CN109160815A - 一种耐高温碳化硅-碳化钽泡沫陶瓷的制备方法 - Google Patents
一种耐高温碳化硅-碳化钽泡沫陶瓷的制备方法 Download PDFInfo
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Abstract
本发明公开了一种以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅‑碳化钽泡沫陶瓷的制备方法。该方法以可热固化特性聚碳硅烷和五氧化二钽粉体和聚氨酯三种物料充分研磨混匀后,加入模具中,施加一定压力,排出粉体内部的气体得到预制体,再对该泡沫预制体进行热处理,实现聚碳硅烷的自身交联固化,最后在惰性气氛中进行高温烧结,得到碳化硅‑碳化钽泡沫陶瓷。该制备方法简单,工艺流程少,成本低,避免了溶剂的使用,有利于环境保护,制备出的泡沫陶瓷线收缩率小于10%,体积密度小1.0g/cm3,开气孔率介于60%~80%之间,抗折强度达2.0~2.3MPa,可以在1500℃长时间使用。
Description
技术领域
本发明属于陶瓷泡沫技术领域,具体涉及一种以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备方法。
背景技术
传统的碳化硅泡沫陶瓷制备工艺复杂,其主要以碳化硅粉体与分散剂、烧结助剂等共混制成浆料,再与有机泡沫模版浸渍得到预制体,预制体经干燥、排除有机物等工序烧成得到碳化硅泡沫陶瓷。(梁汉琴,姚秀敏,黄政仁,刘学建.碳化硅陶瓷液相烧结时的液相生成过程[J].机械工程材料,2015,39(02):34-37.;)梁汉琴研究了SiC泡沫陶瓷烧结机理:SiC泡沫陶瓷主要是玻璃相对SiC颗粒的包覆、连接作用及新相莫来石生成。而烧结助剂的引入也不利于制备SiC物质量比相近的碳化硅泡沫陶瓷。过高的烧结温度会生成大的方石英相,从而在以后的冷却过程中出现微裂纹,影响材料的强度。
近几十年来,聚合物先驱体,如聚碳硅烷、聚硅氮烷等,作为制备陶瓷材料的前驱体近年来引起人们极大的兴趣,在专利CN 105272266 A中,李思维仅用聚碳硅烷作为泡沫陶瓷的先驱体,与溶剂二甲苯配制浆料,以处理过的聚氨酯泡沫为模板,制得挂浆产物,先经过鼓风烘箱中预氧化处理,再经高温炉中烧结得碳化硅泡沫。其制备的泡沫陶瓷中含有8wt%以上的氧,氧以SiOxCy相存在。其在600℃以上,SiOxCy发生剧烈的分解反应,如下式所示。
SiOxCy→SiC(s)+CO(g)+SiO(g)
以上分解反应导致泡沫陶瓷骨架的强度损伤,限制碳化硅泡沫陶瓷的使用温度在600℃以下。
以聚二甲基硅烷裂解制备的聚碳硅烷为先驱体,制备碳化硅陶瓷方法中,在惰性气氛中,热解得到的碳化硅陶瓷中富余碳,碳在高温有氧条件下不稳定,如下式所示。
C(s)+O2(g)→CO(g)
以上氧化反应导致泡沫陶瓷的损伤,限制碳化硅泡沫陶瓷的使用条件。
结合碳化硅泡沫陶瓷的应用环境,有可能在高温空气气氛中,减少碳化硅陶瓷中富余碳,是提高其使用性能的关键所在。
现有技术总结:以碳化硅颗粒与粘结剂和溶剂配成浆料,以泡沫结构的有机物为模板,浸渍后,在1300℃左右进行烧结,但是缺点明显:浆料的均匀性很难保证,制备过程有溶剂的使用,不利于环境保护;以有机硅烷化合物聚碳硅烷为先驱体,先驱体法制备泡沫陶瓷,这一部分研究不多见,技术尚待开发。
发明内容
针对上述技术现状,本发明旨在提供一种以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备方法。
以可热固化聚碳硅烷和五氧化二钽粉体和聚氨酯三种物料为原料。进过充分研磨混匀后,粉体加入模具中,对模具施加一定压力,排出粉体内部的气体得到预制体,再对该预制体进行热处理,实现聚碳硅烷的自身交联固化,最后在惰性气氛中进行烧结,得到碳化硅-碳化钽泡沫陶瓷。该制备方法简单,工艺流程少,成本低,避免了溶剂的使用,此工艺制备流程简单,避免了溶剂的使用,保护环境,原料来源充足,具有很大的实际应用价值和环境保护价值。
为了实现上述技术目的,本发明在一定温度下,充分研磨可热固化聚碳硅烷和五氧化二钽粉体和聚氨酯三种物料,得到混合均匀的粉体。再粉体加入模具中,对模具施加一定压力,排出粉体内部的气体得到预制体,在惰性气氛中,对该预制体进行热处理,在此过程中,五氧化二钽粉体和聚氨酯不发生任何化学反应和融化、气化等,完成聚碳硅烷的自身交联固化,得到泡沫预制体。最后在惰性气氛中对泡沫预制体进行烧结,在此过程中,不发生发泡和严重的体积收缩现象,聚氨酯完全分解,质量无残留,留下了体积,造成了孔隙,可热固化聚碳硅烷转变为碳化硅陶瓷和富余的碳,此碳与五氧化二钽发生碳热还原反应得到碳化钽陶瓷,最终得到耐高温碳化硅-碳化钽泡沫陶瓷。此泡沫陶瓷结构致密,可以在1500℃长时间应用。
即,本发明的技术方案为:一种可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备方法,包括如下步骤:
(1)一定温度下,充分研磨可热固化聚碳硅烷、五氧化二钽和聚氨酯,得到粉体;
(2)粉体加入模具,施加压力,排出粉体内部的气体,得到泡沫预制体,在惰性气氛中对泡沫预制体进行热处理,实现热固化聚碳硅烷的自身交联固化和溶剂的脱除;
(3)在惰性气氛中对泡沫预制体进行热处理,实现热固化聚碳硅烷的自身交联固化;
(4)在惰性气氛中,对交联固化的泡沫预制体进行烧结,得到碳化硅-碳化钽泡沫陶瓷;
进一步,所述步骤(1)作为一种实现方式,具体过程如下:所述步骤(1)中,具体过程如下:
以可热固化聚碳硅烷、五氧化二钽和聚氨酯在球磨罐中高速低温研磨混匀,得到均匀混合的粉体。聚氨酯在本发明中起到制造孔隙的作用。可热固化聚碳硅烷、五氧化二钽和聚氨酯为1:0.6:0.3~0.6。
球磨罐的转速为900~100r/min,时间5~20min;
作为优选,所述的研磨温度不高于60℃;
作为优选,所述的热固化聚碳硅烷仅含有硅、碳、氢三种元素;
作为优选,可热固化聚碳硅烷是:聚碳硅烷(由聚二甲基硅烷高温裂解重排合成,软化点220~230℃)与烯基硅烷通过硅氢加成反应得到。热固化聚碳硅烷中乙烯基的量占聚碳硅烷的硅氢键含量的20~50%。
进一步,所述步骤(2)作为一种实现方式,具体过程如下:将混合好的粉体加入模具中,施加压力,排出粉体内部的气体后,得到预制体;本发明的泡沫陶瓷的孔隙由于聚氨酯在高温下完全分解无残留造成的,通过调节聚氨酯与热固化聚碳硅烷的比例可以调节泡沫陶瓷的孔隙率和孔隙的尺寸。排出预制体内部空气,减少可以干扰孔隙率控制的因素,泡沫陶瓷的孔隙率和孔隙的尺寸仅由聚氨酯的添加量来控制。排出空气可以很好的达到控制孔隙的目的。不排出空气,空气中的氧气会与热固化聚碳硅烷反应,引入氧元素,对最终泡沫陶瓷的纯度有不利影响;孔隙不能很好地控制。
作为优选,所述的模具内部形状不限,可以是管状,棒状,片状或者其他几何形貌;
作为优选,所述的压力为0.1~10MPa;
进一步,所述步骤(3)中作为一种实现方式,具体过程如下:将预制体在惰性气氛中,以1℃/min~5℃/min的升温速率升温到200℃~300℃,保温1.5h~15h。
进一步,所述步骤(4)中,作为一种实现方式,具体过程如下:具体过程如下:将步骤(3)处理后的预制体在惰性气氛下,以1℃/min~30℃/min的升温速率,加热至1400℃~1800℃,保温0.5h~5h小时,然后冷却至室温,得到泡沫陶瓷。
作为优选,制备出的泡沫陶瓷线收缩率小于20%,体积密度小1.0g/cm3,开气孔率介于60%~80%之间,抗折强度达2.0~2.3Mpa。
作为优选,制备出的SiC泡沫陶瓷可以在1500℃长时间使用。
本发明以热固化聚碳硅烷(PVCS)、五氧化二钽和聚氨酯为原料,如图1所示,为了实现上述技术目的,本发明在一定温度下,充分研磨可热固化聚碳硅烷、五氧化二钽粉体和聚氨酯三种物料,得到混合均匀的粉体。再粉体加入模具中,对模具施加一定压力,排出粉体内部的气体得到预制体,在惰性气氛中,对该预制体进行热处理,在此过程中,五氧化二钽粉体和聚氨酯不发生任何化学反应和融化、气化等,完成聚碳硅烷的自身交联固化,得到泡沫预制体。最后在惰性气氛中对泡沫预制体进行烧结,在此过程中,不发生发泡和严重的体积收缩现象聚氨酯完全分解,质量无残留,留下了体积,造成了孔隙,可热固化聚碳硅烷转变为碳化硅陶瓷和富余的碳,此碳与五氧化二钽发生碳热还原反应得到碳化钽陶瓷,最终得到耐高温碳化硅-碳化钽泡沫陶瓷。此泡沫陶瓷结构致密。1500℃,空气气氛中处理1h后,强度保留率在90%以上。
本发明和现有技术相比的优点:
1、本发明原料易得并且制备简单:聚碳硅烷商业产品,热固化聚碳硅烷制备过程简单,易得,五氧化钽,商业产品,易得,聚氨酯,商业产品,易得;
2、本发明制备过程中,不使用溶剂,有利于环境保护;
3、本发明制备过程简单,可制备多种形貌的泡沫陶瓷结构件;
4、本发明泡沫陶瓷孔隙度可控制;
5、本发明以热固化聚碳硅烷制备碳化硅陶瓷,陶瓷产物中含有碳化硅和碳,碳不利于陶瓷的抗氧化性,以五氧化钽和碳在高温下的碳热还原形成碳化钽,把碳转变为耐超高温的碳化钽,变“废”为“宝”,最终得到碳化硅和碳化钽的复相陶瓷,提高了陶瓷泡沫的耐温性能;
6、本发明制备得到的泡沫陶瓷强度高,耐温性能优良。
附图说明
图1是本发明一种可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备流程示意图;
图2是本发明聚氨酯与泡沫陶瓷孔隙率;
表1实施例在空气中处理前后的强度;
具体实施方式
下面结合实施例对本发明作进一步详细描述,需要指出的是,以下所述实施例旨在便于对本发明的理解,而对其不起任何限定作用。
实施例1:
以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备过程如下:
(一)研磨原料
质量比,PVCS:Ta2O5:聚氨酯为1:0.6:0.3,30℃下,惰性气氛中,充分混合研以上三种物料,得到混合均匀的粉体。
(二)塑型
粉体加入模具中,内部形貌为圆盘形状,施加0.3Mpa压力,排出粉体内部的气体,得到泡沫预制体。
(三)热处理有机泡沫预制体
将有机泡沫预制体放入炉中,抽真空置换高纯氮气三次后,将有机泡沫在惰性气氛中,以3℃/min的升温速率升温到220℃,保温3h。
(四)热解烧成制备碳化硅-碳化钽泡沫陶瓷
在氩气气氛中,将步骤(三)处理后的预制体以1℃/min的升温速率,加热至1600℃,保温4h小时,然后冷却至室温,得到黑色光亮泡沫陶瓷。体积密度0.7g/cm3,开气孔率60%,抗折强度达2.3MPa。
将上述制得的碳化硅泡沫陶瓷在空气气氛中1500℃处理1h后;强度保留率为96%。
实施例2:
以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备过程如下:
(一)研磨原料
质量比,PVCS:Ta2O5:聚氨酯为1:0.6:0.4,30℃下,惰性气氛中,充分混合研以上三种物料,得到混合均匀的粉体。
(二)塑型
粉体加入模具中,内部形貌为正方形形状,施加0.5Mpa压力,排出粉体内部的气体,得到泡沫预制体。
(三)热处理有机泡沫预制体
将有机泡沫预制体放入炉中,抽真空置换高纯氮气三次后,将有机泡沫在惰性气氛中,以2℃/min的升温速率升温到220℃,保温6h。
(四)热解制备碳化硅-碳化钽泡沫陶瓷
在氩气气氛中,将步骤(三)处理后的预制体以3℃/min的升温速率,加热至1650℃,保温3h小时,然后冷却至室温,得到黑色光亮泡沫陶瓷。体积密度0.6g/cm3,开气孔率70%,抗折强度达2.1MPa。
将上述制得的碳化硅泡沫陶瓷在空气气氛中1500℃处理1h后;强度保留率为95%。
实施例3:
以可热固化聚碳硅烷和五氧化二钽制备耐高温碳化硅-碳化钽泡沫陶瓷的制备过程如下:
(一)研磨原料
质量比,PVCS:Ta2O5:聚氨酯为1:0.6:0.6,30℃下,惰性气氛中,充分混合研以上三种物料,得到混合均匀的粉体。
(二))塑型
粉体加入模具中,内部形貌为圆柱形状,施加0.3Mpa压力,排出粉体内部的气体,得到泡沫预制体。
(三)热处理有机泡沫预制体
将有机泡沫预制体放入炉中,抽真空置换高纯氮气三次后,将有机泡沫在惰性气氛中,以2℃/min的升温速率升温到220℃,保温6h。
(五)热解制备碳化硅-碳化钽泡沫陶瓷
在氩气气氛中,将步骤(三)处理后的预制体以5℃/min的升温速率,加热至1700℃,保温6h小时,然后冷却至室温,得到黑色光亮泡沫陶瓷。体积密度0.5g/cm3,开气孔率81%,抗折强度达2.0MPa。
将上述制得的碳化硅泡沫陶瓷在空气气氛中1500℃处理1h后;强度保留率为95%。
表1实施例在空气中处理前后强度。
Claims (9)
1.一种以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:包括如下步骤:
(1)将可热固化聚碳硅烷、二氧化铪和聚氨酯研磨混匀,得到均匀混合的粉体;
(2)将混合好的粉体加入模具中,施加压力,排出粉体内部的气体,得到预制体;
(3)在惰性气氛中对预制体进行热处理,实现聚碳硅烷的自身交联固;
(4)在惰性气氛中对交联固化后的预制体进行高温烧结,得到碳化硅‐碳化铪泡沫陶瓷。
2.如权利要求1所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅-碳化铪泡沫陶瓷的制备方法,其特征是:所述的可热固化聚碳硅烷是:聚碳硅烷和乙烯基硅烷通过硅氢加成反应得到;所述聚碳硅烷由聚二甲基硅烷高温裂解重排合成的;
作为优选,所述的热固化聚碳硅烷仅含有硅、碳、氢三种元素。热固化聚碳硅烷中乙烯基的量占聚碳硅烷的硅氢键含量的20~50%;
作为优选,,聚碳硅烷分子量1700~1900左右,软化点220~240℃,由聚二甲基硅烷高温裂解重排合成。
3.如权利要求1所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:所述步骤(1)中,具体过程如下:
以可热固化聚碳硅烷、二氧化铪和聚氨酯在球磨罐中高速低温研磨混匀,得到均匀混合的粉体;可热固化聚碳硅烷、二氧化铪和聚氨酯三者的质量1:0.6:0.3~0.6;
作为优选,所述的研磨温度不高于60℃。
4.如权利要求1所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅-碳化铪泡沫陶瓷的制备方法,其特征是:所述步骤(2)中,具体过程如下:将混合好的粉体加入模具中,施加压力,排出粉体内部的气体后,得到预制体;
作为优选,所述的模具内部形状不限,可以是管状,棒状,片状或者其他几何形貌;作为优选,所述的压力为0.1~10MPa。
5.如权利要求1所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:所述步骤(3)中,具体过程如下:
将预制体在惰性气氛中,以1℃/min~5℃/min的升温速率升温到200℃~300℃,保温1.5h~15h。
6.如权利要求1所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:所述步骤(4)中,具体过程如下:
将步骤(3)处理后的预制体在惰性气氛下,以1℃/min~30℃/min的升温速率,加热至1400℃~1800℃,保温0.5h~5h小时,然后冷却至室温,得到泡沫陶瓷;二氧化铪和碳在高温下的碳热还原形成碳化铪:
C(s)+HfO2(s)→CO(g)+fC(s)。
7.如权利要求6所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:所述步骤(4)制备出的泡沫陶瓷线收缩率小于12%,体积密度小1.0g/cm3,开气孔率介于60%~80%之间,抗折强度达2.0~2.3Mpa。
8.如权利要求6所述的以可热固化聚碳硅烷和二氧化铪制备耐高温碳化硅‐碳化铪泡沫陶瓷的制备方法,其特征是:制备出的泡沫陶瓷可以在1500℃长时间使用。
9.一种耐高温碳化硅‐碳化铪泡沫陶瓷,其使用上述权利要求1‐8所述制备方法制得。
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