CN105565806A - 一种陶瓷及其制备方法 - Google Patents

一种陶瓷及其制备方法 Download PDF

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Publication number
CN105565806A
CN105565806A CN201410742426.4A CN201410742426A CN105565806A CN 105565806 A CN105565806 A CN 105565806A CN 201410742426 A CN201410742426 A CN 201410742426A CN 105565806 A CN105565806 A CN 105565806A
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pottery
preparation
hour
additive
oxide compound
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CN201410742426.4A
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CN105565806B (zh
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宫清
林信平
陈戈
林勇钊
吴波
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BYD Co Ltd
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BYD Co Ltd
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Priority to CN201410742426.4A priority Critical patent/CN105565806B/zh
Priority to US15/533,563 priority patent/US10106465B2/en
Priority to JP2017530325A priority patent/JP6640225B2/ja
Priority to KR1020177017018A priority patent/KR101941092B1/ko
Priority to EP15868073.6A priority patent/EP3231781B1/en
Priority to PCT/CN2015/095458 priority patent/WO2016091062A1/zh
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Abstract

本发明涉及一种陶瓷，该陶瓷含有氧化锆基体和分散在氧化锆基体内部和外表面的黑色微粒，所述黑色微粒为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种；本发明还涉及一种陶瓷的制备方法，本发明还涉及该方法制备的陶瓷。本发明的陶瓷同时具有韧性强、耐摔性好和黑度大的优异性能。

Description

一种陶瓷及其制备方法
技术领域
本发明涉及一种陶瓷，一种陶瓷的制备方法，以及该方法制备的陶瓷。
背景技术
氧化锆陶瓷由于具有比常规陶瓷耐腐蚀性好、硬度高、强度高的特点，因此有着广泛的应用，其韧性可达5-6MPam1/2。虽然其韧性较其他常规陶瓷要高，但在做成大面积外观件时，有着不耐摔，颜色本身为白色，太过单一等缺点，然而，由于用作外观件的陶瓷必须同时满足韧性强、耐摔以及色度要黑的条件，因此，目前的氧化锆陶瓷产品均不能够满足外观件上所需陶瓷的要求，严重影响了氧化锆陶瓷在外观件上的应用。
由于市面上钇稳定的氧化锆粉体已经很成熟，所以现有增韧的技术方案都是建立在钇稳定的基础上。现有增韧技术里，最常用的就是相变以及第二相增韧等方案，但这些方案要么只针对白色陶瓷，要么在染黑的同时无法达到增韧抗摔的效果。例如专利申请CN1170787C所提及的Mg稳定TZP陶瓷，虽然具有一定的增韧效果，但不明显，而且制备出的样品强度偏低只有590MPa左右，采用该强度的陶瓷制备出大面积的外观件薄片，易发生断裂，无法制备出大面积的薄片，并且，该陶瓷为白色，可应用范围也较低。
因此，目前急需一种兼具韧性强、耐摔和黑度大优异性能的氧化锆陶瓷及其制备方法。
发明内容
本发明的目的是为了克服现有技术中氧化锆陶瓷韧性低、不耐摔和黑度低缺陷，提供一种陶瓷，一种陶瓷的制备方法，以及该方法制备的陶瓷。
本发明的发明人在研究中发现，陶瓷含有氧化锆基体和分散在氧化锆基体内部和外表面的黑色微粒，所述黑色微粒为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种时，该陶瓷能够同时具有韧性强、耐摔和黑度大的优异性能。
因此，为了实现上述目的，一方面，本发明提供了一种陶瓷，该陶瓷含有氧化锆基体和分散在氧化锆基体内部和外表面的黑色微粒，所述黑色微粒为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
另一方面，本发明还提供了一种陶瓷的制备方法，该方法包括以下步骤：
(1)将含有氧化锆和添加剂的陶瓷原料与烧结助剂在有机溶剂中混合均匀，然后加入粘结剂混合均匀，得到混合浆料；
(2)将步骤(1)得到的混合浆料干燥除去有机溶剂，得到球形粉体；
(3)将步骤(2)得到的球形粉体成型，然后烧结，得到陶瓷；
所述添加剂为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
第三方面，本发明还提供了上述方法制备的陶瓷。
本发明陶瓷的制备方法中，由于向氧化锆基体中添加了含有A和B元素的氧化物的上述的添加剂，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种，在烧结时能在陶瓷中形成一种黑色的微粒物质，这种黑色微粒均匀分散在陶瓷内部及外表面，能够增大陶瓷的黑度，并且其还能够阻止裂纹的扩展，使得陶瓷的耐摔性增强。因此，本发明的陶瓷同时具有韧性强、耐摔和黑度大的优异性能。
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
图1是实施例1制得的陶瓷表面的电镜图；
图2是实施例1制得的陶瓷中黑色微粒的X射线能谱仪测定图；
图3是对比例1制得的陶瓷表面的电镜图；
图4为样品板A1连续与地面接触3次后的陶瓷表面的电镜图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明提供了一种陶瓷，该陶瓷含有氧化锆基体和分散在氧化锆基体内部和外表面的黑色微粒，所述黑色微粒为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
根据本发明所述的陶瓷，其中，只要陶瓷含有氧化锆基体和上述黑色微粒，即可同时提高陶瓷的韧性，耐摔性和黑度。但是，为了进一步提高陶瓷的韧性，耐摔性和黑度，优选地，所述氧化物为AxByOz，其中，x为0.5～2，y为0.5～2，z为3～5。
根据本发明所述的陶瓷，其中，黑色微粒的大小只要不影响陶瓷的外观即可，为了进一步提高陶瓷的韧性，耐摔性和黑度，优选地，黑色微粒的平均粒径为0.5～10微米，更优选为1～7微米。
本领域技术人员应该理解的是，其中，陶瓷含有烧结助剂，烧结助剂的种类可以为本领域常规的用于制备陶瓷的烧结助剂，优选地，烧结助剂为Ta2O5、Nb2O5、CuO、ZnO和TiO2中的至少一种时，能够进一步提高陶瓷的韧性，耐摔性和黑度。
根据本发明所述的陶瓷，其中，陶瓷中氧化锆、添加剂和烧结助剂的含量可以为本领域常规的陶瓷中的用量，但是，优选地，以氧化锆的总重量为基准，添加剂的含量为1～10重量％，烧结助剂的含量为0.1～5重量％，能够进一步提高陶瓷的韧性，耐摔性和黑度。
本发明中，陶瓷的韧性可以为10～12MPam1/2，陶瓷的抗摔次数可以为10～15次。
本发明中，相对于红绿值a为0.08、蓝黄值b为-0.04的和表面反射光的强度L为44的标准陶瓷样品，陶瓷的红绿值a可以为0.06～0.07，蓝黄值b可以为-0.02～-0.03，表面反射光的强度L可以为42～44。
本领域技术人员应该理解的是，氧化锆可以为本领域常规的用于制备氧化锆陶瓷的钇稳定的四方相氧化锆。
另一方面，本发明还提供了一种陶瓷的制备方法，该方法包括以下步骤：
(1)将含有氧化锆和添加剂的陶瓷原料与烧结助剂在有机溶剂中混合均匀，然后加入粘结剂混合均匀，得到混合浆料；
(2)将步骤(1)得到的混合浆料干燥除去有机溶剂，得到球形粉体；
(3)将步骤(2)得到的球形粉体成型，然后烧结，得到陶瓷；
所述添加剂为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
根据本发明所述的制备方法，其中，只要采用上述方法制备陶瓷，即可同时提高陶瓷的韧性，耐摔性和黑度。但是，为了进一步提高陶瓷的韧性，耐摔性和黑度，优选地，所述氧化物为AxByOz，其中，x为0.5～2，y为0.5～2，z为3～5。
根据本发明所述的制备方法，其中，添加剂的制备方法可以为本领域常规的制备方法，但是，为了进一步提高陶瓷的韧性，耐摔性和黑度，优选地，所述添加剂的制备方法包括：将含有A元素的氧化物、碳酸盐、硝酸盐和草酸盐中的至少一种与含有B元素的氧化物、碳酸盐、硝酸盐和草酸盐中的至少一种进行混合，并在900～1350℃下烧结，更优选地，烧结时间为2-5小时。
根据本发明所述的制备方法，其中，步骤(3)中的烧结程序可以为本领域常规的烧结程序，例如可以为：室温经5-7小时升至500～700℃保温1-2小时，500～700℃经5-7小时升至900～1100℃保温1-2小时，900～1100℃经0.5-2小时升至1200℃保温1-2小时，1200℃经2-5小时升至1350-1450℃保温3～4小时，然后经过2-5小时降至900℃，最后自然冷却至室温。
在本发明的一种优选的实施方式中，该方法还包括在步骤(1)中，在将含有氧化锆和添加剂的陶瓷原料与烧结助剂在有机溶剂中混合均匀后，在加入粘结剂混合均匀前，加入分散剂，能够使得氧化锆、添加剂和烧结助剂间更加充分地混合，从而更有利于陶瓷中黑色微粒的形成，使得最终制备的陶瓷的内部结构和外观颜色都更加均匀，并且使得陶瓷各部分的韧性和耐摔性也更加一致。
根据本发明所述的制备方法，其中，对分散剂的种类和用量没有特殊要求，例如分散剂种类可以为羟丙甲纤维素、羧甲基纤维素钠和三乙醇胺中的至少一种，相对于100重量份的基体材料，分散剂的用量可以为1～2重量份。
根据本发明所述的制备方法，步骤(1)中，为了更好地发挥氧化锆基体材料本身的良好性能，并进一步提高陶瓷的韧性，耐摔性和黑度，优选地，以氧化锆的总重量为基准，所述添加剂的用量为1～10重量％，所述烧结助剂的用量为0.1～5重量％，所述粘结剂的用量为0.5～1.5重量％。
根据本发明所述的制备方法，烧结助剂可以为本领域常规的用于制备陶瓷的烧结助剂，为了进一步降低烧结温度，并进一步促进陶瓷的致密化，从而使得制得的陶瓷韧性更大、更耐摔和黑度更好，优选地，烧结助剂为Ta2O5、Nb2O5、CuO、ZnO和TiO2中的至少一种。
根据本发明所述的制备方法，其中，所述粘结剂可以为聚乙烯醇和/或聚乙二醇4000，为了更好地粘结用于制备陶瓷的原料，优选地，所述粘结剂为聚乙烯醇和聚乙二醇4000，聚乙烯醇和聚乙二醇4000的摩尔比优选为1：1～2。
根据本发明所述的制备方法，对有机溶剂的种类和用量均没有特殊要求，例如有机溶剂的种类可以为乙醇、丙酮和水中的至少一种；相对于100重量份的基体材料，有机溶剂的用量可以为50～80重量份。
根据本发明所述的制备方法，在步骤(1)中，对于混合的方式无特殊要求，只要能够混合均匀即可，例如，混合的方式可以为球磨，球磨的时间优选为4～8小时，球磨优选在球磨罐中进行。
根据本发明所述的制备方法，在步骤(2)中，所述干燥可以为常规的干燥方式，优选地，所述干燥为喷雾干燥，采用喷雾干燥能够形成流动性较强的球形粉体，更便于后续的成型。其中，喷雾干燥可以在常规的喷雾塔中进行。
根据本发明所述的制备方法，成型可以为本领域常规的成型工艺，例如可以为干压成型、等静压成型、注射成型、热压铸成型中的一种，优选为干压成型。当成型工艺为干压成型，干压成型的参数可以为本领域常规的参数，例如可以为吨位180吨的压机使用6MPa的油压压强。
根据本发明所述的制备方法，其中，所述方法还可以包括将得到的所述陶瓷进行抛光，从而获得外观光亮的陶瓷材料。
第三方面，本发明还提供了上述方法制备的陶瓷。
在本发明中，采用本发明的方法制备陶瓷，能够同时提高陶瓷的韧性、耐水性和黑度，例如可以使制备的陶瓷的韧性达到10～12MPam1/2，抗摔次数达到10～15次，并且可以提高制备的陶瓷的黑度，例如相对于红绿值a为0.08、蓝黄值b为-0.04的和表面反射光的强度L为44的标准陶瓷样品，可以使制得的陶瓷的红绿值a为0.06～0.07，蓝黄值b为-0.02～-0.03，L表面反射光的强度为42～44。
在本发明中，韧性测试根据GBT23806测定，黑度测定根据色度仪测定。
实施例
以下实施例和对比例中，氧化锆购自东方锆业。
色度仪的型号为美国爱色丽X-Rite生产的SP64。
电镜型号为JSM-7600F扫描电镜，X射线能谱仪型号为SmartLab型。
实施例1
本实施例用于说明本发明的陶瓷及其制备方法。
(1)添加剂的制备：将SrO、La2O3和MnO2按照重量比1：1：1混合均匀，然后烘干，再在900℃下保温2h，然后球磨粉碎至微米级，制得添加剂，按照元素的用量计算可得添加剂为Sr1La0.5Mn1O3的氧化物。
(2)将陶瓷原料(200g氧化锆、10g添加剂)与10g的Ta2O5在120mL的乙醇中球磨4个小时混合均匀，然后加入4g的羟丙甲纤维素，再加入3g的聚乙二醇4000与聚乙烯醇的混合物(质量比1：1)继续球磨半个小时，得到混合浆料；然后将混合浆料送入喷雾塔中进行喷雾干燥，直至混合浆料全部干燥为球形粉体为止，然后将球形粉体在吨位180吨的压机使用6MPa的油压压强的参数条件下干压成型，在下述烧结程序下进行烧结，打磨抛光后得到陶瓷样品，然后激光切割后制得样品板A1，样品板的厚度为0.8mm。在电镜下观察到陶瓷表面附有黑色微粒(参见图1)，测得黑色微粒的平均粒径为1微米，采用X射线能谱仪测定黑色微粒的元素组成(参见图2)。
烧结程序：室温经5小时升至600℃保温2小时，600℃经5小时升至1100℃保温2小时，1100℃经0.5小时升至1200℃保温2小时，1200℃经2小时升至1400℃保温3小时，然后经过2小时降至900℃，最后自然冷却至室温。
实施例2
本实施例用于说明本发明的陶瓷及其制备方法。
(1)添加剂的制备：将Y2O3、CaO、和CoO按照重量比1：1：2混合均匀，然后烘干，再在1200℃下保温1.5h，然后球磨粉碎至微米级，制得添加剂，按照元素的用量计算可得添加剂为Ca1.5Y0.5Co0.5O3的氧化物。
(2)将陶瓷原料(200g氧化锆、8g添加剂)与10g的ZnO在100mL的乙醇中球磨7个小时混合均匀，然后加入2g的三乙醇胺，再加入3g的聚乙二醇4000与聚乙烯醇的混合物(质量比1：1.5)继续球磨半个小时，得到混合浆料；然后将混合浆料送入喷雾塔中进行喷雾干燥，直至混合浆料全部干燥为球形粉体为止，然后将球形粉体在吨位180吨的压机使用6MPa的油压压强的参数条件下干压成型，在下述烧结程序下进行烧结，打磨抛光后得到陶瓷样品，然后激光切割后制得样品板A2，样品板的厚度为0.8mm。在电镜下观察到陶瓷表面附有黑色微粒，测得黑色微粒的平均粒径为5微米。
烧结程序：室温经7小时升至500℃保温2小时，500℃经7小时升至900℃保温2小时，900℃经2小时升至1200℃保温1小时，1200℃经5小时升至1450℃保温3.5小时，然后经过4小时降至900℃，最后自然冷却至室温。
实施例3
本实施例用于说明本发明的陶瓷及其制备方法。
(1)添加剂的制备：将SrO、BaO、MnO2和Fe2O3按照重量比1：1.3：1：0.5混合均匀，然后烘干，再在1500℃下保温4h，然后球磨粉碎至微米级，制得添加剂，按照元素的用量计算可得添加剂为Sr1Ba0.5Mn0.5Fe0.5O3的氧化物。
(2)将陶瓷原料(200g氧化锆、2g添加剂)与10g的Ta2O5在160mL的乙醇中球磨6个小时混合均匀，然后加入2g的羧甲基纤维素钠，再加入3g的聚乙二醇4000与聚乙烯醇的混合物(质量比1：2)继续球磨半个小时，得到混合浆料；然后将混合浆料送入喷雾塔中进行喷雾干燥，直至混合浆料全部干燥为球形粉体为止，然后将球形粉体在吨位180吨的压机使用6MPa的油压压强的参数条件下干压成型，在下述烧结程序下进行烧结，打磨抛光后得到陶瓷样品，然后激光切割后制得样品板A3，样品板的厚度为0.8mm。在电镜下观察到陶瓷表面附有黑色微粒，测得黑色微粒的平均粒径为7微米。
烧结程序：室温经6小时升至700℃保温1小时，700℃经6小时升至1100℃保温1小时，1100℃经2小时升至1200℃保温2小时，1200℃经4小时升至1450℃保温4小时，然后经过4小时降至900℃，最后自然冷却至室温。
对比例1
按照实施例1的方法制备陶瓷，不同的是，将实施例1中的添加剂替换为Ta2O5。最终制得样品板D1，在电镜下观察到陶瓷表面没有黑色微粒形成(参见图3)。
测试例
韧性根据GBT23806断裂韧性测试标准对样品板A1～A3和D1分别进行测试，测试结果如表1所示。
抗摔测试：将A1～A3和D1四组样品板(长宽同苹果iPhone4s的后壳，厚度0.8mm)(每组样品板的数量为10个)分别进行自由落体式的下落，下落的初始高度为1.3m，且下落时，样品板表面积较大的面与陶瓷砖地面接触，每组样品板的抗摔次数为组内10个样品板抗摔次数的平均数，其中，只要完全断裂即可停，不管裂纹大小，测试结果如表1所示。另外，采用该抗摔测试方法，挑取A1连续与地面接触3次的样品板，在电镜下观察该样品板的表面，结果见图4。
黑度测试采用色度仪对标准样、样品板A1～A3和D1分别进行测定，测定结果如表2所示。
表1
样品板 韧性(MPa m1/2) 抗摔次数(次)
A1 12 15
A2 10 10
A3 12 13
D1 2 2
表2
注：L为样品表面反射光的强度，a为红绿值(正值代表偏红，负值代表偏绿)，b为蓝黄值(正值代表偏黄，负值代表偏蓝)。
将实施例1～3与对比例1进行比较，从图1-3中可以看出在电镜图中陶瓷表面附有黑色颗粒，而图3中的陶瓷表面没有黑色颗粒，因此，本发明方法制备的陶瓷由于形成了黑色颗粒，其韧性较强、黑度较高，且更抗摔。
另外，从图4可以看出，黑色颗粒在抗摔测试时能够阻止裂纹的扩展，从而能够显著增强陶瓷的耐摔性。
本发明陶瓷的制备方法中，由于向氧化锆基体中添加了含有A和B元素的氧化物的上述的添加剂，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种，在烧结时能在陶瓷中形成一种黑色的微粒物质，这种黑色微粒均匀分散在陶瓷内部及外表面，能够增大陶瓷的黑度，并且其还能够阻止裂纹的扩展，使得陶瓷的耐摔性增强。因此，本发明的陶瓷同时具有韧性强、耐摔和黑度大的优异性能。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (19)

1.一种陶瓷，其特征在于，该陶瓷含有氧化锆基体和分散在氧化锆基体内部和外表面的黑色微粒，所述黑色微粒为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
2.根据权利要求1所述的陶瓷，其中，所述氧化物为AxByOz，其中，x为0.5～2，y为0.5～2，z为3～5。
3.根据权利要求1所述的陶瓷，其中，所述黑色微粒的平均粒径为0.5～10微米，优选为1～7微米。
4.根据权利要求1～3中任意一项所述的陶瓷，其中，该陶瓷还含有烧结助剂，所述烧结助剂为Ta2O5、Nb2O5、CuO、ZnO和TiO2中的至少一种。
5.根据权利要求4所述的陶瓷，其中，以氧化锆的总重量为基准，添加剂的含量为1～10重量％，烧结助剂的含量为0.1～5重量％。
6.根据权利要求1～3中任意一项所述的陶瓷，其中，所述陶瓷的韧性为10～12MPam1/2。
7.根据权利要求1～3中任意一项所述的陶瓷，其中，所述陶瓷的抗摔次数为10～15次。
8.根据权利要求1～3中任意一项所述的陶瓷，其中，相对于红绿值a为0.08、蓝黄值b为-0.04的和表面反射光的强度L为44的标准陶瓷样品，所述陶瓷的红绿值a为0.06～0.07，蓝黄值b为-0.02～-0.03，表面反射光的强度L为42～44。
9.一种陶瓷的制备方法，其特征在于，该方法包括以下步骤：
(1)将含有氧化锆和添加剂的陶瓷原料与烧结助剂在有机溶剂中混合均匀，然后加入粘结剂混合均匀，得到混合浆料；
(2)将步骤(1)得到的混合浆料干燥除去有机溶剂，得到球形粉体；
(3)将步骤(2)得到的球形粉体成型，然后烧结，得到陶瓷；
所述添加剂为含有A和B元素的氧化物，其中，A选自Ca、Sr、Ba、Y和La中的至少一种，B选自Cr、Mn、Fe、Co和Ni中的至少一种。
10.根据权利要求9所述的制备方法，其中，所述氧化物为AxByOz，其中，x为0.5～2，y为0.5～2，z为3～5。
11.根据权利要求9所述的制备方法，其中，所述添加剂的制备方法包括：将含有A元素的氧化物、碳酸盐、硝酸盐和草酸盐中的至少一种与含有B元素的氧化物、碳酸盐、硝酸盐和草酸盐中的至少一种进行混合，并在900～1350℃下烧结。
12.根据权利要求9～11中任意一项所述的制备方法，其中，步骤(3)中，所述烧结的程序为：室温经5-7小时升至500～700℃保温1-2小时，500～700℃经5-7小时升至900～1100℃保温1-2小时，900～1100℃经0.5-2小时升至1200℃保温1-2小时，1200℃经2-5小时升至1350-1450℃保温3-4小时，然后经过2-5小时降至900℃，最后自然冷却至室温。
13.根据权利要求9～11中任意一项所述的制备方法，其中，所述方法还包括：步骤(1)中，在加入所述粘结剂之前加入分散剂。
14.根据权利要求13所述的制备方法，其中，所述分散剂选自羟丙甲纤维素、羧甲基纤维素钠和三乙醇胺中的至少一种。
15.根据权利要求9～11中任意一项所述的制备方法，其中，所述烧结助剂为Ta2O5、Nb2O5、CuO、ZnO和TiO2中的至少一种。
16.根据权利要求9～11中任意一项所述的制备方法，其中，以氧化锆的总重量为基准，所述添加剂的用量为1～10重量％，所述烧结助剂的用量为0.1～5重量％，所述粘结剂的用量为0.5～1.5重量％。
17.根据权利要求9～11中任意一项所述的制备方法，其中，所述粘结剂为聚乙烯醇和/或聚乙二醇4000，优选地，所述粘结剂为聚乙烯醇和聚乙二醇4000，所述聚乙烯醇和聚乙二醇4000的摩尔比为1：1～2。
18.根据权利要求9～11中任意一项所述的制备方法，其中，步骤(3)中，所述成型为干压成型、等静压成型、注射成型、热压铸成型中的一种，优选为干压成型。
19.根据权利要求9～18中任意一项所述的方法制备的陶瓷。
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