CN111118472B - 一种碳化硅膜连续碳纤维板的制备方法 - Google Patents

一种碳化硅膜连续碳纤维板的制备方法 Download PDF

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CN111118472B
CN111118472B CN202010014239.XA CN202010014239A CN111118472B CN 111118472 B CN111118472 B CN 111118472B CN 202010014239 A CN202010014239 A CN 202010014239A CN 111118472 B CN111118472 B CN 111118472B
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唐竹兴
田露
苏秋歌
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Abstract

一种碳化硅膜连续碳纤维板的制备方法,其特征在于,连续碳纤维板是在碳化硅膜连续碳纤维板镀膜机中通入工艺气体在被加热的碳纤维束表面连续沉积碳化硅形成碳化硅膜,随着碳化硅薄膜的增厚把相邻碳纤维束链接成一体形成碳化硅膜连续碳纤维板。本发明是采用碳化硅膜连续碳纤维板镀膜机直接加热碳纤维束,工艺气体高温裂解生成的碳化硅绝大部分沉积在碳纤维束的表面,极少部分沉积在隔热屏上,碳纤维束的间距、碳化硅膜连续碳纤维板和碳化硅膜的厚度可以随机任意选择,不但节省原材料、节能且生产效率高。

Description

一种碳化硅膜连续碳纤维板的制备方法
技术领域
本发明涉及一种碳纤维和陶瓷复合材料的制备方法,属于复合材料制备技术领域。
背景技术
碳纤维表面沉积碳化硅膜通常是将碳纤维放入沉积炉内间歇式制备,效率非常低,且碳纤维的长度和形态无法满足多样性的需要。另外,碳纤维在间歇式炉内为被动受热,大部分碳化硅沉积在温度较高的坩埚内壁上,耗能大,且事倍功半。另外,大型热工设备使用碳化硅陶瓷板、碳化硅陶瓷管、碳化硅陶瓷方梁等,其结构强度较低,急需高强度的碳纤维-陶瓷复合材料替代。
发明内容
本发明的目的在于提供一种能克服上述缺陷、实现低成本高效制备碳化硅膜连续碳纤维板的制备方法。其技术方案为:
连续碳纤维板是在碳化硅膜连续碳纤维板镀膜机中通入工艺气体在被加热的碳纤维束表面连续沉积碳化硅形成碳化硅膜,随着碳化硅薄膜的增厚把相邻碳纤维束链接成一体形成碳化硅膜连续碳纤维板,其中,碳化硅膜连续碳纤维板镀膜机是由碳纤维室(1)、气相沉积室(2)、混合气体室(3)、氮气室(4)、碳化硅膜连续碳纤维板载物平台(5)、碳纤维滚(6)、碳纤维板(7)、通道(8)、对棍石墨滚(9)、对棍石墨滚(10)、对棍石墨滚(11)、通道(12)、通道(13)、通道(14)、切刀(15)、气体入口(16)、排出口(17)、进口(18)、气相沉积室隔热屏(19)组成的;
碳化硅膜连续碳纤维板是由多股或多层碳纤维束并列紧凑排布,每股碳纤维束间距为0.5~100µm;
对棍石墨滚(9)和对棍石墨滚(10)分别与电源的两极相接,通电后将碳纤维板加热到900~1100℃,对棍石墨滚(9)、对棍石墨滚(10)和对棍石墨滚(11)的转速协调一致;
工艺气体为三氯甲基硅烷气、氢气和氩气的混合气体,三氯甲基硅烷气:氢气:氩气的摩尔比为1:6~10:8~12,流量控制在100~1200ml/min;
碳化硅膜连续碳纤维板中碳化硅膜的厚度是由工艺气体的摩尔比、碳纤维板(7)的温度和对棍石墨滚(9)对棍石墨滚(10)对棍石墨滚(11)的转速共同控制。
本发明与现有技术相比,其优点为:
1、本发明是采用碳化硅膜连续碳纤维板镀膜机,通入工艺气体在被加热的碳纤维束表面连续沉积碳化硅制成碳化硅膜连续碳纤维板,碳纤维束的间距、碳化硅膜连续碳纤维板和碳化硅膜的厚度可以随机任意选择,生产效率高;
2、由于本发明是直接加热碳纤维束,高温裂解生成的碳化硅绝大部分沉积在碳纤维束的表面,极少部分沉积在隔热屏上,不但节省原材料、节能且生产效率高;
3、本发明制备的碳化硅膜连续碳纤维板其显微结构特殊,可以应用于电子、机械、化工、生物、航空、航天等领域。
附图说明
图1是本发明所使用的碳化硅膜连续碳纤维板镀膜机结构示意图:
1.碳纤维室,2.气相沉积室,3.混合气体室,4.氮气室,5.碳化硅膜连续碳纤维板载物平台,6.碳纤维滚,7.碳纤维板,8.通道,9.对棍石墨滚,10.对棍石墨滚,11.对棍石墨滚,12.通道,13.通道,14.通道,15.切刀,16.气体入口,17.排出口,18.进口,19.气相沉积室隔热屏。
具体实施方式
碳化硅膜连续碳纤维板镀膜机是由5主要部分组成的,包括:碳纤维室1;气相沉积室2;混合气体室3;氮气室4;碳化硅膜连续碳纤维板载物平台5;
工作时,碳纤维滚6释放碳纤维板7,通过通道8进入气相沉积室2,经过两组接入电极的对棍石墨滚9和10被加热后在连续碳纤维束表面沉积碳化硅薄膜,随着碳化硅薄膜的增厚把相邻碳纤维束链接成一体形成碳化硅膜连续碳纤维板,对棍石墨滚(9)、对棍石墨滚(10)和对棍石墨滚(11)的转速协调一致,然后通过通道12进入混合气体室3,再通过通道13进入氮气室4,再通过通道14到碳化硅膜连续达碳纤维板载物平台5,经切刀15切割制成规定长度的碳化硅膜连续碳纤维板,并置于碳化硅膜连续碳纤维板载物平台5上收集包装;
气相沉积工作气体是通过气体入口16进入并充满气相沉积室2,在被加热的碳纤维板表面裂解生成碳化硅同时沉积在其表面,过剩气体通过通道12进入混合气体室3,然后从排出口17排出;
氮气从进口18进入氮气室4,从通道13和14排出,通过调整氮气压力阻止混合气体和空气分别从通道13和14进入氮气室4。
实施例1
T300碳纤维束的间距为5µm;
碳纤维板加热到1100℃;
三氯甲基硅烷气:氢气:氩气的摩尔比为1:6:8,流量控制在1200ml/min;
对棍石墨滚(9)(10)的转速的线速度为2cm/ min;
碳化硅膜厚度为9.1µm。
实施例2
T300碳纤维束的间距为3µm;
碳纤维板加热到1000℃;
三氯甲基硅烷气:氢气:氩气的摩尔比为1:8:10,流量控制在600ml/min;
对棍石墨滚(9)(10)的转速的线速度为0.6cm/ min;
碳化硅膜厚度为5.3µm。
实施例3
T300碳纤维束的间距为0.5µm;
碳纤维板加热到900℃;
三氯甲基硅烷气:氢气:氩气的摩尔比为1: 10: 12,流量控制在100ml/min;
对棍石墨滚(9)(10)的转速的线速度为0.8cm/ min;
碳化硅膜厚度为1.6µm。
实施例4
T300碳纤维束的间距为50µm;
碳纤维板加热到1100℃;
三氯甲基硅烷气:氢气:氩气的摩尔比为1:6:8,流量控制在1200ml/min;
对棍石墨滚(9)(10)的转速的线速度为0.1cm/ min;
碳化硅膜厚度为89µm。
实施例5
T300碳纤维束的间距为100µm;
碳纤维板加热到1000℃;
三氯甲基硅烷气:氢气:氩气的摩尔比为1:8:10,流量控制在600ml/min;
对棍石墨滚(9)(10)的转速的线速度为0.02cm/ min;
碳化硅膜厚度为145µm。

Claims (1)

1.一种碳化硅膜连续碳纤维板的制备方法,其特征在于,连续碳纤维板是在碳化硅膜连续碳纤维板镀膜机中通入工艺气体在被加热的碳纤维束表面连续沉积碳化硅形成碳化硅膜,随着碳化硅薄膜的增厚把相邻碳纤维束链接成一体形成碳化硅膜连续碳纤维板,其中,碳化硅膜连续碳纤维板镀膜机是由碳纤维室(1)、气相沉积室(2)、混合气体室(3)、氮气室(4)、碳化硅膜连续碳纤维板载物平台(5)、碳纤维滚(6)、碳纤维板(7)、通道(8)、对棍石墨滚(9)、对棍石墨滚(10)、对棍石墨滚(11)、通道(12)、通道(13)、通道(14)、切刀(15)、气体入口(16)、排出口(17)、进口(18)、气相沉积室隔热屏(19)组成的;
碳化硅膜连续碳纤维板是由多股或多层碳纤维束并列紧凑排布,每股碳纤维束间距为0.5~100µm;
对棍石墨滚(9)和对棍石墨滚(10)分别与电源的两极相接,通电后将碳纤维板加热到900~1100℃,对棍石墨滚(9)、对棍石墨滚(10)和对棍石墨滚(11)的转速协调一致;
工艺气体为三氯甲基硅烷气、氢气和氩气的混合气体,三氯甲基硅烷气:氢气:氩气的摩尔比为1:6~10:8~12,流量控制在100~1200ml/min;
碳化硅膜连续碳纤维板中碳化硅膜的厚度是由工艺气体的摩尔比、碳纤维板(7)的温度和对棍石墨滚(9)对棍石墨滚(10)对棍石墨滚(11)的转速共同控制。
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CN1047147C (zh) * 1995-09-29 1999-12-08 中国科学院山西煤炭化学研究所 一种涂层碳化硅纤维的生产方法及反应器
CN2447170Y (zh) * 2000-08-18 2001-09-12 捷安特(中国)有限公司 单向纤维片结构
CN1211499C (zh) * 2002-05-31 2005-07-20 陈新谋 碳纤维表面涂复碳化硅的工艺和装置
JP2006089331A (ja) * 2004-09-24 2006-04-06 Toray Ind Inc 炭素繊維基材の製造方法
CN105696139B (zh) * 2004-11-09 2019-04-16 得克萨斯大学体系董事会 纳米纤维纱线、带和板的制造和应用
JP5662077B2 (ja) * 2010-08-04 2015-01-28 イビデン株式会社 炭素繊維構造体の製造方法
CN102127753A (zh) * 2011-02-17 2011-07-20 中国航空工业集团公司北京航空材料研究院 一种直流电加热cvd法制备碳化硅纤维的装置和制备方法
CN104647561B (zh) * 2015-03-23 2016-08-24 南京林业大学 高表面密度纤维板及其制造方法
CN105503228A (zh) * 2015-12-25 2016-04-20 重庆乐乎科技有限公司 一种二维碳纤维碳化硅复合材料制备方法
CN105908491B (zh) * 2016-05-31 2018-04-10 哈尔滨工业大学 制备表面生长有碳纳米管的连续碳纤维的装置和方法
US10711344B2 (en) * 2017-08-29 2020-07-14 Taichi Metal Material Technology Co., Ltd. Process for making composite product by plating alloy film on carbon fiber core
WO2019087846A1 (ja) * 2017-10-30 2019-05-09 大阪ガスケミカル株式会社 表面層付き成形断熱材及びその製造方法
CN108409348B (zh) * 2018-03-19 2021-01-01 中南大学 一种纤维表面沉积界面层的设备及其方法
CN109485444A (zh) * 2018-12-25 2019-03-19 中国科学院长春光学精密机械与物理研究所 一种纤维增强碳化硅复合材料的制备方法
CN109987971A (zh) * 2019-05-09 2019-07-09 中国科学院金属研究所 碳纤维增强碳化硅陶瓷基复合材料表面中高温长时间抗氧化涂层及其制备方法
CN110078516A (zh) * 2019-05-14 2019-08-02 西北工业大学 高体积分数短纤维增强准各向同性SiCf/SiC复合材料的制备方法

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