CN108349817A - 抗热冲击的复合材料 - Google Patents
抗热冲击的复合材料 Download PDFInfo
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- CN108349817A CN108349817A CN201680065432.8A CN201680065432A CN108349817A CN 108349817 A CN108349817 A CN 108349817A CN 201680065432 A CN201680065432 A CN 201680065432A CN 108349817 A CN108349817 A CN 108349817A
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- zirconium oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000035939 shock Effects 0.000 title description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 25
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000005084 Strontium aluminate Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004870 electrical engineering Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910002244 LaAlO3 Inorganic materials 0.000 claims description 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims description 2
- 229910003669 SrAl2O4 Inorganic materials 0.000 claims description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- -1 lanthanum aluminate Chemical class 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052651 microcline Inorganic materials 0.000 claims description 2
- 229910052652 orthoclase Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000013001 point bending Methods 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052654 sanidine Inorganic materials 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002635 electroconvulsive therapy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明的主题是陶瓷复合材料、其制造和用途。本发明特别涉及基于氧化锆的复合材料、均匀、多相和多晶的陶瓷。
Description
本发明涉及陶瓷复合材料及其制造和用途。本发明特别涉及基于氧化锆的复合材料、均匀、多相和多晶的陶瓷。
基于氧化锆的复合材料，特别是具有附加成分例如稳定剂或第二相的材料已经为人所知一段时间。这些材料在汽车工业中例如用于制造λ传感器。这些材料的问题时它们必须经得住高温，但是它们也经受温度波动，以使得这可能导致部件毁坏。特别地，热冲击载荷，例如冷凝水接触，可能导致明显损坏或甚至毁坏。
此外，基于更严格的EURO 6规定的对λ传感器的更高要求对于已知材料而言也是有问题的。这些新规定要求在几秒内至操作温度的更高加热速率，但是使用已知材料难以达到这些速率。
因此，目的是提供对出现温度变化时较不易于毁坏的材料。特别地，这些材料应具有高和改进的抗热冲击性。
所述目的通过具有权利要求1中所示特征的（烧结）复合材料来实现。优选实施方案示于从属权利要求中。
本发明的复合材料与现有技术的区别在于改进的抗热冲击性。此外，令人惊讶地发现，除了强度提高外，尽管平均微结构微晶粒度降低，还可以获得等值或甚至更大的离子电导性。
由于其离子电导性能，本发明的复合材料还可用作氧传感器。典型的应用领域是例如汽车或电子领域中的λ传感器。在这些情况下，本发明的复合材料可以以烧结薄膜的形式用作λ传感器的组件。
用于制造本发明复合材料的组合物，即包含于该复合材料中的陶瓷粉末以及可能的添加剂的混合物可以在烧结前成型成为坯体。该复合材料然后可以特别地作为薄膜形式的坯体存在，该薄膜例如或特别通过薄膜浇注而产生。根据使用领域，该薄膜的厚度为10 μm至1 mm，优选100 μm至600 μm。
在一个优选的实施方案中，本发明涉及复合材料，其包含由氧化锆制成的陶瓷基质和其中分散的至少一种第二相，其特征在于所述由氧化锆制成的基质占所述复合材料的最多99重量%的含量，并且所述第二相占所述复合材料的1至30重量%，优选1-15重量%，特别优选1-5重量%的含量，其中基于氧化锆总含量计，所述氧化锆基本上，优选以90至99%，更优选以95至99%，特别优选以98至99%的程度以四方和立方相的形式存在，并且其中氧化锆的四方和立方相是经化学和/或机械稳定化的。
机械稳定化应被理解为，通过在否则相对刚性的陶瓷微结构中在微晶水平上的微移动/-剪切变得可能，根据本发明的第二相的添加抵消在氧化锆的四方晶体结构转变成单斜晶体结构时出现的膨胀，而不必然产生宏观裂纹。
此外，机械稳定化还应被理解为，氧化锆的四方晶体相由于整个微结构中的机械应力而稳定化。在烧结工艺后的冷却时，ZrO2和第二相的不同的热膨胀系数可能导致此类应力。根据本发明，在所述复合材料中的由氧化锆制成的基质可以具有平均0.5至2.0 μm，优选平均0.5至1.5 μm的微结构粒度。该微结构粒度在此借助根据EN 623-3（2003-01）的线性截断法确定为“平均线性截断距离”。
本发明的复合材料可以包含一种或多种化学稳定剂。该化学稳定剂选自MgO、CaO、CeO2、Gd2O3、Sm2O3、Er2O3、Y2O3、Yb2O3或Sc2O3或其混合物，其中化学稳定剂的总含量为< 12摩尔%，优选< 10摩尔%，特别优选< 5摩尔%，基于氧化锆含量计。
本发明的复合材料可以含有附加成分，特别地，氧化锆和/或第二相可以含有可溶性成分。可溶性成分可以是例如Cr、Fe、Mg、Ca、Ti、Si、Y、Ce、镧系元素和/或V。这些成分可以一方面充当着色添加剂，另一方面充当烧结助剂。通常，将它们作为氧化物添加。
本发明的复合材料的第二相还可以包含分散体（Dispersoid），其由于其晶体结构实现微观水平上的剪切形变和/或改进机械性能。
在一个优选的实施方案中，第二相的微结构粒度小于或等于氧化锆的微结构粒度，其中该微结构粒度（d50）优选为0.1至2.0 μm，优选0.1至1.5 μm，特别优选0.1至0.5 μm。该微结构粒度还可以通过线性截断法来确定。
所述第二相特别是选自以下的化合物的一种或多种：铝酸锶（SrAl2O4或SrAl12O19）、铝酸镧（LaAlO3或LaAl11O18）、尖晶石（MgAl2O4）、氧化铝（Al2O3）、硅酸锆（ZrSiO4）、钾长石（KAlSi3O8）和磷酸镧（La(PO)4），优选铝酸锶、氧化铝和硅酸锆，特别优选硅酸锆。
在一个特别优选的实施方案中，本发明的材料还可以具有第三相。后者可以选自已对于第二相提及的化合物。
根据本发明，所述复合材料可以通过非常不同的方法，优选通过薄膜浇注、挤出、干压、增材制造法和/或其它模制法，例如注浆成型或注射成型来制造。
为了获得复合材料，将原料混合物随后烧结，其中该烧结在< 1670°C，优选<1530°C，特别优选< 1400°C的温度下进行。
本发明的复合材料显示出其特征性能的明显改进。特别地，该复合材料优选具有根据DIN EN 843-1（版本EN 843-1: 2006/版次2008-08）的≥ 600 MPa的四点弯曲断裂强度。
用于评估高性能陶瓷的一个特征是“损坏容差（Schädigungstoleranz）”。该测试根据文献中很好描述的“压痕强度法”进行，参见R.F. Cook, Multi-Scale Effects inthe Strength of Ceramics, J.Am.Ceram.Soc. 98 [1] 2933-2947 (2015)和P.Chantikul, G.R. Anstis, B.R. Lawn, D.B. Marshall, A Critical Evaluation ofIndentation Techniques for Measuring Fracture Toughness: II Strength Method,J.Am.Ceram.Soc. 64 [9], 539-543 (1981)。
所确立的方法方式借助不同材料进行制定。在此表明，该测试可以非常好地再现，并对于技术相关的增强机理，例如相变增韧（Umwandlungsverstärkung）而言可视为有说服力的。关于材料变体的选择性（Trennschärfe）相比于例如借助 SEVNB测试的断裂韧性的测量而言明显更可靠。
在该测试本身中，将各3个具有相同载荷的压痕在上部支承辊（Auflagerrollen）内施加到弯曲棒的拉伸侧上。随后将特定损坏的弯曲棒储存在水中至少3天（亚临界裂纹生长的饱和）。然后类似于标准弯曲试验那样测定残余强度。
根据HV5压痕的本发明复合材料的损坏容差或残余强度为> 170 MPa，优选> 190MPa，特别优选> 200 MPa。根据HV20压痕的本发明复合材料的损坏容差或残余强度为> 100MPa，优选> 110 MPa，特别优选 > 120 MPa。
此外，本发明的复合材料具有在850°C下≥ 2.0 S/m和在1000°C下≥ 5.0 S/m，优选在1000°C下≥ 6.0 S/m的电导率。
在热冲击处理后基于DIN EN 820-3（版本EN 820-3: 2004/版次2004.11）的裂纹穿透试验在本发明的复合材料的情况下相比于现有技术的已知材料而言显示出特别有利的结果。该抗热冲击性通过在所准备的弯曲棒上的骤冷试验来测定。在220°C的温度差下，本发明的复合材料未显示出损坏。相反，现有技术的材料由于热应力显示出裂纹形成。
本发明的复合材料优选用于电气工程或传感工程，特别是用于制造氧传感器，特别优选作为未烧结ZrO2薄膜形式的λ传感器的前体或组件，并在制造后作为λ传感器中的组件存在。
权利要求书(按照条约第19条的修改)
1.复合材料用于电气工程或传感工程，特别是用于制造氧传感器，特别优选作为未烧结ZrO2薄膜形式的λ传感器的前体或组件的用途，所述复合材料包含由氧化锆制成的陶瓷基质和其中分散的至少一种第二相，其特征在于所述由氧化锆制成的基质占所述复合材料的最多99重量%的含量，并且所述第二相占所述复合材料的1-5重量%的含量，其中基于氧化锆总含量计，所述氧化锆基本上，优选以90至99%，更优选以95至99%，特别优选以98至99%的程度以四方和立方相的形式存在，并且其中氧化锆的四方和立方相是经化学和/或机械稳定化的。
Claims (10)
1.复合材料，其包含由氧化锆制成的陶瓷基质和其中分散的至少一种第二相，其特征在于所述由氧化锆制成的基质占所述复合材料的最多99重量%的含量，并且所述第二相占所述复合材料的1至30重量%，优选1-15重量%，特别优选1-5重量%的含量，其中基于氧化锆总含量计，所述氧化锆基本上，优选以90至99%，更优选以95至99%，特别优选以98至99%的程度以四方和立方相的形式存在，并且其中氧化锆的四方和立方相是经化学和/或机械稳定化的。
2.根据权利要求1的复合材料，其特征在于所述由氧化锆制成的基质具有平均0.5至2.0 μm，优选平均0.5至1.5 μm的微结构粒度。
3.根据权利要求1或2任一项的复合材料，其特征在于含有MgO、CaO、CeO2、Gd2O3、Sm2O3、Er2O3、Y2O3、Yb2O3或Sc2O3或其混合物作为化学稳定剂，其中化学稳定剂的总含量为< 12摩尔%，优选< 10摩尔%，特别优选< 5摩尔%，基于氧化锆含量计。
4.根据前述权利要求任一项的复合材料，其特征在于所述氧化锆和/或第二相含有可溶性成分。
5.根据前述权利要求任一项的复合材料，其特征在于所述第二相的微结构粒度小于或等于氧化锆的微结构粒度，其中所述微结构粒度为优选0.1至2.0 μm，更优选 0.1至1.5 μm，特别优选0.1至0.5 μm。
6.根据前述权利要求任一项的复合材料，其特征在于所述第二相选自下列化合物的一种或多种：铝酸锶（SrAl2O4或SrAl12O19）、铝酸镧（LaAlO3或LaAl11O18）、尖晶石（MgAl2O4）、氧化铝（Al2O3）、硅酸锆（ZrSiO4）、钾长石（KAlSi3O8）和磷酸镧（La(PO)4），优选铝酸锶、氧化铝和硅酸锆，特别优选硅酸锆。
7.根据前述权利要求任一项的复合材料，其特征在于所述复合材料通过将原料混合物在< 1670°C，优选< 1530°C，特别优选< 1400°C的温度下烧结来制造。
8.根据前述权利要求任一项的复合材料，其特征在于所述复合材料具有根据DIN EN843-1（版本EN 843-1: 2006/版次2008-08）的≥ 600 MPa的四点弯曲断裂强度。
9.根据前述权利要求任一项的复合材料，其特征在于其电导率为在850°C下≥ 2.0 S/m和在1000°C下≥ 5.0 S/m，优选在1000°C下≥ 6.0 S/m。
10.根据前述权利要求任一项的复合材料用于电气工程或传感工程，特别是用于制造氧传感器，特别优选作为未烧结ZrO2薄膜形式的λ传感器的前体或组件的用途。
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| DE102015222143.1 | 2015-11-10 | ||
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| PCT/EP2016/077298 WO2017081174A1 (de) | 2015-11-10 | 2016-11-10 | Thermoschockresistente verbundwerkstoffe |
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| EP (1) | EP3374329B1 (zh) |
| JP (1) | JP2019501097A (zh) |
| KR (1) | KR20180081794A (zh) |
| CN (1) | CN108349817A (zh) |
| DE (1) | DE102016222107A1 (zh) |
| WO (1) | WO2017081174A1 (zh) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112537957A (zh) * | 2019-09-23 | 2021-03-23 | 比亚迪股份有限公司 | 氧化锆陶瓷及其制备方法和应用 |
| CN112537956A (zh) * | 2019-09-23 | 2021-03-23 | 比亚迪股份有限公司 | 黑色氧化锆陶瓷及其制备方法和应用 |
| CN112552041A (zh) * | 2019-09-10 | 2021-03-26 | 比亚迪股份有限公司 | 制备氧化锆陶瓷的组合物、氧化锆陶瓷及其制备方法和应用 |
| CN116535207A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 制备氧化锆陶瓷的组合物、氧化锆陶瓷及其制备方法和电子产品壳体 |
| CN116535225A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 增强氧化锆陶瓷及制备方法与应用 |
| CN116535206A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 氧化锆陶瓷及其制备方法和电子产品壳体 |
| CN117326882A (zh) * | 2022-06-24 | 2024-01-02 | 比亚迪股份有限公司 | 一种陶瓷及其制备方法和应用 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7272250B2 (ja) * | 2019-12-04 | 2023-05-12 | 株式会社デンソー | ガスセンサおよびガスセンサ用粉末 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112552041A (zh) * | 2019-09-10 | 2021-03-26 | 比亚迪股份有限公司 | 制备氧化锆陶瓷的组合物、氧化锆陶瓷及其制备方法和应用 |
| CN112552041B (zh) * | 2019-09-10 | 2021-11-12 | 比亚迪股份有限公司 | 制备氧化锆陶瓷的组合物、氧化锆陶瓷及其制备方法和应用 |
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| CN112537956A (zh) * | 2019-09-23 | 2021-03-23 | 比亚迪股份有限公司 | 黑色氧化锆陶瓷及其制备方法和应用 |
| CN112537957B (zh) * | 2019-09-23 | 2022-01-07 | 比亚迪股份有限公司 | 氧化锆陶瓷及其制备方法和应用 |
| CN116535207A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 制备氧化锆陶瓷的组合物、氧化锆陶瓷及其制备方法和电子产品壳体 |
| CN116535225A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 增强氧化锆陶瓷及制备方法与应用 |
| CN116535206A (zh) * | 2022-01-26 | 2023-08-04 | 比亚迪股份有限公司 | 氧化锆陶瓷及其制备方法和电子产品壳体 |
| CN117326882A (zh) * | 2022-06-24 | 2024-01-02 | 比亚迪股份有限公司 | 一种陶瓷及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180081794A (ko) | 2018-07-17 |
| EP3374329B1 (de) | 2020-02-12 |
| US20180312441A1 (en) | 2018-11-01 |
| EP3374329A1 (de) | 2018-09-19 |
| JP2019501097A (ja) | 2019-01-17 |
| DE102016222107A1 (de) | 2017-05-11 |
| US20200102250A1 (en) | 2020-04-02 |
| WO2017081174A1 (de) | 2017-05-18 |
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