CN113233902A - 一种自定型氮化硅泡沫陶瓷的制备方法 - Google Patents
一种自定型氮化硅泡沫陶瓷的制备方法 Download PDFInfo
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Abstract
一种自定型氮化硅泡沫陶瓷的制备方法,属于先进陶瓷技术领域。1)将无机连续长纤维制备为短切纤维,利用制毡设备获得一定形状、厚度及纤维体积分数的纤维毡;2)将硅粉与氮化硅的混合微粉放入溶剂,添加表面活性剂和粘结剂,球磨后得含硅浆料;3)将纤维毡置于含硅浆料中,在压力作用下使含硅浆料充分浸渍纤维毡,取出,干燥,得挂浆产物;4)将挂浆产物置于氮气或氮氢混合气氛,在高温下使硅粉发生氮化生成氮化硅,并在氮化硅的持续转化过程中实现反应烧结,得纤维增强的氮化硅泡沫陶瓷;5)将氮化硅泡沫陶瓷置于含硅浆料中,重复步骤3)和4),得不同孔隙尺寸和孔隙率的自定型氮化硅泡沫陶瓷。微孔和微裂纹少,结温度低、收缩率小。
Description
技术领域
本发明属于先进陶瓷技术领域,尤其是涉及一种自定型氮化硅泡沫陶瓷的制备方法。
背景技术
氮化硅泡沫陶瓷是一种具有低密度、低热导率、低热膨胀系数、高温稳定性好、抗热震性能好等优点的多孔陶瓷材料,主要应用于热防护、熔融金属过滤、分离膜和催化剂载体等领域。目前氮化硅泡沫陶瓷的制备方法有有机模板法、发泡法等。有机模板法是将多孔有机材料(多为聚氨酯海绵)作为模板,使氮化硅陶瓷浆料黏附于有机多孔膜板之上,而后通过热处理去除模板,陶瓷浆料固化烧结后保留模板形状,形成泡沫陶瓷。如高晓菊等人选用具有贯通气孔的软质聚氨酯海绵作为骨架,以α相氮化硅粉为原料,结合有机前驱体浸渍法,在1600~1800℃的条件下制备氮化硅泡沫陶瓷【高晓菊,金颖,李金富,等.烧结工艺对Si3N4泡沫陶瓷性能的影响[J].硅酸盐通报,2010,29(5):1055-1059】;发泡剂法是指将氮化硅陶瓷粉体与有机发泡材料混合,利用有机物在高温下分解产生气体的原理实现发泡和造孔,空隙结构在高温下陶瓷粉体烧结后保留,进而获得泡沫陶瓷。如专利申请号为CN201810432259.1的中国专利(周新贵,氮化硅泡沫陶瓷增强铝基复合材料及其制备方法和应用),以α相氮化硅为原料,以蛋白粉为发泡剂制备的氮化硅泡沫陶瓷增强铝基复合材料,其开孔率为49%~80%,孔隙尺寸为50~500μm。采用有机模板法制备泡沫陶瓷的过程中需要将模板脱除,在此过程中有机物分解和气体排出过程会在陶瓷骨架上留下孔洞和裂纹,从而破坏泡沫陶瓷的结构均匀性,降低力学性能;采用发泡法制备氮化硅泡沫陶瓷工艺较复杂,且难以精确控制最终制品的形状和微观结构,导致力学性能较差。
发明内容
本发明的目的在于提供陶瓷中的微孔和微裂纹少,结温度低、收缩率小,可在纤维的增强作用下,显著提高泡沫陶瓷的力学性能的一种自定型氮化硅泡沫陶瓷的制备方法。
本发明包括以下步骤:
1)将无机连续长纤维制备为短切纤维,而后利用制毡设备获得具有一定形状、厚度及纤维体积分数的纤维毡;
2)将纯硅粉或硅粉与氮化硅的混合微粉放入溶剂,并在溶剂中添加表面活性剂和粘结剂,经球磨后获得含硅浆料;
3)将纤维毡置于含硅浆料中,在压力作用下使含硅浆料充分浸渍纤维毡,而后将带有浆料的纤维毡从含硅浆料中取出,充分干燥后,获得挂浆产物;
4)将挂浆产物置于氮气或氮氢混合气氛中,在高温下使硅粉发生氮化生成氮化硅,并在氮化硅的持续转化过程中实现反应烧结,获得纤维增强的氮化硅泡沫陶瓷;
5)将氮化硅泡沫陶瓷置于含硅浆料中,重复步骤3)和4),进而获得不同孔隙尺寸和孔隙率的自定型氮化硅泡沫陶瓷。
在步骤1)中,所述无机连续长纤维包括碳纤维、玻璃纤维、氧化铝纤维、碳化硅纤维、氮化硅纤维等无机耐高温连续纤维中的一种;所述纤维毡中纤维的体积分数为1vol.%~10vol.%,所述纤维毡的厚度可为0.3~30mm,可根据实际需要进行调整;所述一定形状可通过裁剪将固定厚度的纤维毡形成特性形状。
在步骤2)中,所述硅粉及氮化硅粉的粒度可为0.5~10μm,优选0.5~2μm,以保证浆料的颗粒能够畅通无阻的进入纤维毡;所述氮化硅粉用于缓解硅粉在后续氮化过程的放热,氮化硅粉的加入量为硅粉总质量的0~80wt.%;所述表面活性剂可选自离子型表面活性剂(PEI等)或非离子型表面活性剂(NP-10等),表面活性剂的添加量可为0.5wt.%~3wt.%;所述粘结剂可为聚乙烯醇(PVA)或聚乙烯醇缩丁醛(PVB),粘结剂的含量可为1wt.%~6wt.%;所述溶剂可采用水或乙醇;所述含硅浆料的固含量可为20wt.%~50wt.%。
在步骤3)中,所述挂浆的压力可为0.5~10MPa,保压时间为5~30min;所述干燥的温度可为60~80℃,干燥的时间可为5~20h;所述挂浆产物可通过调整浆料固含量来调整挂浆量,进而获得不同孔隙率的挂浆产物。
在步骤4)中,所述氮化的反应温度可为1300~1400℃,升温速率为1~5℃/min,反应时间为1~30h;当使用氮氢混合气氛时,氢气的浓度为1%~5%,氢气的存在会抑制硅粉的进一步氧化,进而对氮化反应起到促进作用。
在步骤5)中,所述自定型氮化硅泡沫陶瓷的气孔率可为55%~80%,孔隙尺寸可为100~1000μm,抗弯强度可为15~60MPa,压缩强度可为5~20MPa。
本发明的有益效果是:
(1)以无机纤维毡作为定型骨架,不需要脱除骨架,避免传统发泡法和模板法中直接发泡和脱除模板过程引入气孔和裂纹等结构缺陷的问题,所得泡沫陶瓷的结构更均匀;
(2)以无机纤维毡为增强体,能够利用纤维的强韧化作用提高氮化硅泡沫陶瓷的强度与韧性,显著改善泡沫陶瓷的高温性能及稳定性;
(3)利用反应烧结制备氮化硅泡沫陶瓷,制备温度低于传统方法,且所得氮化硅陶瓷纯度高,烧结收缩率低,结构稳定性好。
具体实施方式
以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
本发明实施例包括以下步骤:
1)将无机连续长纤维制备为短切纤维,而后利用制毡设备获得具有一定形状、厚度及纤维体积分数的纤维毡A。其中,无机纤维包括碳纤维、玻璃纤维、氧化铝纤维、碳化硅纤维、氮化硅纤维等;毡的厚度一般为0.3~30mm之间,且可根据实际需要进行调整;纤维体积分数为1vol.%~10vol.%;通过裁剪,可将固定厚度的纤维毡形成特性形状。
2)将纯硅粉或硅粉与氮化硅的混合微粉放入溶剂,并在溶剂中添加表面活性剂和粘结剂,经球磨后获得含硅浆料B。其中,硅粉及氮化硅粉的粒度应为0.5μm~10μm,最优为0.5~2μm,以保证浆料的颗粒能够畅通无阻的进入纤维毡;加入氮化硅粉的目的是缓解硅粉在后续氮化过程的放热,加入氮化硅粉的量为硅粉总质量的0~80wt.%;加入的表面活性剂可为离子型表面活性剂(PEI等)或非离子型表面活性剂(NP-10等),添加量为0.5wt.%~3wt.%;粘结剂为聚乙烯醇(PVA)或聚乙烯醇缩丁醛(PVB),含量为1wt.%~6wt.%;溶剂为水或乙醇;浆料的固含量为20wt.%~50wt.%之间。
3)将纤维毡A置于含硅浆料B中,在压力作用下使含硅浆料B充分浸渍A,而后将带有浆料的纤维毡A从含硅浆料B中取出,充分干燥后,获得挂浆产物C。其中挂浆的压力为0.5~10MPa;保压时间为5~30min;干燥温度为60~80℃,干燥时间为5~20h;通过调整浆料固含量来调整挂浆量,进而获得不同孔隙率的挂浆产物C;
4)将挂浆产物C置于氮气或氮氢混合气氛中,在高温下使硅粉发生氮化生成氮化硅,并在氮化硅的持续转化过程中实现反应烧结,获得纤维增强的氮化硅泡沫陶瓷D;其中,氮化反应温度为1300~1400℃,升温速率为1~5℃/min,反应时间为1~30h;当使用氮/氢混合气时,氢气的浓度为1%~5%。氢气的存在会抑制硅粉的进一步氧化,进而对氮化反应起到促进作用。
5)将纤维增强的氮化硅泡沫陶D置于含硅浆料B中,重复步骤(3)到步骤(4),进而获得不同孔隙尺寸和孔隙率的氮化硅泡沫陶瓷E。
以下给出具体实施例。
实施例1:
(1)将3K的碳纤维T300制备为短切纤维,而后利用制毡设备获得厚度为5mm、纤维体积分数为8%的碳纤维毡A;
(2)将平均粒度1.5μm的高纯硅粉(99.99%)按照固含量20wt.%的比例放入酒精中,并在溶剂中添加1wt.%的PEI和2wt.%的PVB,经高能球磨2h后,获得硅浆料B;
(3)将碳纤维毡A置于硅浆料B中,在3MPa压力作用下使硅浆料B充分浸渍碳纤维毡A,而后将带有浆料的碳纤维毡A从硅浆料B中取出,而后在60℃干燥10h,获得挂浆产物C;
(4)将挂浆产物C置于96%N2-4%H2的流动的氮氢混合气氛中,气体流速为1L/min,以2℃/min升温速率升至1360℃,而后保温20h,在高温下使硅粉发生氮化生成氮化硅,并在氮化硅的持续转化过程中实现反应烧结,获得纤维增强的氮化硅泡沫陶瓷D;
测试表明,该试样的氮化率为98.5%,所得碳纤维增强氮化硅泡沫陶瓷的气孔率为75.2%,平均孔隙尺寸为900μm,抗弯强度为17.5MPa,压缩强度为5.4MPa。
实施例2:
(1)同实施例1中的步骤(1);
(2)将平均粒度1.5μm的高纯硅粉(99.99%)按照固含量35wt.%的比例放入酒精中,并在溶剂中添加1wt.%的PEI和3wt.%的PVB,经高能球磨2h后,获得硅浆料B;
(3)同实施例1中的步骤(3);
(4)同实施例1中的步骤(4);
测试表明,该试样的平均氮化率为97.8%,所得碳纤维增强氮化硅泡沫陶瓷的气孔率为63.5%,平均孔隙尺寸为450μm,抗弯强度为38.7MPa,压缩强度为9.4MPa。
实施例3:
(1)同实施例2中的步骤(1);
(2)同实施例2中的步骤(2);
(3)同实施例2中的步骤(3);
(4)同实施例2中的步骤(4);
(5)将D置于B中,重复步骤(3)到步骤(4),重复次数为1次,获得氮化硅泡沫陶瓷E;
测试表明,该试样的平均氮化率为96.5%,所得碳纤维增强氮化硅泡沫陶瓷的气孔率为57.5%,平均孔隙尺寸为380μm,抗弯强度为43.8MPa,压缩强度为11.3MPa。
实施例4:
(1)将0.5K的碳化硅纤维制备为短切纤维,而后利用制毡设备获得厚度为3mm、纤维体积分数为5%的碳纤维毡A;
(2)同实施例1中的步骤(2);
(3)同实施例1中的步骤(3);
(4)同实施例1中的步骤(4);
本发明利用短切无机纤维毡作为定型骨架,采用含硅浆料浸渍挂浆,再结合反应烧结技术制备出纤维增强氮化硅泡沫陶瓷。该法免去直接发泡或脱除模板的过程,因此陶瓷中的微孔和微裂纹少;此外,该法烧结温度低、收缩率小,可在纤维的增强作用下,显著提高泡沫陶瓷的力学性能。测试表明,该试样的平均氮化率为99.5%,所得碳化硅纤维增强氮化硅泡沫陶瓷的气孔率为78.5%,平均孔隙尺寸为980μm,抗弯强度为17.2MPa,压缩强度为6.7MPa。
上述实施例仅为本发明的较佳实施例,不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等,均应仍归属于本发明的专利涵盖范围之内。
Claims (10)
1.一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于包括以下步骤:
1)将无机连续长纤维制备为短切纤维,而后利用制毡设备获得具有一定形状、厚度及纤维体积分数的纤维毡;
2)将纯硅粉或硅粉与氮化硅的混合微粉放入溶剂,并在溶剂中添加表面活性剂和粘结剂,经球磨后获得含硅浆料;
3)将纤维毡置于含硅浆料中,在压力作用下使含硅浆料充分浸渍纤维毡,而后将带有浆料的纤维毡从含硅浆料中取出,充分干燥后,获得挂浆产物;
4)将挂浆产物置于氮气或氮氢混合气氛中,在高温下使硅粉发生氮化生成氮化硅,并在氮化硅的持续转化过程中实现反应烧结,获得纤维增强的氮化硅泡沫陶瓷;
5)将氮化硅泡沫陶瓷置于含硅浆料中,重复步骤3)和4),进而获得不同孔隙尺寸和孔隙率的自定型氮化硅泡沫陶瓷。
2.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤1)中,所述无机连续长纤维包括碳纤维、玻璃纤维、氧化铝纤维、碳化硅纤维、氮化硅纤维中的一种。
3.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤1)中,所述纤维毡中纤维的体积分数为1vol.%~10vol.%,所述纤维毡的厚度为0.3~30mm,所述一定形状是通过裁剪将固定厚度的纤维毡形成特性形状。
4.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤2)中,所述硅粉及氮化硅粉的粒度为0.5~10μm,优选0.5~2μm,以保证浆料的颗粒能够畅通无阻的进入纤维毡;所述氮化硅粉用于缓解硅粉在后续氮化过程的放热,氮化硅粉的加入量为硅粉总质量的0~80wt.%。
5.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤2)中,所述表面活性剂可选自离子型表面活性剂或非离子型表面活性剂,表面活性剂的添加量为0.5wt.%~3wt.%。
6.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤2)中,所述粘结剂可为聚乙烯醇或聚乙烯醇缩丁醛,粘结剂的含量为1wt.%~6wt.%;所述溶剂可采用水或乙醇;所述含硅浆料的固含量可为20wt.%~50wt.%。
7.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤3)中,所述挂浆的压力为0.5~10MPa,保压时间为5~30min;所述干燥的温度为60~80℃,干燥的时间为5~20h。
8.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤3)中,所述挂浆产物通过调整浆料固含量来调整挂浆量,进而获得不同孔隙率的挂浆产物。
9.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤4)中,所述氮化的反应温度为1300~1400℃,升温速率为1~5℃/min,反应时间为1~30h;当使用氮氢混合气氛时,氢气的浓度为1%~5%。
10.如权利要求1所述一种自定型氮化硅泡沫陶瓷的制备方法,其特征在于在步骤5)中,所述自定型氮化硅泡沫陶瓷的气孔率为55%~80%,孔隙尺寸为100~1000μm,抗弯强度为15~60MPa,压缩强度为5~20MPa。
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CN114773066A (zh) * | 2022-05-19 | 2022-07-22 | 醴陵市凯德特种陶瓷有限公司 | 一种增韧碳化硅陶瓷窑具平板制造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130167374A1 (en) * | 2011-12-29 | 2013-07-04 | General Electric Company | Process of producing ceramic matrix composites and ceramic matrix composites formed thereby |
CN103224405A (zh) * | 2012-11-08 | 2013-07-31 | 航天特种材料及工艺技术研究所 | 一种制备氮化硅泡沫陶瓷的方法 |
CN104876637A (zh) * | 2015-05-25 | 2015-09-02 | 中航复合材料有限责任公司 | 一种纤维增强纯无机阻燃泡沫复合材料及其制备方法 |
CN105503200A (zh) * | 2016-01-12 | 2016-04-20 | 中钢集团洛阳耐火材料研究院有限公司 | 一种氮化硅纤维过滤材料的制备方法 |
CN106588022A (zh) * | 2016-12-18 | 2017-04-26 | 吴德炳 | 一种利用模板法制备碳化硅泡沫陶瓷的工艺 |
CN106699227A (zh) * | 2017-01-13 | 2017-05-24 | 武汉科技大学 | 一种纳米线自增强多孔氮化硅陶瓷及其制备方法 |
-
2021
- 2021-06-01 CN CN202110608742.2A patent/CN113233902B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130167374A1 (en) * | 2011-12-29 | 2013-07-04 | General Electric Company | Process of producing ceramic matrix composites and ceramic matrix composites formed thereby |
CN103224405A (zh) * | 2012-11-08 | 2013-07-31 | 航天特种材料及工艺技术研究所 | 一种制备氮化硅泡沫陶瓷的方法 |
CN104876637A (zh) * | 2015-05-25 | 2015-09-02 | 中航复合材料有限责任公司 | 一种纤维增强纯无机阻燃泡沫复合材料及其制备方法 |
CN105503200A (zh) * | 2016-01-12 | 2016-04-20 | 中钢集团洛阳耐火材料研究院有限公司 | 一种氮化硅纤维过滤材料的制备方法 |
CN106588022A (zh) * | 2016-12-18 | 2017-04-26 | 吴德炳 | 一种利用模板法制备碳化硅泡沫陶瓷的工艺 |
CN106699227A (zh) * | 2017-01-13 | 2017-05-24 | 武汉科技大学 | 一种纳米线自增强多孔氮化硅陶瓷及其制备方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114773066A (zh) * | 2022-05-19 | 2022-07-22 | 醴陵市凯德特种陶瓷有限公司 | 一种增韧碳化硅陶瓷窑具平板制造方法 |
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