CN107021769A - 一种纳米稀土氧化物合金陶瓷的制备方法 - Google Patents

一种纳米稀土氧化物合金陶瓷的制备方法 Download PDF

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CN107021769A
CN107021769A CN201710245280.6A CN201710245280A CN107021769A CN 107021769 A CN107021769 A CN 107021769A CN 201710245280 A CN201710245280 A CN 201710245280A CN 107021769 A CN107021769 A CN 107021769A
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贾玉川
贾鹏飞
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LUOYANG PENGFEI WEAR-RESISTANT MATERIALS Ltd BY SHARE Ltd
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Abstract

本发明提供了一种纳米稀土氧化物合金陶瓷的制备方法，具体方法为，步骤一、纳米稀土陶瓷球的制备：（1）稀土前体：将Ce(NO3)3·6H2O和H2C2O4·2H2O在研磨机上研磨，得到Ce(C2O4)3·10H2O；（2）稀土陶瓷粉球：将Ce(C2O4)3·10H2O、陶瓷粉干燥，放入球磨机内研磨，加入胶黏剂后进行造粒；（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉预烧结得到复合陶瓷球；步骤二、混料：原陶瓷粉、金属纤维、粘合剂、复合陶瓷球通过球磨制备浆料；经步骤三的装模、步骤四的烧结，得到陶瓷基体。本发明通过预烧结分解得到包含有纳米氧化铈的陶瓷球，纳米稀土氧化物分散均匀，强度韧性得到提高。

Description

一种纳米稀土氧化物合金陶瓷的制备方法
技术领域
本发明涉及一种陶瓷材料，尤其涉及一种纳米稀土氧化物合金陶瓷的制备方法。
背景技术
纳米材料因其独特的表面效应、量子尺寸效应等而表现出不同于常规材料的特殊性能，因而在各个领域得到广泛的应用。作为新材料中的一员，稀土纳米材料的研究也成为世界各国科学家研究的热点之一。二氧化铈作为一种典型的轻稀土氧化物已被广泛用于发光材料、抛光剂、紫外吸收剂、汽车尾气净化催化剂、玻璃化学退色剂、耐辐射玻璃、电子陶瓷等领域。
稀土元素在当今工业生产和科学研究中应用很广，被称为“现代工业的维生素”，在我国陶瓷工业中的应用始于上世纪30年代，在70年代稀土在陶瓷材料中的总用量达70t/年，占国内生产总量的2%到3%左右，目前稀土主要应用于结构陶瓷、功能陶瓷、陶瓷色釉料等领域。随着稀土新材料的不断开发与应用，将稀土作为添加剂、稳定剂、烧结助剂作用于各种陶瓷材料，极大地改善了其性能、降低了生产成本。
同时，金属纤维具有原金属的优良特性，是复合材料良好的增强增韧剂。应用在陶瓷中，以金属纤维增强的陶瓷基复合材料具有很高的压缩强度和冲击韧性，同时具有高温稳定性好、成型好、可进行机械加工等优点。
常规的纳米稀土氧化物在材料中的应用是利用固固掺杂的方法将纳米稀土氧化物与目标粉料，如钼粉、陶瓷粉等，研磨均匀后在球磨罐进行球磨，之后经过过筛、压制成型、在保护气氛下烧结成型，经模锻后得到成品；另有将纳米稀土氧化物在复合陶瓷层的应用，是将陶瓷层经由水砂纸打磨、超声波清洗、清水冲洗、氧化，然后在离子镀装置中镀纳米稀土氧化物膜；这些方法中所用的稀土类氧化物均为预先制备，然后将纳米颗粒混入或者电镀在目标物。而纳米稀土氧化物与粉料直接固固掺杂的方法，纳米颗粒具有高的表面能，极易团聚在一起，容易使混料不均，影响纳米稀土氧化物改良材料的性能；采用离子镀的方法将纳米稀土电镀在复合体表面，纳米稀土类氧化物只是在复合体表面起到金属镀层的作用，应用有限。
发明内容
本发明通过预烧结分解得到包含有纳米氧化铈的陶瓷球，再经由混料、装模、烧结，得到纳米稀土氧化物合金陶瓷，纳米稀土氧化物分散均匀，强度韧性也得到提高。
为了实现上述目的，本发明提供了如下技术方案：一种纳米稀土氧化物合金陶瓷的制备方法，包括以下步骤：
步骤一、纳米稀土陶瓷球的制备：
（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为30~45min，得到Ce(C2O4)3·10H2O，之后分别用水和乙醇淋洗多次；
（2）稀土陶瓷粉球：按重量份数将32~35份的Ce(C2O4)3·10H2O、57~62份的陶瓷粉分别在120~160℃下干燥3~5h，放入球磨机内研磨9~11h，将两种粉末混匀后，加入3~11份胶黏剂后进行造粒，造粒所得稀土陶瓷粉球粒径为1~50mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在360~400℃下预烧结，保持2~3h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：按重量分数，原陶瓷粉40～50份，金属纤维5~18份，粘合剂6~12份，放入球磨机内研磨1h，再将步骤一中的复合陶瓷球20～49份分为若干等份加入，继续球磨9~12h，制成浆料；
步骤三、装模：将步骤二中的浆料填充在模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1382~1643℃，保温4~6h后取出，降温得到陶瓷基体。
进一步的，所述步骤一中的胶黏剂为石蜡、亚硫酸纸浆废液中的一种或多种。
进一步的，所述陶瓷粉成分为碳化硅62~75份、氧化铝23～34份、氧化铁1.2~2份、氧化镁0.3~1.6份、氧化钛0.2~0.9份，将上述成分放入球磨机内研磨8~12h，混合均匀后过目筛选，陶瓷粉粒度为100~500目。
进一步的，步骤二中所述金属纤维成分为铜纤维、铝纤维、镍纤维、铁铬铝合金纤维、钼纤维、锰纤维、高温合金纤维的一种或多种。
进一步的，所述金属纤维为短纤维，纤维直径为1~25μm。
进一步的，所述粘合剂为热塑性粘结剂，成分包括石蜡59~65份、聚乙烯18~24份、邻苯二甲酸二乙酯6~8份、硅烷3~17份。
进一步的，所述步骤二中复合陶瓷球的添加分为3~6次添加，每次间隔30~60min。
进一步的，所述混料过程中加入煤粉、石灰石、白云石中的一种或多种。
本发明通过纳米氧化铈及金属纤维分阶段制备陶瓷材料，纳米氧化铈作为稀土类金属具有独特的储放氧功能与高位快速空位扩散能力；将较大比例的纳米氧化铈的原料预先与陶瓷粉造粒，制备稀土陶瓷粉球，混料更为均匀；根据固相热分解制备纳米氧化铈的方法，陶瓷粉球分阶段加热，氧化铈原料在360~400℃下预烧结分解，得到包含有纳米氧化铈的陶瓷球，又因陶瓷粉球预烧结过程中有气体产生，增加了复合陶瓷球的比表面积，所制备的陶瓷材料可用于汽车尾气处理等方向；在混料过程中加入金属短纤维，金属短纤维均匀填充在陶瓷内部，起到增韧等效果。
本发明的有益效果如下所示：
1.稀土原料与陶瓷粉造粒得到含稀土的陶瓷粉球，进一步分段烧结、混料，与纳米类稀土颗粒直接添加在陶瓷粉料中球磨、混料、烧结的工艺相比，稀土原料在陶瓷材料中的分散更为均匀；
2.根据固相热分解制备纳米氧化铈的方法，造粒所得的含稀土的陶瓷粉球在360~400℃下预烧结分解，得到包含有纳米氧化铈的陶瓷球，且陶瓷粉球预烧结过程中有气体产生，增加了复合陶瓷球的比表面积；
3.混料过程中加入了金属短纤维，金属短纤维均匀填充在陶瓷内部，起到增韧、增韧的效果；
4.复合陶瓷球在混料过程中分阶段添加并搅拌，混合的浆料更为均匀；
5.陶瓷的制备过程中加入致孔剂，生成多孔的纳米稀土氧化物合金陶瓷，预烧结得到的多孔复合陶瓷球，结合具有独特的储放氧功能与高位快速空位扩散能力，可用于汽车尾气处理等需要多孔陶瓷的材料领域。
具体实施方法
一种纳米稀土氧化物合金陶瓷的制备方法，包括以下步骤：
步骤一、纳米稀土陶瓷球的制备：
（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为30~45min，得到Ce(C2O4)3·10H2O，之后分别用水和乙醇淋洗多次；
（2）稀土陶瓷粉球：按重量份数将32~35份的Ce(C2O4)3·10H2O、57~62份的陶瓷粉分别在120~160℃下干燥3~5h，放入球磨机内研磨9~11h，将两种粉末混匀后，加入3~11份胶黏剂后进行造粒，造粒所得稀土陶瓷粉球粒径为1~50mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在360~400℃下预烧结，保持2~3h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：按重量分数，原陶瓷粉40～50份，金属纤维5~18份，粘合剂6~12份，放入球磨机内研磨1h，再将步骤一中的复合陶瓷球20～49份分为若干等份加入，继续球磨9~12h，制成浆料；
步骤三、装模：将步骤二中的浆料填充在模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1382~1643℃，保温4~6h后取出，降温得到陶瓷基体。
进一步的，所述步骤一中的胶黏剂为石蜡、亚硫酸纸浆废液中的一种或多种。
进一步的，所述陶瓷粉成分为碳化硅62~75份、氧化铝23～34份、氧化铁1.2~2份、氧化镁0.3~1.6份、氧化钛0.2~0.9份，将上述成分放入球磨机内研磨8~12h，混合均匀后过目筛选，陶瓷粉粒度为100~500目。
进一步的，步骤二中所述金属纤维成分为铜纤维、铝纤维、镍纤维、铁铬铝合金纤维、钼纤维、锰纤维、高温合金纤维的一种或多种。
进一步的，所述金属纤维为短纤维，纤维直径为1~25μm。
进一步的，所述粘合剂为热塑性粘结剂，成分包括石蜡59~65份、聚乙烯18~24份、邻苯二甲酸二乙酯6~8份、硅烷3~17份。
进一步的，所述步骤二中复合陶瓷球的添加分为3~6次添加，每次间隔30~60min。
进一步的，所述混料过程中加入煤粉、石灰石、白云石中的一种或多种。
为了更好的说明本发明，下面结合具体实施例对其进行解释：
实施例1
一种纳米稀土氧化物合金陶瓷的制备方法，首先制备纳米稀土陶瓷球：
步骤一、（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为30min，得到Ce(C2O4)3·10H2O，分别用水和乙醇清洗三次；
（2）稀土陶瓷粉球：按重量份数将32份的Ce(C2O4)3·10H2O、57份的陶瓷粉分别在120℃下干燥3h，放入球磨机内研磨9~11h，将两种粉末混匀后，加入11份石蜡后进行造粒，造粒所得稀土陶瓷粉球粒径为1mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在360℃下预烧结，保持2h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：陶瓷粉成分为碳化硅62份、氧化铝33.5份、氧化铁2份、氧化镁1.6份、氧化钛0.9份，将上述成分放入球磨机内研磨8h，混合均匀后过目筛选，陶瓷粉粒度为100目；按重量分数，原陶瓷粉40份，锰纤维5份，粘合剂6份，放入球磨机内研磨1h，再将步骤一中的占49份的复合陶瓷球分为3等份加入，每次间隔30min，继续球磨9h，制成浆料；其中粘合剂为石蜡59份、聚乙烯18份、邻苯二甲酸二乙酯6份、硅烷17份；所用锰纤维为短纤维，直径为1μm；混料过程中加入浆料总量8%的石灰石作为致孔剂；
步骤三、装模：将步骤二中的浆料填充在陶瓷板模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1382℃，保温4h后取出，降温得到陶瓷板。
实施例2
一种纳米稀土氧化物合金陶瓷的制备方法，首先制备纳米稀土陶瓷球：
步骤一、（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为40min，得到Ce(C2O4)3·10H2O，分别用水和乙醇淋清洗5次；
（2）稀土陶瓷粉球：按重量份数将33份的Ce(C2O4)3·10H2O、60份的陶瓷粉分别在145℃下干燥4h，放入球磨机内研磨10h，将两种粉末混匀后，加入7份石蜡后进行造粒，造粒所得稀土陶瓷粉球粒径为25mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在380℃下预烧结，保持2.5h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：陶瓷粉成分为碳化硅70份、氧化铝26.5份、氧化铁1.5份、氧化镁1.5份、氧化钛0.5份，将上述成分放入球磨机内研磨10h，混合均匀后过目筛选，陶瓷粉粒度为300目；按重量分数，原陶瓷粉45份，金属纤维10份，粘合剂8份，放入球磨机内研磨1h，再将步骤一中的占37份的复合陶瓷球分为5等份加入，每次间隔45min，继续球磨10h，制成浆料；其中粘合剂为石蜡62份、聚乙烯20份、邻苯二甲酸二乙酯7份、硅烷11份；所用金属纤维为镍纤维与钼纤维按等比例的短纤维，直径为15μm；
步骤三、装模：将步骤二中的浆料填充在陶瓷模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1500℃，保温5h后取出，降温得到陶瓷。
实施例3
一种纳米稀土氧化物合金陶瓷的制备方法，首先制备纳米稀土陶瓷球：
步骤一、（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为45min，得到Ce(C2O4)3·10H2O，分别用水和乙醇清洗四次；
（2）稀土陶瓷粉球：按重量份数将35份的Ce(C2O4)3·10H2O、62份的陶瓷粉分别在160℃下干燥5h，放入球磨机内研磨11h，将两种粉末混匀后，加入3份石蜡后进行造粒，造粒所得稀土陶瓷粉球粒径为50mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在400℃下预烧结，保持3h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：陶瓷粉成分为碳化硅75份、氧化铝23.3份、氧化铁1.2份、氧化镁0.3份、氧化钛0.2份，将上述成分放入球磨机内研磨12h，混合均匀后过目筛选，陶瓷粉粒度为500目；按重量分数，原陶瓷粉50份，铜纤维18份，粘合剂12份，放入球磨机内研磨1h，再将步骤一中的占20份的复合陶瓷球分为6等份加入，每次间隔60min，继续球磨12h，制成浆料；其中粘合剂为石蜡65份、聚乙烯24份、邻苯二甲酸二乙酯8份、硅烷3份；所用铜纤维为短纤维，直径为25μm；混料过程中加入浆料总量6%的白云石作为致孔剂；
步骤三、装模：将步骤二中的浆料填充在陶瓷模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1643℃，保温6h后取出，降温得到纳米稀土氧化物合金陶瓷。

Claims (8)

1.一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：具体步骤为：
步骤一、纳米稀土陶瓷球的制备：
（1）稀土前体：按重量份数，将一份Ce(NO3)3·6H2O和三份H2C2O4·2H2O在研磨机上研磨，研磨时间为30~45min，得到Ce(C2O4)3·10H2O，之后分别用水和乙醇淋洗多次；
（2）稀土陶瓷粉球：按重量份数将32~35份的Ce(C2O4)3·10H2O、57~62份的陶瓷粉分别在120~160℃下干燥3~5h，放入球磨机内研磨9~11h，将两种粉末混匀后，加入3~11份胶黏剂后进行造粒，造粒所得稀土陶瓷粉球粒径为1~50mm；
（3）预烧结：将造粒所得稀土陶瓷粉球送入烧结炉中，在360~400℃下预烧结，保持2~3h，退火，得到纳米稀土氧化物复合的陶瓷球；
步骤二、混料：按重量分数，原陶瓷粉40～50份，金属纤维5~18份，粘合剂6~12份，放入球磨机内研磨1h，再将步骤一中的复合陶瓷球20～49份分为若干等份加入，继续球磨9~12h，制成浆料；
步骤三、装模：将步骤二中的浆料填充在模具中，挤压成型，脱模成胚体；
步骤四、烧结：制成的胚体在干燥室中干燥，在烧结炉中烧结，烧结温度为1382~1643℃，保温4~6h后取出，降温得到陶瓷基体。
2.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述步骤一中的胶黏剂为石蜡、亚硫酸纸浆废液中的一种或多种。
3.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述陶瓷粉成分为碳化硅62~75份、氧化铝23~34份、氧化铁1.2~2份、氧化镁0.3~1.6份、氧化钛0.2~0.9份，将上述成分放入球磨机内研磨8~12h，混合均匀后过目筛选，陶瓷粉粒度为100~500目。
4.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：步骤二中所述金属纤维成分为铜纤维、铝纤维、镍纤维、铁铬铝合金纤维、钼纤维、锰纤维、高温合金纤维的一种或多种。
5.如权利要求4所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述金属纤维为短纤维，纤维直径为1~25μm。
6.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述粘合剂为热塑性粘结剂，成分包括石蜡59~65份、聚乙烯18~24份、邻苯二甲酸二乙酯6~8份、硅烷3~17份。
7.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述步骤二中复合陶瓷球的添加分为3~6次添加，每次间隔30~60min。
8.如权利要求1所述的一种纳米稀土氧化物合金陶瓷的制备方法，其特征在于：所述混料过程中加入煤粉、石灰石、白云石中的一种或多种。
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