CN111253170A - 一种制备硅化石墨结构材料的方法 - Google Patents

一种制备硅化石墨结构材料的方法 Download PDF

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CN111253170A
CN111253170A CN202010177141.6A CN202010177141A CN111253170A CN 111253170 A CN111253170 A CN 111253170A CN 202010177141 A CN202010177141 A CN 202010177141A CN 111253170 A CN111253170 A CN 111253170A
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graphite
preparing
transition metal
fiber yarns
oxide
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薛喜利
董伟
薛明虎
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Jiangsu Jiaming Carbon New Material Co ltd
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Jiangsu Jiaming Carbon New Material Co ltd
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Abstract

本发明公开了一种制备硅化石墨结构材料的方法，通过氧化石墨水热的方法，将纳米级别的过渡金属元素均匀加入到还原氧化石墨的内部，通过过渡金属元素作为催化剂时，分布更加均匀，有利于硅化石墨的均匀形成，同时纳米级材料的高活性及过渡金属的高催化性能，使得反应温度和反应时间大大降低；反应过程不需要加真空保护也不需要加压大大降低了反应能耗。

Description

一种制备硅化石墨结构材料的方法
技术领域
本发明涉及一种制备硅化石墨结构材料的方法。
背景技术
硅化石墨是一种由碳化硅、游离硅以及石墨多种组分组成的新型复合材料，也称为石墨和碳化硅复合材料、浸硅石墨）。硅化石墨材料既保留了石墨材料优秀的自润滑性能、良好的导电、导热性能以及高抗热震性能，又具有碳化硅材料高硬度、耐磨性、抗氧化和耐化学腐蚀等优点，充分体现了两种材料的协同互补性。是理想的结构材料，适于在高载荷、高温环境或大温度冲击等苛刻场合。制品广泛用于航空航天、军事装备、石油化工、太阳能等战略性新兴产业。
目前制造硅化石墨主要有下列几种方法：液硅渗透法、化学气相反应法、化学气相沉积法及反应烧结法。液硅渗透法系利用液态硅对碳素材料的润湿性，在高温下使液态硅渗透入多孔碳素基材而成。化学气相反应法及化学气相沉积法均系在高温反应炉内通过气体反应，在石墨基材表面生成碳化硅涂层。其本质的区别在于：气相沉积法所生成的碳化硅涂层，碳和硅元素均来源于外部导入的气体，而气相反应法只导入硅源，含硅气体在高温下与碳素基材本身发生反应而形成碳化硅涂层。反应烧结法即按常规的粉末冶金工艺将碳化硅粉末、碳素粉末及适量的粘结剂、活化剂混合、球磨、再经压制，然后与硅进行高温反应烧结而成。
但无论采用哪种方法都面临着能耗严重的现实问题，如温度为1800℃、压力30MPa时浸渍深度达20mm。并且随着厚度的增加，所需的温度或者压力也越高，能耗极其严重。并且高温过程中，硅以及石墨都易被氧化，而采用真空反应条件，对设备要求又极高。
发明内容
针对上述现有技术的不足之处，本发明解决的问题为：提供一种耗能低下的制备硅化石墨结构材料的方法。
为解决上述问题，本发明采取的技术方案如下：
一种制备硅化石墨结构材料的方法，步骤如下：
S1、制备氧化石墨：以石墨为原料，采用改性Hummers法制备氧化石墨；
S2、制备初料：以水为溶剂，配置氧化石墨溶液，向制得的氧化石墨溶液中加入可溶性过渡金属盐，搅拌均匀，超声处理4～12h，将混合好的氧化石墨和过渡金属盐溶液加入到水热反应釜中，温度为110～200℃，时间为5～24h，待冷却后过滤、烘干，得到还原氧化石墨和过渡金属氧化物复合材料的初料；
S3、制备原料：将步骤S2中获得的还原氧化石墨和过渡金属氧化物复合材料中加入石墨和硅源；进行球磨之后获得石墨、还原氧化石墨和过渡金属氧化物的复合材料的原料；
S4、制备粘结剂：将硅溶胶液体100份、瓜尔胶20至30份、聚阴离子纤维素15至25份、六方氮化硼5至8份、纳米氧化铝5至6份进行混合搅拌，得到粘结剂；并且将上述原料和粘结剂按照6:1的比例进行混合均匀搅拌；
S5、锁水：将亚麻纤维丝和竹纤维丝按照质量比为4:1～4:3进行混合加入水中，静置5至10min后，将亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中进行搅拌；
S6、成型烘干：将步骤S5的原料采用模具成型，模具压力为5kPa～5Mpa，然后在成型原料表面涂刷石墨涂层，模型烘干，将烘干模型包埋在针状焦中，然后置于马弗炉中温度为1200～1900℃，保温5～24h，冷却后取出，获得硅化石墨材料。
进一步，所述步骤S2中，配置氧化石墨时，采用去离子水，配置的溶液浓度为20～50 wt%；所述的过渡金属盐为Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn中一种或几种的氯化物、硝酸盐或者硫酸盐；可溶性过渡金属盐的添加量为氧化石墨溶液质量的5%～25%；还原氧化石墨和过渡金属氧化物复合材料的烘干温度为60～80℃。
进一步，所述步骤S3中，加入的石墨、硅源、还原氧化石墨和过渡金属氧化物的复合材料的质量比为0.5～10：0.5～10：1；球磨的球料比为10～20:1，转速为200~500 r/min，时间为30至40min。
进一步，所述步骤S4中硅溶胶液体的浓度为30至40％。
进一步，所述步骤S5中亚麻纤维丝和竹纤维丝均为短纤维丝，长度为0.8至1.2cm。
进一步，所述步骤S5中，亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中搅拌的时间为5至10min；搅拌转速为30至40r/min。
本发明的有益效果
1.本发明方法通过氧化石墨水热的方法，将纳米级别的过渡金属元素均匀加入到还原氧化石墨的内部，通过过渡金属元素作为催化剂时，分布更加均匀，有利于硅化石墨的均匀形成，同时纳米级材料的高活性及过渡金属的高催化性能，使得反应温度和反应时间大大降低；反应过程不需要加真空保护也不需要加压大大降低了反应能耗。
2.本发明在增设了锁水步骤，因为在步骤S4的粘结剂中加入了增加表面积的六方氮化硼以及纳米氧化铝，提高了粘结剂和原料的接触面积，但是粘结剂的锁水性能极大的削弱了，如此在原料与粘结剂进行充分搅拌时，使得粘结剂中的水分流失很快，进而使得整个原料更加容易硬化，进而使得步骤S6中的压模成型受阻、效率低下，而步骤S5中利用亚麻纤维丝和竹纤维丝的吸湿性能够将水分进行封锁于原料上，提高了原料的软化性能，如此使得后续步骤S6的压型能够高效顺利的进行。
3.本发明加入的亚麻纤维丝和竹纤维丝可以在原料中形成断断续续的网体结构，配合六面网体叠加晶体结构的六方氮化硼和多孔结构的纳米氧化铝，形成交错的网络体系，使得粘结剂与原料的粘结的更加稳固，提高了本发明的结构强度，所以本发明的亚麻纤维丝和竹纤维丝不仅仅能够提高整个糊料的锁水能力，而且增加了本发明的结构强度，同时利用亚麻纤维丝的韧性好的特点增加了本发明的韧性。
具体实施方式
下面对本发明内容作进一步详细说明。
实施1
一种制备硅化石墨结构材料的方法，步骤如下：
S1、制备氧化石墨：以石墨为原料，采用改性Hummers法制备氧化石墨。
S2、制备初料：以水为溶剂，配置氧化石墨溶液，向制得的氧化石墨溶液中加入可溶性过渡金属盐，搅拌均匀，超声处理4h，将混合好的氧化石墨和过渡金属盐溶液加入到水热反应釜中，温度为110℃，时间为5h，待冷却后过滤、烘干，得到还原氧化石墨和过渡金属氧化物复合材料的初料；配置氧化石墨时，采用去离子水，配置的溶液浓度为20wt%；所述的过渡金属盐为Mn和Fe硝酸盐；可溶性过渡金属盐的添加量为氧化石墨溶液质量的5%；还原氧化石墨和过渡金属氧化物复合材料的烘干温度为60℃。
S3、制备原料：将步骤S2中获得的还原氧化石墨和过渡金属氧化物复合材料中加入石墨和硅源；进行球磨之后获得石墨、还原氧化石墨和过渡金属氧化物的复合材料的原料；加入的石墨、硅源、还原氧化石墨和过渡金属氧化物的复合材料的质量比为0.5：2：1；球磨的球料比为10:1，转速为200 r/min，时间为30 min。
S4、制备粘结剂：将硅溶胶液体100份、瓜尔胶20份、聚阴离子纤维素15份、六方氮化硼5份、纳米氧化铝5份进行混合搅拌，得到粘结剂；并且将上述原料和粘结剂按照6:1的比例进行混合均匀搅拌；硅溶胶液体的浓度为30％。
S5、锁水：将亚麻纤维丝和竹纤维丝按照质量比为4:1进行混合加入水中，静置5min后，将亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中进行搅拌；亚麻纤维丝和竹纤维丝均为短纤维丝，长度为0.8cm。亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中搅拌的时间为5 min；搅拌转速为30 r/min。
S6、成型烘干：将步骤S5的原料采用模具成型，模具压力为3Mpa，然后在成型原料表面涂刷石墨涂层，模型烘干，将烘干模型包埋在针状焦中，然后置于马弗炉中温度为1200℃，保温5h，冷却后取出，获得硅化石墨材料。
实施2
一种制备硅化石墨结构材料的方法，步骤如下：
S1、制备氧化石墨：以石墨为原料，采用改性Hummers法制备氧化石墨；
S2、制备初料：以水为溶剂，配置氧化石墨溶液，向制得的氧化石墨溶液中加入可溶性过渡金属盐，搅拌均匀，超声处理8h，将混合好的氧化石墨和过渡金属盐溶液加入到水热反应釜中，温度为160℃，时间为15h，待冷却后过滤、烘干，得到还原氧化石墨和过渡金属氧化物复合材料的初料；配置氧化石墨时，采用去离子水，配置的溶液浓度为35 wt%；所述的过渡金属盐为Cu和Zn的氯化物；可溶性过渡金属盐的添加量为氧化石墨溶液质量的15%；还原氧化石墨和过渡金属氧化物复合材料的烘干温度为70℃。
S3、制备原料：将步骤S2中获得的还原氧化石墨和过渡金属氧化物复合材料中加入石墨和硅源；进行球磨之后获得石墨、还原氧化石墨和过渡金属氧化物的复合材料的原料；加入的石墨、硅源、还原氧化石墨和过渡金属氧化物的复合材料的质量比为5：8：1；球磨的球料比为15:1，转速为300 r/min，时间为35min。
S4、制备粘结剂：将硅溶胶液体100份、瓜尔胶25份、聚阴离子纤维素20份、六方氮化硼6份、纳米氧化铝5.5份进行混合搅拌，得到粘结剂；并且将上述原料和粘结剂按照6:1的比例进行混合均匀搅拌；硅溶胶液体的浓度为35％。
S5、锁水：将亚麻纤维丝和竹纤维丝按照质量比为4:2进行混合加入水中，静置8min后，将亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中进行搅拌；亚麻纤维丝和竹纤维丝均为短纤维丝，长度为1.0cm。亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中搅拌的时间为8min；搅拌转速为35r/min。
S6、成型烘干：将步骤S5的原料采用模具成型，模具压力为4Mpa，然后在成型原料表面涂刷石墨涂层，模型烘干，将烘干模型包埋在针状焦中，然后置于马弗炉中温度为1600℃，保温15h，冷却后取出，获得硅化石墨材料。
实施例3
一种制备硅化石墨结构材料的方法，步骤如下：
S1、制备氧化石墨：以石墨为原料，采用改性Hummers法制备氧化石墨；
S2、制备初料：以水为溶剂，配置氧化石墨溶液，向制得的氧化石墨溶液中加入可溶性过渡金属盐，搅拌均匀，超声处理12h，将混合好的氧化石墨和过渡金属盐溶液加入到水热反应釜中，温度为200℃，时间为24h，待冷却后过滤、烘干，得到还原氧化石墨和过渡金属氧化物复合材料的初料；配置氧化石墨时，采用去离子水，配置的溶液浓度为50 wt%；所述的过渡金属盐为Sc和Cu硝酸盐；可溶性过渡金属盐的添加量为氧化石墨溶液质量的25%；还原氧化石墨和过渡金属氧化物复合材料的烘干温度为80℃。
S3、制备原料：将步骤S2中获得的还原氧化石墨和过渡金属氧化物复合材料中加入石墨和硅源；进行球磨之后获得石墨、还原氧化石墨和过渡金属氧化物的复合材料的原料；加入的石墨、硅源、还原氧化石墨和过渡金属氧化物的复合材料的质量比为10：5：1；球磨的球料比为20:1，转速为500 r/min，时间为40min。
S4、制备粘结剂：将硅溶胶液体100份、瓜尔胶30份、聚阴离子纤维素25份、六方氮化硼8份、纳米氧化铝6份进行混合搅拌，得到粘结剂；并且将上述原料和粘结剂按照6:1的比例进行混合均匀搅拌；硅溶胶液体的浓度为40％。
S5、锁水：将亚麻纤维丝和竹纤维丝按照质量比为4:3进行混合加入水中，静置10min后，将亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中进行搅拌；亚麻纤维丝和竹纤维丝均为短纤维丝，长度为1.2cm。亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中搅拌的时间为10min；搅拌转速为40r/min。
S6、成型烘干：将步骤S5的原料采用模具成型，模具压力为5Mpa，然后在成型原料表面涂刷石墨涂层，模型烘干，将烘干模型包埋在针状焦中，然后置于马弗炉中温度为1900℃，保温24h，冷却后取出，获得硅化石墨材料。
本发明的结构强度和韧性测试如下表。
实施例 抗压强度MPa 抗折强度MPa
实施例1 55.3 8.8
实施例2 58.5 9.2
实施例3 56.1 8.9
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

1.一种制备硅化石墨结构材料的方法，其特征在于，步骤如下：
S1、制备氧化石墨：以石墨为原料，采用改性Hummers法制备氧化石墨；
S2、制备初料：以水为溶剂，配置氧化石墨溶液，向制得的氧化石墨溶液中加入可溶性过渡金属盐，搅拌均匀，超声处理4～12h，将混合好的氧化石墨和过渡金属盐溶液加入到水热反应釜中，温度为110～200℃，时间为5～24h，待冷却后过滤、烘干，得到还原氧化石墨和过渡金属氧化物复合材料的初料；
S3、制备原料：将步骤S2中获得的还原氧化石墨和过渡金属氧化物复合材料中加入石墨和硅源；进行球磨之后获得石墨、还原氧化石墨和过渡金属氧化物的复合材料的原料；
S4、制备粘结剂：将硅溶胶液体100份、瓜尔胶20至30份、聚阴离子纤维素15至25份、六方氮化硼5至8份、纳米氧化铝5至6份进行混合搅拌，得到粘结剂；并且将上述原料和粘结剂按照6:1的比例进行混合均匀搅拌；
S5、锁水：将亚麻纤维丝和竹纤维丝按照质量比为4:1～4:3进行混合加入水中，静置5至10min后，将亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中进行搅拌；
S6、成型烘干：将步骤S5的原料采用模具成型，模具压力为5kPa～5Mpa，然后在成型原料表面涂刷石墨涂层，然后模型烘干，将烘干模型包埋在针状焦中，然后置于马弗炉中温度为1200～1900℃，保温5～24h，冷却后取出，获得硅化石墨材料。
2.根据权利要求1所述的制备硅化石墨结构材料的方法，其特征在于，所述步骤S2中，配置氧化石墨时，采用去离子水，配置的溶液浓度为20～50 wt%；所述的过渡金属盐为Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn中一种或几种的氯化物、硝酸盐或者硫酸盐；可溶性过渡金属盐的添加量为氧化石墨溶液质量的5%～25%；还原氧化石墨和过渡金属氧化物复合材料的烘干温度为60～80℃。
3.根据权利要求1所述的制备硅化石墨结构材料的方法，其特征在于，所述步骤S3中，加入的石墨、硅源、还原氧化石墨和过渡金属氧化物的复合材料的质量比为0.5～10：0.5～10：1；球磨的球料比为10～20:1，转速为200~500 r/min，时间为30至40min。
4.根据权利要求1所述的制备硅化石墨结构材料的方法，其特征在于，所述步骤S4中硅溶胶液体的浓度为30至40％。
5.根据权利要求1所述的制备硅化石墨结构材料的方法，其特征在于，所述步骤S5中亚麻纤维丝和竹纤维丝均为短纤维丝，长度为0.8至1.2cm。
6.根据权利要求1所述的制备硅化石墨结构材料的方法，其特征在于，所述步骤S5中，亚麻纤维丝和竹纤维丝取出后放入步骤S4中的原料中搅拌的时间为5至10min；搅拌转速为30至40r/min。
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