CN113165983A - 装饰性陶瓷制品 - Google Patents

装饰性陶瓷制品 Download PDF

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CN113165983A
CN113165983A CN201980080469.1A CN201980080469A CN113165983A CN 113165983 A CN113165983 A CN 113165983A CN 201980080469 A CN201980080469 A CN 201980080469A CN 113165983 A CN113165983 A CN 113165983A
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B·伯塞尔
Y·法列特
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Swatch Group Research and Development SA
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Abstract

本发明涉及一种由陶瓷材料制成的装饰性制品，所述陶瓷材料含有碳化物相和氧化物相，所述碳化物相以在70至85％之间的体积百分比存在，且所述氧化物相以在15至30％之间的体积百分比存在。

Description

装饰性陶瓷制品
技术领域
本发明涉及装饰性制品，特别涉及由陶瓷复合材料制成的钟表外部组件。还涉及其制造方法。
现有技术
许多外部组件由复合陶瓷材料制成，其优点尤其在于具有极高硬度以确保它们不被划伤的能力。文献主要报道了以氧化物如氧化铝为主要比例的复合材料，向所述氧化物中添加了碳化物。它们可例如是包含按重量计70％Al2O3和30％用作增强材料的TiC的复合材料。这些复合材料与其它材料，如不锈钢或金属陶瓷相比具有几乎没有金属光泽的特征，这对需要光泽的装饰性制品而言是一个缺点。
发明概述
本发明的目的因此是通过提出具有适用于产生这种金属光泽的组成的陶瓷材料来克服上述缺点。
为此，本发明提供一种由陶瓷制成的装饰性制品，所述陶瓷包含主要比例的碳化物相和次要比例的氧化物相。更具体地，本发明提供一种由陶瓷材料制成的装饰性制品，所述陶瓷材料包含按体积计50至95％，优选51至85％的百分比的碳化物相和5至50％，优选15至49％的百分比的氧化物相。
优选地，碳化物相包括选自TiC、Mo2C和NbC的一种或多种碳化物，且氧化物相包括选自Al2O3、ZrO2、Cr2O3和Y2O3的一种或多种氧化物。
更优选地，碳化物相包括主要比例的TiC或Mo2C，且氧化物相包括主要比例的Al2O3，优选主要比例的α相或α相和γ相的混合物，或ZrO2；后者优选是稳定化氧化锆，例如用Y2O3稳定化。根据一个变体，包括主要比例的氧化铝的氧化物相还包括次要比例的氧化铬。
根据本发明的一个优选实施方案，所述装饰性制品包含包括主要比例的碳化钛的碳化物相，且所述包括主要比例的碳化钛的碳化物相以在55至90％之间，优选在60至85％之间的体积百分比存在，氧化物相以在10至45％之间，优选在15至40％之间的体积百分比存在。根据这一实施方案的一个变体，所述碳化物相可包括次要比例的碳化铌。
根据本发明的装饰性制品的另一实施方案，所述装饰性制品包含包括主要比例的碳化钼的碳化物相，且所述包括主要比例的碳化钼的碳化物相以在50至75％之间，优选在51至75％之间的体积百分比存在，氧化物相以在25至50％之间，优选在25至49％之间的体积百分比存在。
根据本发明的装饰性制品的再一实施方案，所述碳化物相由碳化钛组成，且所述氧化物相由氧化铝组成，所述碳化物相以在65至85％之间，优选在70至80％之间的体积百分比存在，且所述氧化物相以在15至35％之间，优选在20至30％之间的体积百分比存在。
根据本发明的装饰性制品的再一实施方案，所述碳化物相由碳化钛组成，且所述氧化物相由主要比例的氧化铝和次要比例的氧化铬组成，所述碳化物相以在55至75％之间，优选在60至70％之间的体积百分比存在，且所述氧化物相以在25至45％之间，优选在30至40％之间的体积百分比存在。
由此开发的复合材料在抛光后具有类似于在不锈钢或使用镍或钴作为金属粘合剂的金属陶瓷中观察到的类似的金属光泽。这些复合材料具有无致敏元素如Ni、耐腐蚀并且非磁性的其它优点。它们也具有高硬度和足够的韧度以用于生产外部元件。此外，它们可通过常规粉末冶金法，如压制或注射法成型，以获得“近净形”(near-net shape)部件。
从参考附图作为非限制性实例给出的优选实施方案的以下描述中显而易见本发明的其它特征和优点。
附图简述
图1显示包含用根据本发明的陶瓷材料制成的表壳中心的钟表。
图2显示根据本发明的陶瓷材料的电子显微镜图像。
详述
本发明涉及由陶瓷复合材料制成的装饰性制品。该装饰性制品可以是手表、首饰、手镯(bracelets)等的组件，或更通常是便携元件，如移动电话的外部部分。在制表领域中，这一制品可以是外部部件，如表壳中心(middle)、底盖(back)、表圈(bezel)、按钮(push-button)、表带连接(bracelet link)、表盘(dial)、指针(hand)、表盘指数(dial index)等。例如，用根据本发明的陶瓷材料制成的表壳中心1显示在图1中。
该陶瓷材料包括构成基质的碳化物类型的相和分布在基质内的氧化物类型的相。碳化物相以在50至95％之间的体积百分比存在于陶瓷材料中，且互补的氧化物相以在5至50％之间的体积百分比存在。优选地，碳化物相以在51至85％之间的体积百分比存在于陶瓷材料中，且互补的氧化物相以在15至49％之间的体积百分比存在。碳化物相包括一种或多种类型的碳化物。例如，其可以是选自TiC、Mo2C、NbC、WC等的一种或多种碳化物。优选地，碳化物相包括选自TiC、Mo2C和NbC的一种或多种碳化物。更优选地，碳化物相包括主要比例的TiC或Mo2C。氧化物相可包括选自例如Al2O3、ZrO2、Cr2O3、Y2O3等的一种或多种氧化物。优选地，氧化物相包括选自Al2O3、ZrO2和Cr2O3的一种或多种氧化物。更优选地，氧化物相包括主要比例的Al2O3或ZrO2。
由碳化物和氧化物的粉末混合物通过烧结制成该陶瓷制品。本发明因此不涉及具有用定向荷载(directional load)，如陶瓷纤维增强的陶瓷基质的复合材料。制造方法包括以下步骤：
a)可能在潮湿环境中与各种陶瓷粉末混合。起始粉末优选具有小于45μm的d50。可任选在磨机或球磨机中进行混合，这在研磨后将粉末粒子的d50减小到大约几微米(<5μm)的尺寸。这种混合物包括按体积计50至95％的碳化物粉末和5至50％的氧化物粉末，各粉末分别包括如上所示的一种或多种碳化物和一种或多种氧化物。优选地，碳化物粉末包括主要比例的碳化钛(TiC)或碳化钼(Mo2C)。其可以除杂质外完全由TiC或Mo2C组成。或者，其可包括TiC或Mo2C和其它碳化物，如NbC和WC；后者当在磨机中使用WC球将粉末与钴粘合剂混合时以次要比例存在于碳化物粉末中。加入附加碳化物的目的是改变该方法的参数，如烧结温度，和/或改变所得性质。优选地，氧化物粉末包括主要比例的氧化铝(Al2O3)或氧化锆(ZrO2)。其可以除杂质外完全由Al2O3或ZrO2组成。或者，其可包括Al2O3或ZrO2和另一氧化物，如Cr2O3，后者以次要比例存在于氧化物粉末中并具有改变所得性质的目的。例如，该粉末氧化物可包括按体积计的下列分布之一，总计100％：
-在65至85％之间的TiC和在15至35％之间的Al2O3，
-在60至80％之间的TiC、在2至10％之间的NbC和在15至35％之间的Al2O3，
-在55至75％之间的TiC、在2至10％之间的Cr2O3和在20至40％之间的Al2O3，
-在70至90％之间的TiC和在10至30％之间的ZrO2，
-在60至80％之间的Mo2C和在20至40％之间的Al2O3，
-在50至60％之间，优选在51至60％之间的Mo2C和在40至50％之间，优选在40至59％之间的Al2O3，
-在65至85％之间的TiC、在1至5％之间的Cr2O3和在10至30％之间的Al2O3。
b)任选可制造包含上述混合物和有机粘合剂体系(石蜡、聚乙烯等)的第二混合物。
a)通过赋予该混合物所需制品的形状，例如通过注射或压制，形成坯料。
c)在惰性气氛下在1300至2100℃的温度下烧结所述坯料15分钟至20小时的时间。如果该混合物包括粘合剂体系，在这一步骤前可进行在200至800℃的温度范围内将有机粘合剂脱蜡的步骤。
将由此获得的坯料冷却和抛光。其可在烧结前和/或在抛光前机械加工以获得所需制品。
获自所述制造方法的制品包括体积百分比接近起始粉末的含碳化物的相和含氧化物的相。实际上，从理论上说，碳化物和氧化物相在烧结过程中共存而没有形成新的相。但是，无法排除在基础粉末和获自烧结的材料之间的组成和百分比的小变化，例如在污染后。
该制品的CIELAB颜色空间(依照标准CIE n°15、lSO 7724/1、DIN 5033Teil 7、ASTM E-1164)具有在60至85之间，优选在65至80之间的亮度分量L*(代表该材料如何反射光)。根据氧化物的选择，可按需要调制分量a*(红色分量)和b*(黄色分量)。有利地，分量a*和b*分别在-1至5之间和在-2至5之间。优选地，分量a*在-0.5至2之间且分量b*在-0.5至3之间。具有白色金属外观的陶瓷材料可能是优选的。在这种情况下，分量a*和b*等于0。
该陶瓷材料具有在1200至1950之间的硬度HV30，取决于成分的类型和百分比。其具有在2至8.5MPa.m1/2之间的韧度Kic，基于在硬度压痕的对角线的四端的裂纹长度的测量，根据以下公式测定韧度：
Figure BDA0003100929570000051
其中P是外加荷载(N)，a是对角线的一半(m)且l是测得裂纹的长度(m)。
特别地，除杂质外包含由TiC组成的碳化物相和由Al2O3组成的氧化物相的陶瓷材料具有极好的韧度-硬度折衷。因此，当这种碳化物相以在65至85％之间，优选在70至80％之间的体积百分比与Al2O3互补相一起存在时，HV30值大于或等于1800，或甚至等于1900，且Kic值大于或等于3.5MPa.m1/2。
同样地，除杂质外包含由TiC组成的碳化物相和由Al2O3和Cr2O3组成的氧化物相的陶瓷材料具有极好的韧度-硬度折衷。因此，当这种碳化物相以在55至75％之间，优选在60至70％之间的体积百分比与Al2O3和Cr2O3互补相一起存在时，HV30值大于或等于1800，且Kic值大于或等于4.5，或甚至等于5MPa.m1/2。
以下实施例例示本发明的方法和由其获得的材料。
实施例
在磨机中在溶剂存在下制备七种粉末混合物。制造无粘合剂的混合物。它们通过压制成形并在60毫巴的氩气流下在取决于粉末组成的温度下烧结。在烧结后，涂布样品并抛光平面。
在样品表面上进行硬度测量HV30并基于如上所述的硬度测量法测定韧度。
用分光光度计KONICA MINOLTA CM-5在下列条件下在抛光样品上测量Lab比色值：SCI(包括镜面反射(specular reflection))和SCE(排除镜面反射)测量，8°倾斜角，8mm直径的测量面积MAV，
实施例1(按重量计80％TiC和20％Al2O3)
粉末混合物包括按重量计80％TiC和20％Al2O3(为α相)，即按体积计分别为76％和24％。坯料在2000℃下烧结20分钟。样品具有1932HV30的平均硬度和4MPa.m1/2的韧度。Lab分量分别等于66.3、0.44和0.73。
实施例2(按重量计70％TiC、10％NbC和20％Al2O3)
粉末混合物包括按重量计70％TiC、10％NbC和20％Al2O3(为α相)，即按体积计分别为69％、6％和25％。坯料在1800℃下烧结30分钟。样品具有1255HV30的平均硬度和3.8MPa.m1/2的韧度。Lab分量分别等于63.3、0.00和0.09。加入NbC能使烧结温度降低200℃但具有降低硬度的效果。
实施例3(按重量计70％TiC、25％Al2O3和5％Cr2O3)
粉末混合物包括按重量计70％TiC、25％Al2O3(为α相)和5％Cr2O3，即按体积计分别为66％、29.5％和4.5％。坯料在1750℃下烧结90分钟。样品具有1830HV30的平均硬度和5.2MPa.m1/2的韧度。Lab分量分别等于64.5、0.34和0.92。加入5％Cr2O3能够获得高硬度和提高韧度。这种样品的电子显微镜图像显示在图2中，灰色相代表TiC基质且白色相代表氧化物相。
实施例4(按重量计80％TiC和20％ZrO2)
粉末混合物包括按重量计80％TiC和20％ZrO2(含有3摩尔％Y2O3的稳定化氧化锆)，即按体积计分别为82％和18％。坯料在1750℃下烧结90分钟。样品具有1617HV30的平均硬度和2.5MPa.m1/2的韧度。Lab分量分别等于66.5、-0.39和-1.14。用氧化锆替代氧化铝能够降低分量a*和b*，也具有降低韧度的效果。
实施例5(按重量计85％Mo2C和15％Al2O3)
粉末混合物包括按重量计85％Mo2C和15％Al2O3(为α相)，即按体积计分别为72％和28％。坯料在1450℃下烧结90分钟。样品具有1319HV30的平均硬度和5.3MPa.m1/2的韧度。Lab分量分别等于72.5、0.21和2。用碳化钼替代碳化钛能够极大降低烧结温度，同时提高亮度指数L*的值。
实施例6(按重量计70％Mo2C和30％Al2O3)
粉末混合物包括按重量计70％Mo2C和30％Al2O3(为α相)，即按体积计分别为51％和49％。坯料在1450℃下烧结90分钟。样品具有1417HV30的平均硬度和5.0MPa.m1/2的韧度。Lab分量分别等于63.8、0.13和1.49。提高氧化铝的比例能够提高硬度，但导致亮度指数L*降低。
实施例7(按重量计80％TiC、18％Al2O3和2％Cr2O3)
粉末混合物包括按重量计80％TiC、18％Al2O3(为α相)和2％Cr2O3，即按体积计分别为76.5％、21.5和2％。坯料在1650℃下烧结90分钟。样品具有1219HV30的平均硬度和7.8MPa.m1/2的韧度。Lab分量分别等于65、0.06和0.4。加入少量氧化铬能够改进韧度。
总之，观察到样品1和3具有极好的韧度-硬度折衷，硬度和韧度值分别高于1800HV30和3.5MPa.m1/2，且样品7具有大于7MPa.m1/2的极好韧度值。

Claims (14)

1.一种由陶瓷材料制成的装饰性制品，所述陶瓷材料包括碳化物相和氧化物相，所述碳化物相为主要比例并具有在70至85％之间的体积百分比，其中所述氧化物相为次要比例并以在15至30％之间的体积百分比存在，并且
其中所述碳化物相包括选自碳化钛、碳化钼、碳化钨和碳化铌的一种或多种碳化物，碳化钛始终与碳化钼、碳化钨和/或碳化铌组合。
2.根据前一权利要求的制品，其特征在于所述碳化物相包括主要比例的碳化钛或碳化钼。
3.根据权利要求2的制品，其特征在于所述包括主要比例的碳化钛的碳化物相以在55至90％之间，优选在60至85％之间的体积百分比存在，所述氧化物相以在10至45％之间，优选在15至40％之间的体积百分比存在。
4.根据权利要求3的制品，其特征在于所述碳化物相包括次要比例的碳化铌。
5.根据权利要求2的制品，其特征在于所述包括主要比例的碳化钼的碳化物相以在50至75％之间，优选在51至75％之间的体积百分比存在，所述氧化物相以在25至50％之间，优选在25至49％之间的体积百分比存在。
6.根据前述权利要求任一项的制品，其特征在于其还包括次要比例的氧化铬。
7.根据权利要求3的制品，其特征在于所述碳化物相以在65至85％之间，优选在70至80％之间的体积百分比存在，且所述氧化铝相以在15至35％之间，优选在20至30％之间的体积百分比存在。
8.根据权利要求3的制品，其特征在于其进一步包括氧化铬。
9.根据权利要求8的制品，其特征在于所述碳化物相以在55至75％之间，优选在60至70％之间的体积百分比存在，且所述氧化物相以在25至45％之间，优选在30至40％之间的体积百分比存在。
10.根据前述权利要求任一项的制品，其特征在于其具有大于1800，优选大于1900的硬度HV30，且其具有大于或等于3.5MPa.m1/2，优选5MPa.m1/2的韧度KiC。
11.根据前述权利要求任一项的制品，其特征在于其在CIELAB颜色空间中具有在60至85之间，优选在65至80之间的分量L*。
12.根据权利要求11的制品，其特征在于其具有在-1至5之间，优选在-0.5至2之间的分量a*，且其具有在-2至5之间，优选在-0.5至3之间的分量b*。
13.根据权利要求12的制品，其特征在于分量a*和b*等于0。
14.根据前述权利要求任一项的制品，其特征在于其是选自表壳中心、底盖、表圈、按钮、表带连接、表盘、指针和表盘指数的钟表外部组件。
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