JP2005306678A - Zirconia-alumina colored composite ceramic material, and method for manufacturing the same - Google Patents
Zirconia-alumina colored composite ceramic material, and method for manufacturing the same Download PDFInfo
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- JP2005306678A JP2005306678A JP2004127148A JP2004127148A JP2005306678A JP 2005306678 A JP2005306678 A JP 2005306678A JP 2004127148 A JP2004127148 A JP 2004127148A JP 2004127148 A JP2004127148 A JP 2004127148A JP 2005306678 A JP2005306678 A JP 2005306678A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002245 particle Substances 0.000 claims abstract description 52
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 32
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 claims abstract description 29
- 238000004040 coloring Methods 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 35
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 24
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 24
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- -1 rare earth salt Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
本発明は、産業用機械部品、事務・理化学用品、化学部品、生体用材料および医療用具などに好適なジルコニア−アルミナ系着色複合セラミック材料、およびその製造方法に関するものである。 The present invention relates to a zirconia-alumina-based colored composite ceramic material suitable for industrial machine parts, office / physical and chemical supplies, chemical parts, biomaterials, medical devices, and the like, and a method for producing the same.
強度と靭性の両方に優れるセラミック材料として、ジルコニア−アルミナ系複合セラミック材料が知られている。この複合セラミック材料には、たとえば、セリア（ＣｅＯ2）を８〜１２モル％及びチタニア（ＴｉＯ2）を０．０５〜４モル％含有する平均粒子径５μｍ以下の部分安定化ジルコニア（ＺｒＯ2）粒子でなる第１相と、平均粒子径２μｍ以下のアルミナ（Ａｌ2Ｏ３）粒子でなる第２相とを含むものが提案されている（特許文献１参照）。 A zirconia-alumina composite ceramic material is known as a ceramic material excellent in both strength and toughness. The composite ceramic material, for example, ceria (CeO 2) 8-12 mole% and titania average particle size 5μm or less of partially stabilized zirconia containing (TiO 2) 0.05 to 4 mol% (ZrO 2) There has been proposed one including a first phase made of particles and a second phase made of alumina (Al 2 O 3 ) particles having an average particle diameter of 2 μm or less (see Patent Document 1).
また、安定化剤として１０〜１２モル％のセリアを含み、平均粒径が０．１〜１μｍのジルコニア粒子でなる第１相と、平均粒径が０．１〜０．５μｍのアルミナ粒子でなる第２相とで構成され、第２相の含有量が２０〜６０体積％であるという条件の下で、アルミナ粒子の一部がジルコニア粒子内に分散されるとともに、ジルコニア粒子の一部がアルミナ粒子内に分散されてなる相互ナノコンポジット構造を有するジルコニア−アルミナ系複合セラミック材料が提案されている（特許文献２参照）。 Further, the stabilizer comprises 10 to 12 mol% of ceria, a first phase composed of zirconia particles having an average particle diameter of 0.1 to 1 μm, and alumina particles having an average particle diameter of 0.1 to 0.5 μm. And a part of the alumina particles are dispersed in the zirconia particles under the condition that the content of the second phase is 20 to 60% by volume. A zirconia-alumina composite ceramic material having a mutual nanocomposite structure dispersed in alumina particles has been proposed (see Patent Document 2).
さらに、安定化剤としてのセリアと、着色元素としての周期律表６族並びに８〜１０族に属する元素から選ばれ少なくとも１種とを含有し、主として正方晶ジルコニア粒子からなる第１相と、アルミナ粒子からなる第２相とを含む着色ジルコニア系複合セラミック焼結体が提案されている（特許文献３参照）。
ところで、アルミナは結晶粒界を制御することで透光性を示すことが知られているが、焼結により得られる多結晶体は一般に白色であり、ジルコニアも同様に白色もしくは乳白色を呈する。したがって、それらの混合物であるジルコニア−アルミナ系複合セラミックス材料も一般に白色もしくは乳白色である。しかしながら、医療用品、理化学用品、化学部品等の用途にあっては色によって互いに区別することが望まれるものや汚れが目立たないような白以外の色が望まれるものも少なくない。また、アクセサリー等の装飾品、スポーツ・レジャー用品、事務用品等の用途においては着色のニーズも高まっている。したがって、ジルコニアーアルミナ系複合セラミック材料本来の優れた機械的性質を損なうことなく、白色とは異なる色に着色されたジルコニアーアルミナ系複合セラミック材料を提供できれば、上記した用途でのさらなる利用の拡大が期待される。 By the way, alumina is known to exhibit translucency by controlling the crystal grain boundary, but the polycrystalline body obtained by sintering is generally white, and zirconia also exhibits white or milky white. Therefore, the zirconia-alumina composite ceramic material which is a mixture thereof is generally white or milky white. However, in applications such as medical supplies, physics and chemistry supplies, and chemical parts, there are many things that are desired to be distinguished from each other by color, and those that are desired to have a color other than white that does not make dirt noticeable. In addition, there is a growing need for coloring in applications such as accessories such as accessories, sports and leisure goods, and office supplies. Therefore, if it is possible to provide a zirconia-alumina composite ceramic material colored in a color different from white without impairing the original excellent mechanical properties of the zirconia-alumina composite ceramic material, further expansion of use in the above-described applications will be provided. There is expected.
尚、上記した着色ジルコニア系複合セラミック焼結体は、着色元素として周期律表６族並びに８〜１０族に属する元素から選ばれ少なくとも１種、例えば、クロム、鉄あるいはコバルトを添加することでジルコニアーアルミナ系複合セラミック材料の着色を目的としたものであるが、これらの着色元素を添加した場合には、成形性および焼結性が低下して機械的性質の劣化を招く恐れがある。また、クロムを添加する場合は、医療用セラミックスとしての安全性が問題視される恐れがあり、これらの点で依然として改善の余地があった。 The colored zirconia composite ceramic sintered body described above is selected from elements belonging to Groups 6 and 8 to 10 of the periodic table as a coloring element, and added with at least one kind, for example, chromium, iron, or cobalt, to add zirconia. The purpose is to color the ar-alumina-based composite ceramic material. However, when these coloring elements are added, the formability and the sinterability may be lowered and the mechanical properties may be deteriorated. In addition, when chromium is added, there is a possibility that safety as a medical ceramic may be regarded as a problem, and there is still room for improvement in these respects.
そこで、本発明の目的は、優れた強度と靭性を有するとともに、鮮やかなピンク色に着色され、医療用セラミックスとしても安全性の高いジルコニア−アルミナ系複合セラミック材料を提供することにある。すなわち、本発明にかかるジルコニア−アルミナ系着色複合セラミック材料は、安定化剤としてのセリアと着色元素としてのエルビウムを含有し、主として正方晶ジルコニア粒子からなる第１相と、アルミナ粒子からなる第２相とを含むことを特徴とする。 Accordingly, an object of the present invention is to provide a zirconia-alumina composite ceramic material that has excellent strength and toughness, is colored bright pink, and is highly safe as a medical ceramic. That is, the zirconia-alumina-based colored composite ceramic material according to the present invention contains ceria as a stabilizer and erbium as a coloring element, a first phase mainly composed of tetragonal zirconia particles, and a second phase composed of alumina particles. And a phase.
上記した本発明の着色複合セラミック材料において、エルビウムの含有量は、酸化物換算で第１相の正方晶ジルコニア粒子に対して０．０１〜１モル％であることが好ましい。 In the above-described colored composite ceramic material of the present invention, the erbium content is preferably 0.01 to 1 mol% with respect to the first phase tetragonal zirconia particles in terms of oxide.
また、本発明の更なる目的は、上記した着色複合セラミック材料の製造方法を提供することにある。すなわち、本発明の製造方法は、安定化剤としてのセリアと着色剤としての酸化エルビウムとを含有する主として正方晶ジルコニアからなる調合粉末を作製する工程と、前記調合粉末をアルミナ粉末と混合する工程と、得られた混合粉末を所望の形状に成形する工程と、得られた成形体を酸素含有雰囲気下で焼結する工程とを含むことを特徴とする。 Another object of the present invention is to provide a method for producing the above-described colored composite ceramic material. That is, the production method of the present invention includes a step of preparing a mixed powder mainly composed of tetragonal zirconia containing ceria as a stabilizer and erbium oxide as a colorant, and a step of mixing the mixed powder with alumina powder. And a step of molding the obtained mixed powder into a desired shape, and a step of sintering the obtained molded body in an oxygen-containing atmosphere.
上記したように、本発明は、正方晶ジルコニア粒子中にセリアとエルビウムを含有させることにより、従来のジルコニア−アルミナ系複合セラミック材料の優れた強度と靭性を低下させることなく、ピンク色に着色された着色複合セラミック材料を提供するものであり、エルビウムの添加量を制御することにより薄いピンクから濃いピンクまで色調節を行える。したがって、白以外の色を有するジルコニア−アルミナ系複合セラミック材料の登場が待たれていた、医療用品、理化学用品、化学部品等の用途や装飾品、スポーツ・レジャー用品への用途だけでなくさらなる応用分野の開拓が期待される。 As described above, the present invention is colored pink without reducing the excellent strength and toughness of the conventional zirconia-alumina composite ceramic material by containing ceria and erbium in the tetragonal zirconia particles. A colored composite ceramic material is provided, and the color can be adjusted from light pink to dark pink by controlling the amount of erbium added. Therefore, the use of zirconia-alumina composite ceramic materials with colors other than white has been awaited, not only for medical supplies, physics and chemistry supplies, chemical parts, etc. The development of the field is expected.
本発明のジルコニア−アルミナ系着色複合セラミック材料およびその製造方法を以下に詳細に説明する。 The zirconia-alumina-based colored composite ceramic material of the present invention and the production method thereof will be described in detail below.
本発明の着色複合セラミック材料は、安定化剤としてのセリアと着色元素としてのエルビウムを含有し、主として正方晶ジルコニア粒子からなる第１相と、アルミナ粒子からなる第２相とを含む。 The colored composite ceramic material of the present invention contains ceria as a stabilizer and erbium as a coloring element, and includes a first phase mainly composed of tetragonal zirconia particles and a second phase composed of alumina particles.
安定化剤としてのセリアは、結晶学的に低温劣化を起こさないジルコニアを得る上で重要である。第１相のジルコニア粒子中のセリア含有量は特に限定されないが、例えば、８〜１２モル％、特に１０〜１２モル％の範囲とすることが好ましい。セリアの含有量が８モル％未満であると、単斜晶ジルコニアの量が相対的に増加し、複合セラミック材料中にクラックが発生して強度劣化を招く恐れがある。また、セリアの含有量が１２モル％を超えると、高温安定相である立方晶ジルコニアが出現し始め、正方晶ジルコニアの量が相対的に減少し、十分な強度・靭性が得られない恐れがある。例えば、第１相を９０体積％もしくはそれ以上の正方晶ジルコニアと残りを単斜晶ジルコニアとで構成することが好ましい。尚、必要に応じて、第１相は、セリア以外に、マグネシア、カルシアあるいはイットリアのような他の安定化剤を含有してもよい。また、第１相は微量の不純物を含んでもよいが、不純物の含有量を第１相の全量に対して０．５モル％以下とすることが望ましい。 Ceria as a stabilizer is important in obtaining zirconia that does not cause crystallographic deterioration at low temperatures. The ceria content in the first phase zirconia particles is not particularly limited, but is preferably in the range of 8 to 12 mol%, particularly 10 to 12 mol%, for example. If the ceria content is less than 8 mol%, the amount of monoclinic zirconia is relatively increased, and cracks may occur in the composite ceramic material, leading to strength deterioration. Further, when the content of ceria exceeds 12 mol%, cubic zirconia which is a high-temperature stable phase starts to appear, and the amount of tetragonal zirconia is relatively decreased, and sufficient strength and toughness may not be obtained. is there. For example, the first phase is preferably composed of 90% by volume or more of tetragonal zirconia and the remainder of monoclinic zirconia. If necessary, the first phase may contain other stabilizers such as magnesia, calcia, or yttria in addition to ceria. The first phase may contain a small amount of impurities, but it is desirable that the content of impurities is 0.5 mol% or less with respect to the total amount of the first phase.
着色剤としてのエルビウムは、ジルコニア−アルミナ系複合セラミック材料に鮮やかなピンク色をもたらす。エルビウムの含有量は、酸化物換算で第１相の正方晶ジルコニア粒子に対して０．０１〜１モル％、特に０．０２〜０．５モル％であることが好ましい。含有量が０．１モル％に満たない場合は、十分且つ均一な着色が得られない恐れがある。一方、含有量が１モル％を超えると、機械的性質の低下を招く恐れがある。前記した範囲内においてエルビウムの含有量を調節すれば、ジルコニア−アルミナ系複合セラミック材料の色を薄いピンクと濃いピンクとの間において所望のピンク色にすることができる。 Erbium as a colorant brings a bright pink color to zirconia-alumina based composite ceramic materials. The content of erbium is preferably 0.01 to 1 mol%, particularly 0.02 to 0.5 mol%, in terms of oxide, with respect to the first phase tetragonal zirconia particles. If the content is less than 0.1 mol%, sufficient and uniform coloring may not be obtained. On the other hand, if the content exceeds 1 mol%, the mechanical properties may be deteriorated. By adjusting the content of erbium within the above-mentioned range, the color of the zirconia-alumina composite ceramic material can be set to a desired pink color between light pink and dark pink.
着色複合セラミック材料中のアルミナ含有量は特に限定されないが、０．５〜５０体積％、特に３０〜４０体積％の範囲内とすることが好ましい。アルミナの含有量が０．５体積％に満たないと、複合セラミック材料の機械的強度および耐摩耗性を十分に改善できない恐れがある。一方、アルミナ相の含有量が５０体積％を超えると、複合セラミック材料のマトリックス相がアルミナによって形成されるため靱性の低下を招く恐れがある。着色複合セラミック材料が３０〜４０体積％のアルミナを含有する場合は、機械的性質において信頼性の高い複合セラミック材料を提供することができる。 The alumina content in the colored composite ceramic material is not particularly limited, but is preferably in the range of 0.5 to 50% by volume, particularly 30 to 40% by volume. If the content of alumina is less than 0.5% by volume, the mechanical strength and wear resistance of the composite ceramic material may not be sufficiently improved. On the other hand, if the content of the alumina phase exceeds 50% by volume, the matrix phase of the composite ceramic material is formed of alumina, which may cause a decrease in toughness. When the colored composite ceramic material contains 30 to 40% by volume of alumina, a composite ceramic material having high reliability in mechanical properties can be provided.
また、本発明の着色複合セラミック材料は、第２相のアルミナ粒子の一部である数十ナノメートルサイズの極めて微細な粒子が第１相のジルコニア粒子内に分散した、いわゆる「ナノ複合化組織」を有することが好ましい。この場合、複合セラミック材料中に分散される全アルミナ粒子の数に対する、ジルコニア粒子内に分散されるアルミナ粒子の数の比が２数量％以上であることが特に好ましい。この比が２％以下であると、ナノ複合化組織の形成による強度および硬度の改善が十分に得られない。尚、この比の上限は特に限定されず、多ければ多いほど好ましい。 In addition, the colored composite ceramic material of the present invention is a so-called “nanocomposite structure” in which very fine particles of several tens of nanometers, which are part of the second phase alumina particles, are dispersed in the first phase zirconia particles. Is preferable. In this case, the ratio of the number of alumina particles dispersed in the zirconia particles to the number of all alumina particles dispersed in the composite ceramic material is particularly preferably 2% by mass or more. When this ratio is 2% or less, the strength and hardness cannot be sufficiently improved by the formation of the nanocomposite structure. In addition, the upper limit of this ratio is not specifically limited, and it is so preferable that there are many.
後述する焼結過程においてジルコニア粒子内に微細なアルミナ粒子を効率よく分散させるためには、さらにチタニアを添加することが好ましい。チタニアは、第１相のジルコニア粒子の粒成長を適度に促進して、ジルコニア粒子はその内部に微細なアルミナ粒子を取り込みやすくなる。また、応力誘起相転移を起こす臨界応力を高めることができる。チタニアの添加量は特に限定されないが、上記目的を達成する観点から、ジルコニア全量に関して０．０２〜４モル％、特に０．０５〜１モル％の範囲内とすることが好ましい。０．０２モル％未満であると、第１相の粒成長を促進する効果を十分に得られない恐れがある。一方、チタニアの添加量が４モル％を超えると、第１相の異常粒成長が起こりやすく、結果的に複合セラミック材料の強度および耐摩耗性が低下するおそれがある。 In order to efficiently disperse fine alumina particles in the zirconia particles in the sintering process described later, it is preferable to further add titania. Titania moderately promotes the grain growth of the first phase zirconia particles, and the zirconia particles easily incorporate fine alumina particles therein. In addition, the critical stress that causes stress-induced phase transition can be increased. The amount of titania added is not particularly limited, but from the viewpoint of achieving the above object, the amount of titania is preferably in the range of 0.02 to 4 mol%, particularly 0.05 to 1 mol% with respect to the total amount of zirconia. If it is less than 0.02 mol%, the effect of promoting the grain growth of the first phase may not be sufficiently obtained. On the other hand, when the amount of titania added exceeds 4 mol%, abnormal grain growth of the first phase is likely to occur, and as a result, the strength and wear resistance of the composite ceramic material may be reduced.
本発明の複合セラミック材料中にナノ複合化組織を形成する場合は、以下のメカニズムに基づいて機械的性質が改善されると考えられている。すなわち、正方晶ジルコニア粒子内に取り込まれたアルミナ粒子は、ジルコニア結晶粒子内に熱膨張差に起因する局所的な残留応力場を形成する。この残留応力場の影響により、ジルコニア結晶粒子内には転位が発生しやすくなる。転位は互いにパイルアップされ、ジルコニア粒子内にはサブグレインバンダリーが形成される。このサブグレインバンダリーによってジルコニア粒子は仮想的に細分化され、高強度化に有効に寄与する。この結果、セリア系ジルコニア（Ce-TZP）の欠点であった低強度および低硬度をイットリア系ジルコニア（Y−TZP）に匹敵するレベルまで改善し、且つY-TZPの３倍以上の高い靭性値を兼ね備えた強靭な複合セラミックス材料の実現が可能になる。 When a nanocomposite structure is formed in the composite ceramic material of the present invention, it is considered that the mechanical properties are improved based on the following mechanism. That is, the alumina particles taken into the tetragonal zirconia particles form a local residual stress field due to the thermal expansion difference in the zirconia crystal particles. Due to the influence of this residual stress field, dislocations are likely to occur in the zirconia crystal grains. The dislocations are piled up with each other, and subgrain boundaries are formed in the zirconia particles. Due to this subgrain boundary, the zirconia particles are virtually subdivided and contribute effectively to the increase in strength. As a result, the low strength and low hardness that were the disadvantages of ceria-based zirconia (Ce-TZP) have been improved to a level comparable to that of yttria-based zirconia (Y-TZP), and the toughness value is more than three times that of Y-TZP. This makes it possible to realize a tough composite ceramic material that has both.
次に、本発明のジルコニア−アルミナ系着色複合セラミック材料の製造方法について詳細に説明する。 Next, the method for producing the zirconia-alumina-based colored composite ceramic material of the present invention will be described in detail.
本発明の製造方法は、安定化剤としてのセリアと着色剤としての酸化エルビウムとを含有する主として正方晶ジルコニアからなる調合粉末を作製する工程と、前記調合粉末をアルミナ粉末と混合する工程と、得られた混合粉末を所望の形状に成形する工程と、得られた圧粉体を酸素含有雰囲気下で焼結する工程とを必須とする。 The production method of the present invention includes a step of preparing a mixed powder mainly composed of tetragonal zirconia containing ceria as a stabilizer and erbium oxide as a colorant, a step of mixing the mixed powder with alumina powder, The step of forming the obtained mixed powder into a desired shape and the step of sintering the obtained green compact in an oxygen-containing atmosphere are essential.
本発明の製造方法においては、着色元素であるエルビウムの添加によりジルコニア−アルミナ複合セラミック材料をピンク色に均一に着色するため、上記した調合粉末の作製が非常に重要であり、例えば、エルビウムの配合量が正方晶ジルコニア粉末に対して酸化物換算で０．０１〜１モル％となるようにエルビウムを正方晶ジルコニア粉末と混合し、得られた混合物を酸素含有雰囲気下、６００℃〜１３００℃の温度範囲で仮焼して調合粉末を作製することが好ましい。この場合は、ジルコニア粒子内に着色元素であるエルビウムを固溶させることができるので、エルビウムの添加量が少ない場合であっても、ジルコニア−アルミナ複合セラミック材料をピンク色に均一に着色するのに効果的である。 In the production method of the present invention, since the zirconia-alumina composite ceramic material is uniformly colored pink by adding erbium, which is a coloring element, the preparation of the above-mentioned mixed powder is very important. Erbium is mixed with the tetragonal zirconia powder so that the amount is 0.01 to 1 mol% in terms of oxide with respect to the tetragonal zirconia powder, and the resulting mixture is heated to 600 ° C to 1300 ° C in an oxygen-containing atmosphere. It is preferable to prepare the prepared powder by calcining in the temperature range. In this case, erbium, which is a coloring element, can be dissolved in the zirconia particles, so that the zirconia-alumina composite ceramic material can be uniformly colored pink even when the amount of erbium added is small. It is effective.
また、エルビウムを含有する希土類塩、有機希土類錯体、および希土類アルコキシドから選択される酸化エルビウムの前駆体を有機溶媒に溶解してエルビウム含有溶液を調製し、このエルビウム含有溶液にセリアを含有する正方晶ジルコニア粉末を混合し、得られた混合物から有機溶媒を除去することにより調合粉末を作製することも好ましい。さらに、セリアを含有する正方晶ジルコニア粉末と酸化エルビウム（Er2O３）粉末を混合することにより調合粉末を作製してもよい。 An erbium-containing solution is prepared by dissolving an erbium oxide precursor selected from a rare earth salt containing erbium, an organic rare earth complex, and a rare earth alkoxide in an organic solvent, and a tetragonal crystal containing ceria in the erbium-containing solution. It is also preferred to prepare a blended powder by mixing zirconia powder and removing the organic solvent from the resulting mixture. Further, a mixed powder may be prepared by mixing tetragonal zirconia powder containing ceria and erbium oxide (Er 2 O 3 ) powder.
本発明の好ましい実施形態にかかる調合粉末の一例として、例えば、セリアが８〜１２モル％と、酸化エルビウムが０．０１〜１モル％と、残部がジルコニアでなる組成を有し、比表面積が５〜２０ｍ２ｇ−１の正方晶ジルコニア粉末を使用することが好ましい。また、必要に応じて、エルビウムとセリアに加えて上記した他の安定化剤やチタニアをジルコニアに固溶させた正方晶ジルコニア粉末を調合粉末として用いてもよい。 As an example of the blended powder according to a preferred embodiment of the present invention, for example, ceria is 8 to 12 mol%, erbium oxide is 0.01 to 1 mol%, the balance is zirconia, and the specific surface area is It is preferable to use 5-20 m 2 g −1 tetragonal zirconia powder. In addition to erbium and ceria, tetragonal zirconia powder in which other stabilizers and titania described above are dissolved in zirconia as necessary may be used as the preparation powder.
アルミナ粉末は市販のものを用いることができ、平均粒径に関して特に限定するものではないが、微細なアルミナ粒子をジルコニア粒子内に効率よく分散させる場合は、平均粒径が０．１〜０．３μｍのアルミナ粒子を用いることが好ましい。 Commercially available alumina powder can be used, and the average particle size is not particularly limited. However, when fine alumina particles are efficiently dispersed in the zirconia particles, the average particle size is 0.1 to 0.3. It is preferable to use 3 μm alumina particles.
得られた調合粉末とアルミナ粉末を所定の配合比で配合した後、例えば、ボールミル等を用いて均一に混合する。配合比としては、例えば、得られた着色複合セラミック材料中のアルミナ含有量が０．５〜５０体積％、特に３０〜４０体積％の範囲内とすることが好ましい。 After the blended powder and alumina powder obtained are blended at a predetermined blending ratio, they are uniformly mixed using, for example, a ball mill. As a compounding ratio, for example, the alumina content in the obtained colored composite ceramic material is preferably in the range of 0.5 to 50% by volume, particularly 30 to 40% by volume.
得られた混合粉末を所定の形状に成形した後、成形体を酸素含有雰囲気下、例えば、１４００〜１５００℃の焼結温度で焼結する。必要に応じて、焼結後に、酸素含有雰囲気下、焼結温度と１０００℃の間の温度範囲でアニール処理を実施することが好ましい。このアニール処理によれば、着色複合セラミック材料の透光性の改善を図れるので、装飾品等への用途において奥行きのある光沢を付加して商品価値を高めるのに有効である。 After shape | molding the obtained mixed powder to a defined shape, a molded object is sintered by the sintering temperature of 1400-1500 degreeC by oxygen containing atmosphere, for example. If necessary, after the sintering, it is preferable to carry out an annealing treatment in a temperature range between the sintering temperature and 1000 ° C. in an oxygen-containing atmosphere. According to this annealing treatment, the translucency of the colored composite ceramic material can be improved, so that it is effective in increasing the commercial value by adding a gloss with a depth in applications such as decorations.
本発明を好ましい実施例に基づいて以下に具体的に説明するが、本発明はこれらの実施例に限定されない。 The present invention will be specifically described below based on preferred examples, but the present invention is not limited to these examples.
（実施例１〜３および比較例１）
着色成分として、Er(NO3)3からなる硝酸塩を、１０モル％のセリアを含有する正方晶ジルコニア(TZP)粉末に対して酸化物換算（Er2O３）で表１に示す割合で添加した後、エタノール溶媒中、２４時間湿式ボールミル混合し、得られた混合粉末を乾燥し、上記着色成分をジルコニアに固溶させるために、大気中、８００℃、１時間の条件下で仮焼処理して調合粉末を得た。次いで、調合粉末にアルミナ粉末を３０体積％添加し、水溶媒中２４時間湿式ボールミルにて混合、乾燥して焼結用粉末とした。この焼結用粉末を直径φ６８ｍｍの金型を用い、７MPaの条件下で一軸加圧成形した。さらに１７６MPaの条件下でCIP成形してタブレット状の成形体を得た。この成形体を大気中、１４５０℃で２時間焼結して各実施例のジルコニア−アルミナ系着色複合セラミックス材料を得た。
(Examples 1 to 3 and Comparative Example 1)
Nitrate consisting of Er (NO 3 ) 3 was added as a coloring component at a ratio shown in Table 1 in terms of oxide (Er 2 O 3 ) with respect to tetragonal zirconia (TZP) powder containing 10 mol% of ceria. After that, wet ball mill mixing is performed in an ethanol solvent for 24 hours, and the obtained mixed powder is dried, and calcined at 800 ° C. for 1 hour in the atmosphere in order to dissolve the colored component in zirconia. As a result, a blended powder was obtained. Next, 30% by volume of alumina powder was added to the prepared powder, mixed in an aqueous solvent for 24 hours by a wet ball mill, and dried to obtain a powder for sintering. This powder for sintering was uniaxially pressed under a condition of 7 MPa using a mold having a diameter of φ68 mm. Furthermore, CIP molding was performed under the condition of 176 MPa to obtain a tablet-like molded body. This molded body was sintered in the atmosphere at 1450 ° C. for 2 hours to obtain zirconia-alumina-based colored composite ceramic materials of each example.
得られた複合セラミック材料は、エルビウムの添加量に応じて薄いピンク〜濃いピンク色を有し、相対密度９９％以上の緻密な焼結体であった。焼結体中のジルコニアの結晶相は単斜晶が１体積％以下でほぼ正方晶でなることをＸ線回折により確認した。また、エルビウムイオンのジルコニアへの固溶によって生じる格子定数の変化をＸ線回折より確認した。 The obtained composite ceramic material was a dense sintered body having a light pink to deep pink color depending on the amount of erbium added and a relative density of 99% or more. It was confirmed by X-ray diffraction that the crystal phase of zirconia in the sintered body was almost tetragonal with a monoclinic crystal of 1 vol% or less. In addition, the change in lattice constant caused by the solid solution of erbium ions in zirconia was confirmed by X-ray diffraction.
また、得られた複合セラミック材料からダイヤモンドカッタにより３ｍｍｘ４ｍｍｘ４０ｍｍの角柱試験片を切り出し、機械的性質評価用サンプルとした。尚、試料の稜線は、0.1ｍｍの面取りを行い、側面は約６００〜８００番のダイヤモンド砥石にて研削した。曲げ試験時の引っ張り面については、最終ダイヤモンドペーストにて鏡面仕上げした。これらの試料を用いて、下部スパン３０ｍｍ、クロスヘッドスピード０．５ｍｍ／minの条件下で３点曲げ試験を行い、強度を求めた。また、試料鏡面に荷重４９０N（１０ｋｇ）、保持時間１５秒の条件下、ビッカース圧子を打痕し、IF法によって破壊靱性値を測定した。破壊靭性値（KIC）は、ビッカース圧子を押し込むことによって生じたクラックの長さと圧痕の大きさを測定し、下記に示すpalmqvist型のクラックに対応したNiiharaの式を用いて算出した。結果を表１に示す。
KIC ＝ 0.018・Hｖ・a1/2・（１／a）1/2・（Hv／E）-2/5
尚、比較例１として、エルビウムを添加しないことを除いては上記実施例と同様にして着色していない白色のジルコニア−アルミナ系複合セラミック材料を作製し、機械的性質を評価した。結果を表１に示す。各実施例の着色複合セラミック材料の機械的性質は、比較例１のエルビウム添加なしの複合セラミック材料と遜色ない結果となった。これより、着色元素のエルビウムを第１相であるジルコニアに固溶させた場合において、ジルコニア−アルミナ系複合セラミック材料の優れた機械的性質（高強度、高靭性）を維持しつつ、ピンクの色調を付加できることを確認した。
Further, a 3 mm × 4 mm × 40 mm prism test piece was cut out from the obtained composite ceramic material with a diamond cutter, and used as a sample for evaluating mechanical properties. The ridge line of the sample was chamfered by 0.1 mm, and the side surface was ground with a diamond grindstone of about 600 to 800. The tensile surface during the bending test was mirror finished with the final diamond paste. Using these samples, a three-point bending test was performed under the conditions of a lower span of 30 mm and a crosshead speed of 0.5 mm / min to obtain strength. Further, a Vickers indenter was imprinted on the sample mirror surface under the conditions of a load of 490 N (10 kg) and a holding time of 15 seconds, and the fracture toughness value was measured by the IF method. The fracture toughness value (K IC ) was calculated using the Niihara equation corresponding to the palmqvist type crack shown below by measuring the length of the crack and the size of the indentation caused by indenting the Vickers indenter. The results are shown in Table 1.
K IC = 0.018 ・ Hv ・ a 1/2・ (1 / a) 1/2・ (Hv / E) -2/5
As Comparative Example 1, an uncolored white zirconia-alumina composite ceramic material was prepared in the same manner as in the above example except that erbium was not added, and the mechanical properties were evaluated. The results are shown in Table 1. The mechanical properties of the colored composite ceramic material of each example were comparable to the composite ceramic material of Comparative Example 1 without erbium addition. As a result, when the colored element erbium is dissolved in the first phase zirconia, it maintains the excellent mechanical properties (high strength and high toughness) of the zirconia-alumina composite ceramic material, while maintaining a pink color tone. It was confirmed that can be added.
また、これらの複合セラミック材料の微細組織を走査型電子顕微鏡および透過型電子顕微鏡により観察した結果、いずれにおいても、第２相のアルミナ粒子のうち、数十〜数百ナノメーターサイズの極めて微細なアルミナ粒子の一部が、第１相のジルコニア結晶粒子内に分散した所謂「ナノ複合化組織」を呈していることが確認された。尚。複合セラミック材料の微細組織への着色元素の添加による影響は認められなかった。 Moreover, as a result of observing the microstructure of these composite ceramic materials with a scanning electron microscope and a transmission electron microscope, in any case, among the alumina particles of the second phase, extremely fine particles having a size of several tens to several hundreds of nanometers. It was confirmed that a part of the alumina particles exhibited a so-called “nanocomposite structure” dispersed in the first phase zirconia crystal particles. still. There was no effect of the addition of coloring elements to the microstructure of the composite ceramic material.
（実施例４）
実施例２で作製した複合セラミック材料の一つを大気中、１３４０℃で３時間熱処理し、その焼結温度から１０００℃まで０．５℃／minの速度で降温する常圧アニール処理を実施した。アニール処理後、実施例１〜３と同様の手法で機械的性質を評価した。結果を表１に示す。
Example 4
One of the composite ceramic materials produced in Example 2 was heat-treated in air at 1340 ° C. for 3 hours, and an atmospheric annealing process was performed in which the temperature was lowered from the sintering temperature to 1000 ° C. at a rate of 0.5 ° C./min. . After the annealing treatment, the mechanical properties were evaluated in the same manner as in Examples 1 to 3. The results are shown in Table 1.
また、上記アニール処理を施した試料を厚さ０．２ｍｍまで薄片化し、可視光による透過度を目視にて観察した。エルビウムの添加量が同じでアニール処理を行わなかった実施例２の複合セラミック材料に比べ、実施例４の複合セラミック材料においてはアニール処理による透光性の改善が認められた。これは、複合セラミック材料の粒界界面での整合性が向上し、粒界での光散乱が抑制された結果と考えられる。さらに、上記アニール処理よって約１０％の強度向上を確認できた。これは、アニール処理により複合セラミック材料の粒界結晶性が高められ、粒界強度が改善された結果と考えられる。尚、このアニール処理による粒成長は認められなかった。 Further, the sample subjected to the annealing treatment was sliced to a thickness of 0.2 mm, and the transmittance with visible light was visually observed. Compared to the composite ceramic material of Example 2 in which the amount of erbium added was the same and the annealing treatment was not performed, in the composite ceramic material of Example 4, an improvement in translucency was observed by the annealing treatment. This is considered to be a result of improved matching at the grain boundary interface of the composite ceramic material and suppression of light scattering at the grain boundary. Furthermore, about 10% strength improvement was confirmed by the annealing treatment. This is considered to be a result of the grain boundary crystallinity of the composite ceramic material being increased by the annealing treatment and the grain boundary strength being improved. In addition, grain growth by this annealing treatment was not recognized.
上記実施例からもわかるように、本発明のジルコニア−アルミナ複合セラミック材料は、エルビウムを着色元素として用いることによって鮮やかなピンク色を有し、その添加量を調節することにより薄いピンク色と濃いピンク色との間において所望のピンク色を得ることができる。したがって、本発明のジルコニア−アルミナ系着色複合セラミック材料は、耐薬品性や耐熱性に加えて高い強度と靭性が要求される用途でだけでなく、色によって互いから区別することが必要とされるような医療用品、理化学用品、化学部品等、あるいは着色による付加価値が重視されるような装飾品、スポーツ・レジャー用品、事務用品等の幅広い用途への利用が期待できる。 As can be seen from the above examples, the zirconia-alumina composite ceramic material of the present invention has a bright pink color by using erbium as a coloring element, and light pink and dark pink by adjusting the amount of addition. A desired pink color can be obtained between the colors. Therefore, the zirconia-alumina-based colored composite ceramic material of the present invention is required to be distinguished from each other not only by the application that requires high strength and toughness in addition to chemical resistance and heat resistance, but also by color. It can be expected to be used in a wide range of applications such as medical supplies, physics and chemistry supplies, chemical parts, etc., or decorative items, sports / leisure items, office supplies, etc. where added value by coloring is important.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012085875A2 (en) | 2010-12-22 | 2012-06-28 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Coloured sintered part |
| KR101179050B1 (en) | 2009-05-13 | 2012-09-03 | 이광호 | Method for producing pink colored zirconia ceramics |
| EP2505163A1 (en) | 2011-03-31 | 2012-10-03 | GC Corporation | Zirconia-based composite ceramic sintered compact and method for producing the same |
| CN108585813A (en) * | 2018-06-13 | 2018-09-28 | 厦门市仿真美义齿科技有限公司 | A kind of novel all-ceramic prosthesis and preparation method thereof |
| CN109704730A (en) * | 2019-03-07 | 2019-05-03 | 昆山卡德姆新材料科技有限公司 | A kind of ceramic ornament and preparation method thereof having double-colored jade texture |
| JP2020132519A (en) * | 2019-02-15 | 2020-08-31 | 東ソー株式会社 | Pink-colored zirconia sintered body and method for producing the same |
| US10858293B2 (en) | 2018-03-30 | 2020-12-08 | Tosoh Corporation | Zirconia sintered body and manufacturing method of the same |
| US11124457B2 (en) * | 2019-02-15 | 2021-09-21 | Tosoh Corporation | Pink zirconia sintered body and manufacturing method of the same |
| CN115974569A (en) * | 2022-12-23 | 2023-04-18 | 华中师范大学深圳研究院 | Colored zirconia ceramic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3838248B1 (en) * | 2012-12-28 | 2024-10-09 | Tosoh Corporation | Colored translucent zirconia sintered body and its use |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6259571A (en) * | 1985-09-06 | 1987-03-16 | 東レ株式会社 | Colored zirconia sintered body and its producton |
| JPH01234364A (en) * | 1988-03-16 | 1989-09-19 | Sumitomo Electric Ind Ltd | High-strength colored zirconia-based sintered body |
| JPH042658A (en) * | 1990-04-17 | 1992-01-07 | Nippon Soda Co Ltd | High-strength colored zirconia sintered material and production thereof |
| JPH04193760A (en) * | 1990-11-26 | 1992-07-13 | Nkk Corp | Colored light-transmissive alumina sintered body and its production |
| JPH08268755A (en) * | 1995-01-30 | 1996-10-15 | Matsushita Electric Works Ltd | Zirconia-based composite ceramic sintered compact and its production |
| JP2004059374A (en) * | 2002-07-29 | 2004-02-26 | Matsushita Electric Works Ltd | Colored zirconia-based composite ceramic sintered compact and method of manufacturing the same |
-
2004
- 2004-04-22 JP JP2004127148A patent/JP4379189B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6259571A (en) * | 1985-09-06 | 1987-03-16 | 東レ株式会社 | Colored zirconia sintered body and its producton |
| JPH01234364A (en) * | 1988-03-16 | 1989-09-19 | Sumitomo Electric Ind Ltd | High-strength colored zirconia-based sintered body |
| JPH042658A (en) * | 1990-04-17 | 1992-01-07 | Nippon Soda Co Ltd | High-strength colored zirconia sintered material and production thereof |
| JPH04193760A (en) * | 1990-11-26 | 1992-07-13 | Nkk Corp | Colored light-transmissive alumina sintered body and its production |
| JPH08268755A (en) * | 1995-01-30 | 1996-10-15 | Matsushita Electric Works Ltd | Zirconia-based composite ceramic sintered compact and its production |
| JP2004059374A (en) * | 2002-07-29 | 2004-02-26 | Matsushita Electric Works Ltd | Colored zirconia-based composite ceramic sintered compact and method of manufacturing the same |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101179050B1 (en) | 2009-05-13 | 2012-09-03 | 이광호 | Method for producing pink colored zirconia ceramics |
| WO2012085875A2 (en) | 2010-12-22 | 2012-06-28 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Coloured sintered part |
| EP2740717A2 (en) | 2010-12-22 | 2014-06-11 | Saint-Gobain Centre de Recherches et d'Etudes Européen | Sintered coloured ceramic object |
| US9340679B2 (en) | 2010-12-22 | 2016-05-17 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Decorative article containing an equipped, coloured and sintered zirconia part |
| EP2505163A1 (en) | 2011-03-31 | 2012-10-03 | GC Corporation | Zirconia-based composite ceramic sintered compact and method for producing the same |
| US8845954B2 (en) | 2011-03-31 | 2014-09-30 | Gc Corporation | Zirconia-based composite ceramic sintered compact and method for producing the same |
| US10858293B2 (en) | 2018-03-30 | 2020-12-08 | Tosoh Corporation | Zirconia sintered body and manufacturing method of the same |
| CN108585813A (en) * | 2018-06-13 | 2018-09-28 | 厦门市仿真美义齿科技有限公司 | A kind of novel all-ceramic prosthesis and preparation method thereof |
| JP2020132519A (en) * | 2019-02-15 | 2020-08-31 | 東ソー株式会社 | Pink-colored zirconia sintered body and method for producing the same |
| US11124457B2 (en) * | 2019-02-15 | 2021-09-21 | Tosoh Corporation | Pink zirconia sintered body and manufacturing method of the same |
| JP7432816B2 (en) | 2019-02-15 | 2024-02-19 | 東ソー株式会社 | Pink zirconia sintered body and its manufacturing method |
| CN109704730A (en) * | 2019-03-07 | 2019-05-03 | 昆山卡德姆新材料科技有限公司 | A kind of ceramic ornament and preparation method thereof having double-colored jade texture |
| CN109704730B (en) * | 2019-03-07 | 2024-01-02 | 昆山卡德姆新材料科技有限公司 | Ceramic ornament with double-color jade texture and preparation method thereof |
| CN115974569A (en) * | 2022-12-23 | 2023-04-18 | 华中师范大学深圳研究院 | Colored zirconia ceramic and preparation method thereof |
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