CN111848175A - 湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺 - Google Patents

湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺 Download PDF

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CN111848175A
CN111848175A CN202010558775.6A CN202010558775A CN111848175A CN 111848175 A CN111848175 A CN 111848175A CN 202010558775 A CN202010558775 A CN 202010558775A CN 111848175 A CN111848175 A CN 111848175A
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王鹏
周立娟
孟凡涛
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Shandong University of Technology
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Abstract

本发明提供一种湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于采用以下步骤：1）先将固化剂和增塑剂加入有机溶剂中搅拌溶解，再分别加入纤维独石前驱体胞体和纤维独石前驱体界面层的陶瓷粉料、搅拌均匀，形成两种不同组分的喷丝料浆，在机械压力下，通过共挤出喷丝头喷入盛满水的凝胶槽中，凝固成型，即得具有界面层的纤维独石前驱体；2）温压成型；3）真空脱脂；4）热压烧结，即得弱界面纤维独石硼化铪陶瓷，其断裂韧性可达9MPa·m1/2以上。本发明湿纺共挤出法成型纤维独石前驱体简化工艺，有利于机械排布，所得的纤维独石硼化铪超高温陶瓷，达到微观结构的精确控制，断裂方式为非脆性断裂，性能优良。

Description

湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺
技术领域
本发明提供一种湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，属于超高温陶瓷的制备技术领域。
背景技术
硼化铪作为一种优良的特种陶瓷材料，具有陶瓷和金属的双重特性，因为具有高熔点（3250℃），高硬度和优良的导电性，导热等性能，是一种性能优异的超高温陶瓷材料。但硼化铪陶瓷断裂韧性较低，韧值仅为4～5 MPa•m1/2，限制了其在苛刻作业环境下的应用，如超声速飞行器鼻锥和前沿、超燃冲压发动机热端部件等。因此，为了保证使用过程中的可靠性和安全性，必须改善硼化铪陶瓷的脆性问题，从而提高其耐热冲击性能。受自然界中贝壳、竹子的微观组织结构的启发，在脆性陶瓷材料中加入耐高温软质材料，设计和制备仿生层状和纤维独石状复合物以提高陶瓷的韧性。
对于仿生纤维独石复合材料的研究。清华大学通过泥料挤出法制备出Si3N4纤维独石前驱体，纤维独石前驱体的直径为1mm，然后，浸涂BN悬浮液，制备出Si3N4/BN纤维独石陶瓷，其弯曲强度为700MPa，断裂韧性为23.9MPa·m1/2。美国密苏里大学以乙烯-丙烯酸乙酯为结合剂，高温矿物油为增塑剂，120℃共挤出泥料制备出具有界面层结构的纤维独石前驱体，然后定向排布，经800℃裂解后，1900℃、32MPa下热压烧结制备出纤维独石ZrB2复合材料，胞体组成为ZrB2-30vol.%SiC，界面层组成为石墨-15vol%ZrB2，纤维独石ZrB2复合材料弯强度为375MPa，临界热震温差△Tc为1400℃。
传统的纤维独石前驱体成型工艺为泥料挤出成型，即干纺法成型，生坯经过陈腐、真空练泥使其具有一定可塑性，然后通过挤出机喷丝头挤出成型，喷丝头的大小决定了纤维独石前驱体的直径大小，喷丝头直径越小所受到的阻力越大，也就是说，小的喷丝头需要更大的挤出压力，挤出成型制备小于1mm的纤维独石前驱体非常困难，因此，研究人员在原有挤出成型工艺基础上进行了改进，通过将泥料预热到120℃，提高泥料的流动性，使其挤出成型更细的纤维独石前驱体，但没有改变泥料流动性差这一本质属性，喷丝头直径越小，挤出压力越大，挤出成型越困难，纤维独石前驱体挤出后，由于溶剂的挥发迅速固化，纤维独石前驱体韧性差，呈细棒状，连续性差，因此，制备高韧性纤维独石陶瓷，必须开发新型的纤维独石前驱体的成型工艺。
另外，传统的纤维独石前驱体胞体界面层成型为浸渍涂覆，浸渍涂覆的界面层厚度不均，使得纤维独石陶瓷的微观结构不能精确控制；并且反复浸渍也使纤维独石前驱体容易断裂，浸渍涂覆后的纤维独石前驱体胞体，变硬变脆，材料性能大大降低。
发明内容
本发明的目的是为了解决现有硼化铪超高温陶瓷韧性差、纤维独石前驱体成型困难的问题，而提供一种湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺。其技术方案为：
一种湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于采用以下步骤：
1）采用湿纺共挤出法制备具有界面层的纤维独石前驱体：先将固化剂和增塑剂加入有机溶剂中搅拌溶解，再分别加入纤维独石前驱体胞体的陶瓷粉料和纤维独石前驱体界面层的陶瓷粉料、搅拌均匀，形成两种不同组分的喷丝料浆，然后将喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为0～10℃，凝固成型后浸泡8～24h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为200～1000µm，界面层厚度为50～100µm，其中固化剂为聚醚砜，增塑剂为邻苯二甲酸二辛酯，有机溶剂为N-甲基吡咯烷酮和丙酮的混合物，N-甲基吡咯烷酮和丙酮质量比为(4～9): 1；
2）温压成型：根据热压烧结用石墨模具大小裁切具有界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在60～100℃，20～50 MPa下，温压使其致密得到陶瓷生坯；
3）真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0.2～0.5℃/min，升温至600～700℃，保温0.5～1h；
4）热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为1900～2000℃，保温0.5～2h，压力为20～60 MPa，即得弱界面纤维独石硼化铪陶瓷。
所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，步骤1）中，制备纤维独石前驱体胞体的陶瓷粉料由硼化铪粉末和碳化硅粉末按质量百分比70～90%：10～30%混合而成。
所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，步骤1）中，制备纤维独石前驱体界面层的陶瓷粉料由片状氮化硼粉末和硼化铪粉末按质量百分比70～90%：10～30%混合而成。
所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，步骤1）中，以制备纤维独石前驱体胞体的陶瓷粉料重量为基础计算，按重量百分比称取固化剂10～20%、增塑剂1～4%和有机溶剂100～200%。
所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，步骤1）中，以制备纤维独石前驱体界面层的陶瓷粉料重量为基础计算，按重量百分比称取固化剂10～20%、增塑剂1～4%和有机溶剂200～500%。
本发明的工作原理是：提出湿纺共挤出法制备具有界面层的纤维独石前驱体的新工艺，先将固化剂和增塑剂加入有机溶剂中搅拌溶解，再分别加入纤维独石前驱体胞体和纤维独石前驱体界面层的陶瓷粉料、搅拌均匀，形成两种不同组分的喷丝料浆，再将两种不同的喷丝料浆在水面下，从共挤出喷丝头中压出，呈细流状，然后在盛满水的凝胶槽中固化成形，即得到具有界面层的纤维独石前驱体，界面层厚度均匀，其结构示意图如图1所示。纤维独石前驱体形貌有椭球体、菱形体、纺锤体、扁平体、圆柱体。通过调控固化剂、增塑剂、固液比、喷丝料浆粘度、挤出速度、凝固液温度等参数，进而实现纤维独石前驱体形貌的可控，提高纤维独石前驱体致密性，减少热压烧结时纤维独石材料胞体形貌的变形，制备出连续、超细、高韧、致密的圆柱状纤维独石前驱体。其中固液比通过有机溶剂和陶瓷粉料比控制；喷丝料浆粘度通过固化剂、增塑剂、有机溶剂、陶瓷粉料、搅拌时间控制；挤出速度通过机械压力控制；凝固速度通过凝胶槽水温控制。
通过具有界面层的纤维独石前驱体，制备的弱界面纤维独石硼化铪陶瓷，其结构示意图如图2所示，由纤维独石硼化铪陶瓷胞体和界面层组成。试样断裂时，裂纹发生偏转和分叉，增加了裂纹的扩展路径，从而提高了材料的断裂韧性，断裂可达9MPa•m1/2以上。
本发明与现有技术相比，具有如下优点：
1、湿纺共挤出法成型具有界面层的纤维独石前驱体，制备出连续、超细、高韧、致密的具有界面层的纤维独石前驱体，胞体直径可达200µm，界面层厚度可达50µm；加入增塑剂邻苯二甲酸二辛酯，可以提高纤维独石前驱体的可塑性，直径更细，韧性更好，长度可达10米以上，180°弯曲不断裂。彻底解决了泥料挤出成型，泥料流动性差，纤维独石前驱体直径粗、韧性差、不连续的缺点；
2、喷丝料浆通过喷丝头在水面下成型，快速固化，纤维独石前驱体界面层厚度均匀。湿纺共挤出法成型纤维独石前驱体，改变了浸渍法涂覆涂层厚度不均，降低纤维独石前驱体韧性的缺点，简化工艺，达到纤维独石硼化铪陶瓷微观结构的精确控制，微观结构的精确控制是纤维独石硼化铪陶瓷高韧性的关键因素；
3、有机溶剂为N-甲基吡咯烷酮和丙酮的混合物，N-甲基吡咯烷酮和丙酮质量比为(4～9): 1，使得固化剂聚醚砜溶解速度快、均匀，无大分子团聚物，得到的纤维独石前驱体粗细均匀；
4、凝胶槽水温为0～10℃，低温快速凝固，纤维独石前驱体不粘连；
5、在本发明制得的纤维独石超高温陶瓷中，胞体组成为硼化铪-碳化硅，界面层组成为片状氮化硼，断裂时，裂纹发生偏转和分叉，增加了裂纹的扩展路径，消耗更多断裂功，从而提高了材料的断裂韧性，断裂韧性可达9MPa•m1/2以上；
6、块体陶瓷为脆性断裂，而纤维独石硼化铪陶瓷为非脆性断裂，对裂纹损伤具有一定容忍能力的逐次断裂。
附图说明
图1是本发明所述具有界面层的纤维独石前驱体的结构示意图；
图2是本发明所述弱界面纤维独石硼化铪陶瓷结构示意图。
图中：1、具有界面层的纤维独石前驱体的胞体；2、具有界面层的纤维独石前驱体的界面层； 3、弱界面纤维独石硼化铪陶瓷胞体；4、弱界面纤维独石硼化铪陶瓷界面层。
具体实施方式
实施例1
1、制备纤维独石前驱体胞体喷丝料浆：先将10克聚醚砜和1克邻苯二甲酸二辛酯在80克N-甲基吡咯烷酮和20克丙酮中搅拌溶解，再加入纤维独石前驱体胞体的陶瓷粉料，纤维独石前驱体胞体的陶瓷粉料由70克硼化铪粉末和30克碳化硅粉末按质量百分比70%： 30%混合而成，搅拌均匀，制成纤维独石前驱体胞体喷丝料浆；
2、制备纤维独石前驱体界面层喷丝料浆：先将10克聚醚砜和1克邻苯二甲酸二辛酯在160克N-甲基吡咯烷酮和40克丙酮中搅拌溶解，再加入纤维独石前驱体界面层的陶瓷粉料，纤维独石前驱体界面层的陶瓷粉料由70克片状氮化硼粉末和30克硼化铪粉末按质量百分比70%：30%混合而成，搅拌均匀，制成纤维独石前驱体界面层喷丝料浆；
3、湿纺共挤出法制备具有界面层的纤维独石前驱体：将纤维独石前驱体胞体喷丝料浆和纤维独石前驱体界面层喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为0℃，凝固成型后浸泡8h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为1000µm，胞体界面层厚度为100µm；
4、温压成型：根据热压烧结用石墨模具大小裁切浸渍涂覆后的界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在60℃，20MPa下，温压使其致密得到陶瓷生坯；
5、真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0.2℃/min，升温至600℃，保温0.5h；
6、热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为1900℃，保温0.5h，压力为20MPa，即得弱界面纤维独石硼化铪陶瓷。
实施例2
1、制备纤维独石前驱体胞体喷丝料浆：先将20克聚醚砜和4克邻苯二甲酸二辛酯在180克N-甲基吡咯烷酮和20克丙酮中搅拌溶解，再加入纤维独石前驱体胞体的陶瓷粉料，纤维独石前驱体胞体的陶瓷粉料由90克硼化铪粉末和10克碳化硅粉末按质量百分比90%：10%混合而成，搅拌均匀，制成纤维独石前驱体胞体喷丝料浆；
2、制备纤维独石前驱体界面层喷丝料浆：先将20克聚醚砜和4克邻苯二甲酸二辛酯在450克N-甲基吡咯烷酮和50克丙酮中搅拌溶解，再加入纤维独石前驱体界面层的陶瓷粉料，纤维独石前驱体界面层的陶瓷粉料由90克片状氮化硼粉末和10克硼化铪粉末按质量百分比90%：10%混合而成，搅拌均匀，制成纤维独石前驱体界面层喷丝料浆；
3、湿纺共挤出法制备具有界面层的纤维独石前驱体：将纤维独石前驱体胞体喷丝料浆和纤维独石前驱体界面层喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为10℃，凝固成型后浸泡24h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为200µm，胞体界面层厚度为50µm；
4、温压成型：根据热压烧结用石墨模具大小裁切浸渍涂覆后的界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在100℃，50MPa下，温压使其致密得到陶瓷生坯；
5、真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0.5℃/min，升温至700℃，保温1h；
6、热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为2000℃，保温2h，压力为60MPa，即得弱界面纤维独石硼化铪陶瓷。
实施例3
1、制备纤维独石前驱体胞体喷丝料浆：先将15克聚醚砜和2克邻苯二甲酸二辛酯在125克N-甲基吡咯烷酮和25克丙酮中搅拌溶解，再加入纤维独石前驱体胞体的陶瓷粉料，纤维独石前驱体胞体的陶瓷粉料由80克硼化铪粉末和20克碳化硅粉末按质量百分比80%： 20%混合而成，搅拌均匀，制成纤维独石前驱体胞体喷丝料浆；
2、制备纤维独石前驱体界面层喷丝料浆：先将15克聚醚砜和2克邻苯二甲酸二辛酯在350克N-甲基吡咯烷酮和50克丙酮中搅拌溶解，再加入纤维独石前驱体界面层的陶瓷粉料，纤维独石前驱体界面层的陶瓷粉料由80克片状氮化硼粉末和20克硼化铪粉末按质量百分比80%：20%混合而成，搅拌均匀，制成纤维独石前驱体界面层喷丝料浆；
3、湿纺共挤出法制备具有界面层的纤维独石前驱体：将纤维独石前驱体胞体喷丝料浆和纤维独石前驱体界面层喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为5℃，凝固成型后浸泡12h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为800µm，胞体界面层厚度为60µm；
4、温压成型：根据热压烧结用石墨模具大小裁切浸渍涂覆后的界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在80℃，30MPa下，温压使其致密得到陶瓷生坯；
5、真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0. 4℃/min，升温至650℃，保温0.75h；
6、热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为1950℃，保温1h，压力为40MPa，即得弱界面纤维独石硼化铪陶瓷。
实施例4
1、制备纤维独石前驱体胞体喷丝料浆：先将18克聚醚砜和3克邻苯二甲酸二辛酯在105克N-甲基吡咯烷酮和15克丙酮中搅拌溶解，再加入纤维独石前驱体胞体的陶瓷粉料，纤维独石前驱体胞体的陶瓷粉料由85克硼化铪粉末和15克碳化硅粉末按质量百分比85%： 15%混合而成，搅拌均匀，制成纤维独石前驱体胞体喷丝料浆；
2、制备纤维独石前驱体界面层喷丝料浆：先将18克聚醚砜和3克邻苯二甲酸二辛酯在250克N-甲基吡咯烷酮和50克丙酮中搅拌溶解，再加入纤维独石前驱体界面层的陶瓷粉料，纤维独石前驱体界面层的陶瓷粉料由85克片状氮化硼粉末和15克硼化铪粉末按质量百分比85%：15%混合而成，搅拌均匀，制成纤维独石前驱体界面层喷丝料浆；
3、湿纺共挤出法制备具有界面层的纤维独石前驱体：将纤维独石前驱体胞体喷丝料浆和纤维独石前驱体界面层喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为2℃，凝固成型后浸泡10h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为700µm，胞体界面层厚度为80µm；
4、温压成型：根据热压烧结用石墨模具大小裁切浸渍涂覆后的界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在70℃，40MPa下，温压使其致密得到陶瓷生坯；
5、真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0.3℃/min，升温至650℃，保温0.5h；
6、热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为1950℃，保温1h，压力为30MPa，即得弱界面纤维独石硼化铪陶瓷。

Claims (5)

1.一种湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于采用以下步骤：
1）采用湿纺共挤出法制备具有界面层的纤维独石前驱体：先将固化剂和增塑剂加入有机溶剂中搅拌溶解，再分别加入纤维独石前驱体胞体的陶瓷粉料和纤维独石前驱体界面层的陶瓷粉料、搅拌均匀，形成两种不同组分的喷丝料浆，然后将喷丝料浆分别倒入不同的注射器中，在机械压力下, 将喷丝料浆通过共挤出喷丝头喷入盛满水的凝胶槽中，喷丝头在水面下，凝胶槽水温为0～10℃，凝固成型后浸泡8～24h，即得具有界面层的纤维独石前驱体，具有界面层的纤维独石前驱体由纤维独石前驱体胞体和界面层组成，纤维独石前驱体胞体直径为200～1000µm，界面层厚度为50～100µm，其中固化剂为聚醚砜，增塑剂为邻苯二甲酸二辛酯，有机溶剂为N-甲基吡咯烷酮和丙酮的混合物，N-甲基吡咯烷酮和丙酮质量比为(4～9 ): 1；
2）温压成型：根据热压烧结用石墨模具大小裁切具有界面层的纤维独石前驱体，在石墨模具中进行平行排布，再在60～100℃，20～50MPa下，温压使其致密得到陶瓷生坯；
3）真空脱脂：将陶瓷生坯连同石墨模具放入真空脱脂炉中，真空脱脂，升温速度为0.2～0.5℃/min，升温至600～700℃，保温0.5～1h；
4）热压烧结：脱脂后，在氩气气氛下热压烧结，烧结温度为1900～2000℃，保温0.5～2h，压力为20～60MPa，即得弱界面纤维独石硼化铪陶瓷。
2.如权利要求1所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于：步骤1）中，制备纤维独石前驱体胞体的陶瓷粉料由硼化铪粉末和碳化硅粉末按质量百分比70～90%：10～30%混合而成。
3.如权利要求1所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于：步骤1）中，制备纤维独石前驱体界面层的陶瓷粉料由片状氮化硼粉末和硼化铪粉末按质量百分比70～90%：10～30%混合而成。
4.如权利要求1所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于：步骤1）中，以制备纤维独石前驱体胞体的陶瓷粉料重量为基础计算，按重量百分比称取固化剂10～20%、增塑剂1～4%和有机溶剂100～200%。
5.如权利要求1所述的湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺，其特征在于：步骤1）中，以制备纤维独石前驱体界面层的陶瓷粉料重量为基础计算，按重量百分比称取固化剂10～20%、增塑剂1～4%和有机溶剂200～500%。
CN202010558775.6A 2020-06-18 2020-06-18 湿纺共挤出法制备弱界面纤维独石硼化铪陶瓷的工艺 Withdrawn CN111848175A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113860881A (zh) * 2021-10-12 2021-12-31 中山大学 相转化法制备纤维独石结构氮化硅陶瓷材料

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