CN115626834A - 一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法 - Google Patents
一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,涉及聚酰亚胺石墨膜技术领域,包括以下步骤:利用低温等离子体技术对碳化硅纤维和碳纤维进行表面修饰改性;将经表面修饰改性后的碳化硅纤维和碳纤维加入到有机溶剂中,超声分散,然后加入芳香族二胺,搅拌,得到纤维‑二胺溶液;在氮气保护下,将芳香族二酐分批加入到纤维‑二胺溶液中进行缩聚反应,得到纤维/聚酰胺酸树脂溶液;将纤维/聚酰胺酸树脂溶液凝胶化成膜,再经热亚胺化处理,得到纤维/聚酰亚胺薄膜,然后进行碳化处理、石墨化处理,即得聚酰亚胺石墨膜。本发明制得的聚酰亚胺石墨膜柔韧性增强,石墨化程度提高使得导热性能增强。
Description
技术领域
本发明涉及聚酰亚胺石墨膜技术领域,尤其涉及一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法。
背景技术
随着现代科技的不断发展,电子元器件逐渐向高频率、高集成和高能量密度发展,导致器件表面产生的热量集中,聚集的热量会影响电子元器件的寿命和系统的稳定性。传统导热系数较高的金属基散热材料,如铜、铝、金、银等已经难以满足现代电子器件高散热需求。与传统散热材料相比,金刚石、石墨和石墨烯等碳基材料,拥有更高的理论热导率,特别是石墨材料是解决上述散热难题的优选材料。人工石墨膜具有高度有序的石墨片层结构,聚酰亚胺由于其独特分子结构,被认为是制备石墨薄膜优良的碳源,是采用聚酰亚胺为前驱体,通过高温碳化和石墨化热处理获得,此方法制备工艺简单、成本较低。
然而,利用聚酰亚胺薄膜制备的石墨膜存在韧性差、石墨化程度低、导热率有待提高等问题,造成聚酰亚胺薄膜在制备石墨膜领域的局限性。因此对于提高聚酰亚胺石墨膜韧性和提高导热率的研究具有现实社会价值,受到了越来越多的科研工作者的关注。
发明内容
基于背景技术存在的技术问题,本发明提出了一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,制备的石墨膜具有高导热率和强柔韧性。
本发明提出的一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1、利用低温等离子体技术对碳化硅纤维和碳纤维进行表面修饰改性;
S2、将经表面修饰改性后的碳化硅纤维和碳纤维加入到有机溶剂中,超声分散,然后加入芳香族二胺,搅拌,得到纤维-二胺溶液;
S3、在氮气保护下,将芳香族二酐分批加入到纤维-二胺溶液中进行缩聚反应,得到纤维/聚酰胺酸树脂溶液;
S4、将纤维/聚酰胺酸树脂溶液凝胶化成膜,再经热亚胺化处理,得到纤维/聚酰亚胺薄膜;
S5、将纤维/聚酰亚胺薄膜依次进行碳化处理、石墨化处理,即得碳化硅纤维、碳纤维增强聚酰亚胺石墨膜。
在本发明中,经表面修饰改性后的碳化硅纤维和碳纤维表面的羟基和羧基能够与芳香族二胺形成氢键,得到纤维-二胺溶液。
优选地,碳化硅纤维和碳纤维的总量占芳香族二胺和芳香族二酐总质量的0.1~1%,碳化硅纤维和碳纤维的质量比为1~3:1~3。
优选地,S1中,在氧气气氛下对碳化硅纤维和碳纤维进行低温等离子体处理,处理功率100~300W、处理时间6~10min。
优选地,S2中,芳香族二胺为对苯二胺或4,4'-二氨基二苯醚中的一种或其组合,有机溶剂为N,N'-二甲基乙酰胺或N,N'-二甲基甲酰胺。
优选地,S3中,芳香族二酐为均苯四甲酸二酐或3,3',4,4'-联苯四甲酸二酐。
优选地,S3中,缩聚反应的反应温度为10~30℃,反应时间为4~8h;优选地,纤维/聚酰胺酸树脂溶液中的固含量为10~20%、旋转粘度为100000~150000mPa·s。
优选地,S4中,凝胶化成膜是将纤维/聚酰胺酸树脂溶液涂布在基板上,涂布厚度30~60μm,然后再热处理得到凝胶膜,热处理是以2~10℃/min升温至80~110℃,保温25~40min;优选地,热亚胺化处理的操作如下:以2~10℃/min升温至150~200℃保温30min,再以2~10℃/min升温至200~250℃保温30min进行亚胺化处理,然后以2~10℃/min升温至300~340℃保温30min进行退火处理。
在本发明中,上述S4中的凝胶化成膜也可以采用产业化生产的流延成膜法来实现。
优选地,S5中,碳化处理是将纤维/聚酰亚胺薄膜与石墨片叠放,置于碳化炉中,抽真空,以2~4℃/min升温至900~1200℃,保温2~3h。
在本发明中,产业化生产中,上述S5中的碳化处理可以直接将纤维/聚酰亚胺薄膜进行碳化处理,无需与石墨片叠放。
优选地,S5中,石墨化处理是将碳化后的纤维/聚酰亚胺薄膜置于石墨化炉中,在氩气气氛下,以1~10℃/min升温至2000℃,然后以1~5℃/min升温至3000℃,并分别在2000℃、2400℃、2800℃、3000℃下各保温0.5~1h,最后以10℃/min冷却至室温,得到聚酰亚胺石墨膜。
本发明还提出了采用上述方法制备的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜。
与现有技术相比,本发明的有益效果体现在以下几个方面:
1.本发明中利用低温等离子体对碳化硅纤维和碳纤维进行表面改性,引入大量羟基、羧基活性基团,提高了碳化硅纤维、碳纤维与聚酰亚胺的相容性,避免了因相容性导致石墨膜开裂的问题。
2.本发明中低温等离子体处理方法较常规的酸化氧化等方法,更能减少对碳化硅纤维和碳纤维材料表面的破坏,减少纤维材料表面SP3无定型杂化碳生成,对后续诱导聚酰亚胺石墨化起促进作用,提高石墨化程度,增强导热性能。
3.本发明中利用碳化硅纤维与碳纤维在聚酰亚胺基体中构造网状结构,在聚酰亚胺高温石墨化过程中,碳纤维起到支撑作用避免薄膜破裂,碳化硅纤维则热分解形成石墨烯提高石墨化过程中的取向性,共同作用抑止聚酰亚胺薄膜在碳化和石墨化过程中产生的内应力导致的微裂纹扩展,保证石墨膜的完整性和一体性,增强石墨膜的韧性;而直接采用片层石墨烯和碳纤维制备的聚酰亚胺薄膜表面褶皱,外观性能较差。
本发明制备的聚酰亚胺石墨膜柔韧性增强,导热率可达1600W/(m·K)以上。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
一种碳化硅纤维/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.094g、碳纤维0.094g,质量比为1:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维、碳纤维和二胺形成接枝物,得到碳化硅纤维/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维/碳纤维二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维与碳纤维含量为4‰的碳化硅纤维/碳纤维聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50μm,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
实施例2
一种碳化硅纤维/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.18g、碳纤维0.094g,质量比为2:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维、碳纤维和二胺形成接枝物,得到碳化硅纤维/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维/碳纤维二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维与碳纤维含量为6‰的碳化硅纤维/碳纤维聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50μm,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
实施例3
一种碳化硅纤维/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.094g、碳纤维0.18g,质量比为2:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维、碳纤维和二胺形成接枝物,得到碳化硅纤维/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维/碳纤维二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维与碳纤维含量为6‰的碳化硅纤维/碳纤维聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50um,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
实施例4
一种碳化硅纤维/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.18g、碳纤维0.18g,质量比为1:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维、碳纤维和二胺形成接枝物,得到碳化硅纤维/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维、碳纤维/二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维与碳纤维含量为8‰的碳化硅纤维/碳纤维聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50μm,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
实施例5
一种碳化硅纤维/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.047g、碳纤维0.047g,质量比为1:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维、碳纤维和二胺形成接枝物,得到碳化硅纤维/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维/碳纤维二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维与碳纤维含量为2‰的碳化硅纤维/碳纤维聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50μm,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
对比例1
一种碳化硅纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳化硅纤维0.18g,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性后碳化硅纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳化硅纤维和二胺形成接枝物,得到碳化硅纤维/二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳化硅纤维/二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳化硅纤维含量为4‰的碳化硅纤维/聚酰胺酸溶液;
S4:利用涂布机将碳化硅纤维/聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50um,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳化硅纤维/聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
对比例2
一种碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取碳纤维0.18g,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将表面改性碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,使碳纤维和二胺形成接枝物,得到碳纤维/二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到碳纤维/二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、碳纤维含量为4‰的碳纤维/聚酰胺酸溶液;
S4:利用涂布机将碳纤维/聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50um,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到碳纤维/聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
对比例3
一种聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:称取3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),置于205mL N,N’-二甲基乙酰胺(DMAc)中,室温机械搅拌2h;
S2:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)的聚酰胺酸溶液;
S3:利用涂布机将聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50um,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S4:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到聚酰亚胺膜。
S5:将薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S6:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2℃/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
对比例4
一种石墨烯/碳纤维增强聚酰亚胺石墨膜的制备方法,包括以下步骤:
S1:取石墨烯0.094g、碳纤维0.094g,质量比为1:1,在氧气气氛下进行低温等离子体处理,处理功率200W、处理时间8min;
S2:将石墨烯与碳纤维置于205mL N,N’-二甲基乙酰胺(DMAc)中,超声处理2h使其分散均匀;然后加入3.934g对苯二胺(36mmol)和17.0g 4,4’-二氨基二苯醚(85mmol),室温机械搅拌反应3h,得到石墨烯/碳纤维二胺溶液;
S3:在氮气保护下,将26.16g均苯四甲酸二酐(120mmol)分批加入到石墨烯/碳纤维二胺溶液,室温反应6h,得到固含量20%、粘度为120000(mPa·s)、石墨烯与碳纤维含量为4‰的石墨烯/碳纤维聚酰胺酸溶液;
S4:利用涂布机将石墨烯/碳纤维聚酰胺酸溶液涂覆在玻璃基板上,涂布厚度50um,置于烘箱中,以4℃/min的速率升温至100℃,保温30min,得到凝胶膜;
S5:将凝胶膜固定在针板上,置于烘箱中以4℃/min升温至180℃保温30min,再以4℃/min升温至240℃保温30min进行亚胺化处理;最后以4℃/min升温至340℃保温30min进行退火处理,即制备得到石墨烯/碳纤维聚酰亚胺复合膜。
S6:将复合薄膜裁成10cm×10cm的尺寸,放在两层石墨片中间,置于碳化炉中,抽真空:以3℃/min的升温速率升温至1200℃,保温3h,冷却到室温取出碳化膜;
S7:将碳化的样品置于石墨化炉中,整个石墨化过程保持氩气气氛,以2/min升到2000℃,然后以2℃/min升到3000℃,并分别在2000℃、2400℃、2800℃、3000℃时各保温1h,最后,以10℃/min的冷却速率降至室温,得到聚酰亚胺石墨膜。
对本发明实施例和对比例所得到的聚酰亚胺石墨膜进行性能测试,测试结果参照表1所示。
表1 聚酰亚胺石墨膜性能测试结果
由表1可以看出,实施例1-5与对比例3对比,碳化硅纤维与碳纤维的加入促进了聚酰亚胺的石墨化,石墨膜导热率与韧性均大幅度提高,这是因为碳化硅纤维在高温石墨化过程中表面热分解形成石墨烯,由于石墨烯的平面诱导作用,使聚酰亚胺分子在石墨烯表面产生显著的取向作用,从而改善其结构的规整性,对石墨化起到诱导作用;碳化硅与碳纤维在聚酰亚胺基体中构造的网状结构做为石墨膜的增强材料,抑止聚酰亚胺薄膜在碳化和石墨化过程中产生的内应力导致的微裂纹扩展,保证石墨膜的完整性和一体性,增强石墨膜的韧性。实施例1~5与对比例1~2对比,单独加入碳化硅纤维与碳纤维其中一种,所制备的石墨膜性能和外观与两者复配使用制备的石墨膜差距较大。实施例1~5与对比例4对比,碳化硅纤维与石墨烯均能促进聚酰亚胺的石墨化,石墨膜导热率大幅度提高,但碳化硅纤维与碳纤维制备的石墨膜韧性与膜外观性能更佳。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,包括以下步骤:
S1、利用低温等离子体技术对碳化硅纤维和碳纤维进行表面修饰改性;
S2、将经表面修饰改性后的碳化硅纤维和碳纤维加入到有机溶剂中,超声分散,然后加入芳香族二胺,搅拌,得到纤维-二胺溶液;
S3、在氮气保护下,将芳香族二酐分批加入到纤维-二胺溶液中进行缩聚反应,得到纤维/聚酰胺酸树脂溶液;
S4、将纤维/聚酰胺酸树脂溶液凝胶化成膜,再经热亚胺化处理,得到纤维/聚酰亚胺薄膜;
S5、将纤维/聚酰亚胺薄膜依次进行碳化处理、石墨化处理,即得碳化硅纤维、碳纤维增强聚酰亚胺石墨膜。
2.根据权利要求1所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,碳化硅纤维和碳纤维的总量占芳香族二胺和芳香族二酐总质量的0.1~1%,碳化硅纤维和碳纤维的质量比为1~3:1~3。
3.根据权利要求1或2所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S1中,在氧气气氛下对碳化硅纤维和碳纤维进行低温等离子体处理,处理功率100~300W、处理时间6~10min。
4.根据权利要求1-3任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S2中,芳香族二胺为对苯二胺或4,4'-二氨基二苯醚中的一种或其组合,有机溶剂为N,N'-二甲基乙酰胺或N,N'-二甲基甲酰胺。
5.根据权利要求1-4任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S3中,芳香族二酐为均苯四甲酸二酐或3,3',4,4'-联苯四甲酸二酐。
6.根据权利要求1-5任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S3中,缩聚反应的反应温度为10~30℃,反应时间为4~8h;优选地,纤维/聚酰胺酸树脂溶液中的固含量为10~20%、旋转粘度为100000~150000mPa·s。
7.根据权利要求1-6任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S4中,凝胶化成膜是将纤维/聚酰胺酸树脂溶液涂布在基板上,涂布厚度30~60μm,然后再热处理得到凝胶膜,热处理是以2~10℃/min升温至80~110℃,保温25~40min;优选地,热亚胺化处理的操作如下:以2~10℃/min升温至150~200℃保温30min,再以2~10℃/min升温至200~250℃保温30min进行亚胺化处理,然后以2~10℃/min升温至300~340℃保温30min进行退火处理。
8.根据权利要求1-7任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S5中,碳化处理是将纤维/聚酰亚胺薄膜与石墨片叠放,置于碳化炉中,抽真空,以2~4℃/min升温至900~1200℃,保温2~3h。
9.根据权利要求1-8任一项所述的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜的制备方法,其特征在于,S5中,石墨化处理是将碳化后的纤维/聚酰亚胺薄膜置于石墨化炉中,在氩气气氛下,以1~10℃/min升温至2000℃,然后以1~5℃/min升温至3000℃,并分别在2000℃、2400℃、2800℃、3000℃下各保温0.5~1h,最后以10℃/min冷却至室温,得到聚酰亚胺石墨膜。
10.如权利要求1-9任一项所述方法制备的碳化硅纤维、碳纤维增强聚酰亚胺石墨膜。
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