.1 to 2.0% by weight, and the total is 0.5.
The black zirconia ceramics sintered body according to claim 1, wherein the black zirconia ceramics sintered body is contained in an amount of up to 5.0% by weight.
Ｃ，ＨｆＣの内の少なくとも１種、第２成分にＣｒ，Ｍ
ｏ，Ｗ，Ｖ，Ｔａの内の少なくとも１種の酸化物、第３
成分にＦｅ，Ｃｏ，Ｎｉ，Ｍｇの内の少なくとも１種以
上の酸化物を各々０．１〜２．０重量％、合計にして
０．５〜５．０重量％含む事を特徴とする請求項１又は
２に記載の黒色ジルコニアセラミックス焼結体。3. The first component as the blackening agent is Ti
At least one of C and HfC, and Cr and M as the second component
o, W, V, Ta, at least one oxide, third
0.1 to 2.0% by weight of each of at least one oxide of Fe, Co, Ni, and Mg is contained in the component, and a total of 0.5 to 5.0% by weight is contained. Item 3. A black zirconia ceramics sintered body according to Item 1 or 2.
成分としてＡｌ2Ｏ3を０．１〜２．０重量％含む事を特
徴とする請求項第２又は３に記載の黒色ジルコニアセラ
ミックス焼結体。4. The black zirconia ceramic has a fourth structure.
The black zirconia ceramics sintered body according to claim 2 or 3, which contains 0.1 to 2.0% by weight of Al 2 O 3 as a component.
５重量％と、黒色化剤として、炭化物と酸化物の各々少
なくとも１種を０．１〜２．０重量％、合計にして０．
５〜５．０重量％添加し、これらを混合した粉末を１０
Ｔｏｒｒ以下の真空中において１３００〜１６００℃の
範囲で焼結し、相対密度９３％以上の焼結体を得る事を
特徴とする請求項１乃至４に記載の黒色ジルコニアセラ
ミックス焼結体の製造方法。5. The partially stabilized ZrO 2 powder is added to 95-99.
5% by weight and 0.1 to 2.0% by weight of at least one of each of a carbide and an oxide as a blackening agent, and a total of 0.1.
5 to 5.0% by weight is added, and the mixed powder is mixed with 10
The method for producing a black zirconia ceramics sintered body according to any one of claims 1 to 4, wherein the sintered body is sintered in a temperature range of 1300 to 1600 ° C in a vacuum of Torr or lower to obtain a sintered body having a relative density of 93% or higher. .
族の炭化物、第２成分に第Ｖａ族、第VIａ族の酸化物、
第３成分に第IIａ族、第VIII族の酸化物を各々少なくと
も１種を各々０．１〜２．０重量％、合計にして０．５
〜５．０重量％添加することを特徴とする請求項５に記
載の黒色ジルコニアセラミックス焼結体の製造方法。6. The first component as the blackening agent is IVa
Group III carbides, second component Va, VIa oxides,
The third component is at least one oxide of Group IIa and Group VIII, and each is 0.1 to 2.0% by weight, and the total is 0.5.
The method for producing a black zirconia ceramics sintered body according to claim 5, characterized in that the addition amount is ˜5.0 wt%.
Ｃ、ＨｆＣの内の少なくとも１種、第２成分にＣｒ，Ｍ
ｏ，Ｗ，Ｖ，Ｔａの内の少なくとも１種の酸化物、第３
成分にＦｅ，Ｃｏ，Ｎｉ，Ｍｇの内の少なくとも１種の
酸化物を添加する事を特徴とする請求項５又は６に記載
の黒色ジルコニア焼結体の製造方法。7. The first component of the blackening agent is Ti
At least one of C and HfC, and Cr and M as the second component
o, W, V, Ta, at least one oxide, third
The method for producing a black zirconia sintered body according to claim 5 or 6, wherein at least one oxide of Fe, Co, Ni, and Mg is added to the component.
してＡｌ2Ｏ3を０．１〜２．０重量％混合する事を特徴
とする請求項６又は７に記載の黒色ジルコニアセラミッ
クス焼結体の製造方法。8. The black zirconia ceramics sinter according to claim 6 or 7, wherein 0.12 to 2.0 wt% of Al 2 O 3 is mixed as a fourth component with the black zirconia sintered body. Body manufacturing method.
の製造方法において、焼結の後に２００ｋｇ／ｃｍ2以
上の加圧下、１３００〜１６００℃にて熱間静水圧プレ
スする焼結工程を含む事を特徴とする請求項５乃至８に
記載の黒色ジルコニアセラミックス焼結体の製造方法。9. The method for producing a black zirconia ceramics sintered body, comprising a sintering step of hot isostatic pressing at 1300 to 1600 ° C. under a pressure of 200 kg / cm 2 or more after sintering. The method for producing a black zirconia ceramics sintered body according to any one of claims 5 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7138674A JPH08310860A (en) | 1995-05-12 | 1995-05-12 | Black zirconia ceramics sintered body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7138674A JPH08310860A (en) | 1995-05-12 | 1995-05-12 | Black zirconia ceramics sintered body and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08310860A true JPH08310860A (en) | 1996-11-26 |
Family
ID=15227463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7138674A Pending JPH08310860A (en) | 1995-05-12 | 1995-05-12 | Black zirconia ceramics sintered body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08310860A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233671A (en) * | 2000-02-23 | 2001-08-28 | Toshiba Corp | Zirconium oxide sintered body, bearing ball and bearing member using the same |
| US7067085B1 (en) | 1999-06-29 | 2006-06-27 | Nippon Steel Corporation | Black ceramic sinter with low thermal expansion and high specific rigidity and process for producing the same |
| JPWO2007108416A1 (en) * | 2006-03-20 | 2009-08-06 | 京セラ株式会社 | Colored zirconia sintered body, method for producing the same, and decorative member |
| US7749931B2 (en) * | 2006-02-13 | 2010-07-06 | Fujifilm Corporation | Ceramic optical parts and production methods thereof |
| JP2010234436A (en) * | 2009-03-31 | 2010-10-21 | Taiheiyo Cement Corp | Capstan |
| KR101044337B1 (en) * | 2009-06-22 | 2011-06-29 | 이광호 | Method for producing black zirconia ceramics by graphite impregnation method and black zirconia ceramics produced thereby |
| EP3012239A1 (en) * | 2014-10-22 | 2016-04-27 | Comadur S.A. | Method for manufacturing a coloured item, in particular coloured grey, made of zirconia, and coloured zirconia decorative item obtained according to said method |
| JP2017520679A (en) * | 2014-06-25 | 2017-07-27 | エフエムインダストリーズ, インクFm Industries, Inc. | Emissivity-tuned coating for semiconductor chamber components |
| CN118005389A (en) * | 2023-11-30 | 2024-05-10 | 江南大学 | A preparation method for light-curing additive manufacturing of black zirconium oxide |
-
1995
- 1995-05-12 JP JP7138674A patent/JPH08310860A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7067085B1 (en) | 1999-06-29 | 2006-06-27 | Nippon Steel Corporation | Black ceramic sinter with low thermal expansion and high specific rigidity and process for producing the same |
| JP2001233671A (en) * | 2000-02-23 | 2001-08-28 | Toshiba Corp | Zirconium oxide sintered body, bearing ball and bearing member using the same |
| US7749931B2 (en) * | 2006-02-13 | 2010-07-06 | Fujifilm Corporation | Ceramic optical parts and production methods thereof |
| JPWO2007108416A1 (en) * | 2006-03-20 | 2009-08-06 | 京セラ株式会社 | Colored zirconia sintered body, method for producing the same, and decorative member |
| JP2010234436A (en) * | 2009-03-31 | 2010-10-21 | Taiheiyo Cement Corp | Capstan |
| KR101044337B1 (en) * | 2009-06-22 | 2011-06-29 | 이광호 | Method for producing black zirconia ceramics by graphite impregnation method and black zirconia ceramics produced thereby |
| JP2017520679A (en) * | 2014-06-25 | 2017-07-27 | エフエムインダストリーズ, インクFm Industries, Inc. | Emissivity-tuned coating for semiconductor chamber components |
| EP3012239A1 (en) * | 2014-10-22 | 2016-04-27 | Comadur S.A. | Method for manufacturing a coloured item, in particular coloured grey, made of zirconia, and coloured zirconia decorative item obtained according to said method |
| US10059629B2 (en) | 2014-10-22 | 2018-08-28 | Comadur S.A. | Process for the production of a zirconia-based, coloured, in particular grey, article and a zirconia-based coloured decorative article obtained using this process |
| CN118005389A (en) * | 2023-11-30 | 2024-05-10 | 江南大学 | A preparation method for light-curing additive manufacturing of black zirconium oxide |
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