CN115448745A - 一种定向导热导电石墨碳膜及定向导热碳件的制备方法 - Google Patents
一种定向导热导电石墨碳膜及定向导热碳件的制备方法 Download PDFInfo
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Abstract
本发明涉及一种定向导热导电石墨碳膜及定向导热碳件的制备方法,属于石墨烯技术领域,解决了现有导热炭材料整体导热效果不佳、导热炭材料特定方向的热导率低等技术问题。解决方案为:一种定向导热导电石墨碳膜及定向导热碳件的制备方法,包括以下步骤:1)超声粉碎:将可溶性中间相沥青通过液氮冷却至‑90~‑60℃,并对冷却后的可溶性中间相沥青进行超声波粉碎、去静电;2)制备混合液体;3)制备碳浆膜;4)高温蒸汽脱除溶剂;5)制备辊压碳膜;6)碳化处理;7)石墨化处理;8)制备定向导热碳件。与现有技术相比,本发明具有可大幅面连续化生产、实现成膜到碳件性能可调控的组合生产、导热炭材料整体导热效果增强等优点。
Description
技术领域
本发明属于石墨烯技术领域,具体涉及一种定向导热导电石墨碳膜及定向导热碳件的制备方法。
背景技术
随着现代工业、国防和科学技术的飞速发展,导热和散热问题成为制约许多领域发展的关键。在微电子及通讯技术领域,高频、高速以及大规模集成电路的密集和小型化,使得单位容积电子器件的发热量迅速增大。目前,微电子芯片的发热量一般为60-90W·cm-2,最高可达200W·cm-2以上。因此,电子器件的散热技术越来越成为新产品研发中的关键,其散热性能的好坏直接影响电子产品的工作性能,这是因为过高的温度会危及半导体的结点和焊点,损伤电路连接界面的同时增加导体的阻值。电子元件的温度较正常工作温度降低1℃,其故障率可减少4%;若其温度增加10~20℃,则故障率将提高100%。通常,微电子芯片的表面温度必须维持在较低温度才能以高性能稳定工作。此外,许多电子器件需要在40~60℃的环境温度下才能正常工作,这就对作为热控重要组成部分的导热材料提出了越来越高的要求,因此迫切需要开发出轻质、高热导率和优异热稳定性的材料。
传统的金属导热材料,如铝、铜、银等由于存在密度较大、易氧化、比热导率(热导率和体积密度之比)较低、热膨胀系数较高等局限性,已经很难满足当前微电子领域电子器件日益增长的散热需求。对于导热型热管理材料而言,材料自身具有较高的比热导率和良好的热态环境服役性能尤为重要。高导热炭材料种类繁多、形态多样,包括纤维、粉体、块体和薄膜等,因此在导热、散热、热疏导、热防护等热管理领域具有非常广泛的应用前景和市场。粉末状炭材料根据个体尺寸特征可直接用于微纳小型器件散热,或作为导热膏/散热脂的导热填料用于界面散热;形态、尺寸以及石墨微晶结构定向可控的高导热炭材料可用作宏观散热器件或热沉材料。这两类炭材料在热传导应用中各有所长,可以在小型微纳电子元件和大型高功率集成器件等领域复合使用实现互补,从而解决高速、高功率、集成化5G通信等领域的热管理难题。
微电子及通讯技术领域的快速发展对热管理材料提出了更高要求,迫切需要设计和开发高定向导热炭材料。高定向炭材料因其较高的石墨微晶结晶度和石墨化度、有序规整堆叠的石墨烯层片,而具有典型的各向异性高导热特性。粉末状炭材料(如鳞片石墨、气相生长炭纤维、纳米碳管、石墨烯等)的热导率虽然很高,但作为导热填料制备的复合材料的整体导热效果不佳,因此其在大型高功率集成器件散热领域的应用会受到一定限制。
发明内容
为了克服现有技术的不足,解决现有导热炭材料整体导热效果不佳、导热炭材料特定方向的热导率低等技术问题,本发明提供一种定向导热导电石墨碳膜及定向导热碳件的制备方法。
本发明通过以下技术方案予以实现。
本发明提供了一种定向导热导电石墨碳膜及定向导热碳件的制备方法,包括以下步骤:
1)超声粉碎:将可溶性中间相沥青通过液氮冷却至-90~-60℃,并对冷却后的可溶性中间相沥青进行超声波粉碎、去静电,制得物质A1;
2)制备混合液体:将质量份为7~9份的物质A1与质量份为1份的短切及研磨碳纤维充分混合,形成混合物B1;
将质量份为1份的混合物B1加入到质量份为1.5~2份的60~70℃乙二醇溶剂中充分搅拌,并在搅拌状态下冷却至20~30℃,制得均匀浆状可流态的混合液体B2;
3)制备碳浆膜:将混合液体B2均匀倒入循环转动的碳纤维编织的覆带布面上,控制混合液体B2在碳纤维编织的覆带布面上维持长度0.5-0.8m,碳纤维编织的覆带布面下方设交变磁场,控制交变磁场的强度与方向来改变混合液体B2中碳颗粒晶体的排列结构,制得磁化排列规则的碳浆膜C;
4)高温蒸汽脱除溶剂:将载有碳浆膜C的碳纤维编织的履带布面穿过高温蒸汽箱,高温蒸汽箱箱内碳纤维编织的履带布面下方10-15cm处设有强力交变磁场,保持碳浆膜C内的乙二醇溶剂在渗流过程中晶体移动后取向不变;
5)制备辊压碳膜:对经过高温蒸汽箱后的载有碳浆膜C的碳纤维编织的履带布面进行第一道热轧辊和第二道热轧辊处理,制得碳源膜D1;
通过碳膜辊将碳源膜D1从碳纤维编织的履带布面上分离并卷绕在陶瓷卷辊上,制得新的碳膜D2;
对碳膜D2进行第三道热轧辊处理,制得辊压碳膜D3;
将辊压碳膜D3通过轴传送至氧化固化箱,辊压碳膜D3在氧化固化箱的停留时间不低于60-150min,并向所述氧化固化箱中通入净化空气,制得氧化固化后的碳膜D4;
将氧化固化后的碳膜D4通过轴传送至第四道热压辊进行处理,制得辊压碳膜D5,所述辊压碳膜D5卷绕在陶瓷卷辊上;
6)碳化处理:将卷绕在陶瓷卷辊上的辊压碳膜D5和陶瓷卷辊一起放入碳化箱中,碳化箱内部通过氮气完全置换保护,碳化箱以5℃/min的速率升温到1700-1800℃后保温30min,待自然降温至室温后取出辊压碳膜D5,将其反方向卷绕在另一个陶瓷卷辊上,制得碳化碳膜E1;
7)石墨化处理:将碳化碳膜E1放入高纯氩气保护的石墨箱中进行石墨处理,石墨箱以5-10℃/min的速率升温到2800-3200℃后保温30min,待自然降温至室温后取出,制得定向导热导电碳膜F1;
8)制备定向导热碳件:将质量份为1.5份的可溶性聚酰亚胺和质量份为0.05份的氧化石墨烯溶解于质量份为1份的二甲基乙酰胺溶剂中,通过超声波搅拌处理,制得粘接剂G1;
将定向导热导电碳膜F1放到卷辊上并粘粘接剂G1后,往复折叠若干次,制得碳膜件H1;
将碳膜件H1在温度260-450℃、压力2-2.5mpa下压紧成块,保持压紧件温度内外均匀,蒸发掉溶剂后,继续在温度350-400℃、压力2-2.5mpa下压紧10-30min,制得定向导热碳件I1。
进一步,所述步骤1)中可溶性中间相沥青为各向异性体含量100%的AR沥青,超声波粉碎后的颗粒孔径为5-15um。
进一步,所述步骤3)中碳纤维编织的覆带布面的转动速度为6-20m/min,交变磁场覆盖碳纤维编织的覆带布面长度为0.6-1.2m。
进一步,所述步骤4)中高温蒸汽箱长度不低于2m,高温蒸汽箱内温度为116-135℃。
进一步,所述步骤5)中第一道热轧辊的温度为150-180℃,压力维持在0.2-0.6mpa,辊压厚度为0.4-0.8mm;第二道热轧辊的温度为230-280℃,压力维持在0.8-1.2mpa,辊压厚度为0.2-0.4mm;第三道热压辊的温度为350-480℃,压力维持在1.5-2.5mpa,辊压厚度为0.05-0.1mm;氧化固化箱的温度维持在160-350℃,第四道热压辊的压力维持在2.5-4mpa,辊压厚度为0.02-0.05mm。
进一步,所述步骤8)中的往复折叠次数Y=目标件厚度X/2×氧化固化后的碳膜D4厚度Z。
本发明所达到的有益效果是:本发明提供了一种定向导热导电石墨碳膜及定向导热碳件的制备方法,采用交变磁场控制材料内部石墨微晶的尺寸、取向以及取向的连续性,可使石墨晶体沿晶面方向保持高导热特性,实现连续高定向、多维度可调控热传导产品的生产,且生产过程中的物质可回收循环利用。
与现有技术相比,本发明具有可大幅面连续化生产、实现成膜到碳件性能可调控的组合生产、导热炭材料整体导热效果增强等优点。
具体实施方式
下面结合实施例对本发明作进一步的详细描述。
一种定向导热导电石墨碳膜及定向导热碳件的制备方法,包括以下步骤:
1)超声粉碎:将可溶性中间相沥青通过液氮冷却至-90~-60℃,并对冷却后的可溶性中间相沥青进行超声波粉碎、去静电,制得物质A1,所述步骤1)中可溶性中间相沥青为各向异性体含量100%的AR沥青,超声波粉碎后的颗粒孔径为5-15um;
2)制备混合液体:制备混合液体:将质量份为7~9份的物质A1与质量份为1份的短切及研磨碳纤维充分混合,形成混合物B1;
将质量份为1份的混合物B1加入到质量份为1.5~2份的60~70℃乙二醇溶剂中充分搅拌,并在搅拌状态下冷却至20~30℃,制得均匀浆状可流态的混合液体B2;
3)制备碳浆膜:将混合液体B2均匀倒入循环转动的碳纤维编织的覆带布面上,其中碳纤维编织的覆带布面的转动速度为6-20m/min,控制混合液体B2在碳纤维编织的覆带布面上维持长度0.5-0.8m,碳纤维编织的覆带布面下方设交变磁场,交变磁场覆盖碳纤维编织的覆带布面长度为0.6-1.2m,控制交变磁场的强度与方向来改变混合液体B2中碳颗粒晶体的排列结构,制得磁化排列规则的碳浆膜C,采用交变磁场控制材料内部石墨微晶的尺寸、取向以及取向的连续性,可使石墨晶体沿晶面方向保持高导热特性,实现连续高定向、多维度可调控热传导产品的生产,碳浆膜C的宽度可以通过碳纤维编织的覆带布面宽度来调节,碳纤维编织的覆带布面底部渗留出的液体可循环使用;
4)高温蒸汽脱除溶剂:将载有碳浆膜C的碳纤维编织的履带布面穿过高温蒸汽箱,高温蒸汽箱箱内碳纤维编织的履带布面下方10-15cm处设有强力交变磁场,保持碳浆膜C内的乙二醇溶剂在渗流过程中晶体移动后取向不变,其中高温蒸汽箱长度不低于2m,高温蒸汽箱内温度为116-135℃;
5)制备辊压碳膜:对经过高温蒸汽箱后的载有碳浆膜C的碳纤维编织的履带布面进行第一道热轧辊和第二道热轧辊处理,制得碳源膜D1,其中第一道热轧辊的温度为150-180℃,压力维持在0.2-0.6mpa,辊压厚度为0.4-0.8mm;第二道热轧辊的温度为230-280℃,压力维持在0.8-1.2mpa,辊压厚度为0.2-0.4mm;
通过碳膜辊将碳源膜D1从碳纤维编织的履带布面上分离并卷绕在陶瓷卷辊上,制得新的碳膜D2;
对碳膜D2进行第三道热轧辊处理,制得辊压碳膜D3,其中第三道热压辊的温度为350-480℃,压力维持在1.5-2.5mpa,辊压厚度为0.05-0.1mm;
将辊压碳膜D3通过轴传送至氧化固化箱,氧化固化箱的温度维持在160-350℃,辊压碳膜D3在氧化固化箱的停留时间不低于60-150min,并向所述氧化固化箱中通入净化空气,制得氧化固化后的碳膜D4;
将氧化固化后的碳膜D4通过轴传送至第四道热压辊进行处理,制得辊压碳膜D5,所述辊压碳膜D5卷绕在陶瓷卷辊上,其中第四道热压辊的压力维持在2.5-4mpa,辊压厚度为0.02-0.05mm;
6)碳化处理:将卷绕在陶瓷卷辊上的辊压碳膜D5和陶瓷卷辊一起放入碳化箱中,碳化箱内部通过氮气完全置换保护,碳化箱以5℃/min的速率升温到1700-1800℃后保温30min,待自然降温至室温后取出辊压碳膜D5,将其反方向卷绕在另一个陶瓷卷辊上,制得碳化碳膜E1;
7)石墨化处理:将碳化碳膜E1放入高纯氩气保护的石墨箱中进行石墨处理,石墨箱以5-10℃/min的速率升温到2800-3200℃后保温30min,待自然降温至室温后取出,制得定向导热导电碳膜F1;
8)制备定向导热碳件:将质量份为1.5份的可溶性聚酰亚胺和质量份为0.05份的氧化石墨烯溶解于质量份为1份的二甲基乙酰胺溶剂中,通过超声波搅拌处理,制得粘接剂G1;
将定向导热导电碳膜F1放到卷辊上并粘粘接剂G1后,往复折叠若干次,制得碳膜件H1,按照所需要的目标件的厚度计算往复折叠多少次,目标件厚度X,折叠次数Y,碳膜D4厚度为Z,得到往复折叠次数Y=目标件厚度X/2×氧化固化后的碳膜D4厚度Z;同时可以通过轴放方向的不同,以及轴放方向的层叠数控制二维方向的导热比,实现导热方向的定量可控;
将碳膜件H1在温度260-450℃、压力2-2.5mpa下压紧成块,保持压紧件温度内外均匀,蒸发掉溶剂后,继续在温度350-400℃、压力2-2.5mpa下压紧10-30min,制得定向导热碳件I1。
表1石墨碳膜、碳件的性能指标
通过上述工艺之后在室温下(~25℃)测量定向导热导电碳膜F1及定向导热碳件I1的具体性能指标如上表1:两者的电阻均维持在0.74Ω,面向导热提升到940-1180W·m-1·K-1,定向导热导电碳膜F1的轴向导热提升至154±8W·m-1·K-1,定向导热碳件I1的轴向导热提升至122±7W·m-1·K-1。
Claims (6)
1.一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:包括以下步骤:
1)超声粉碎:将可溶性中间相沥青通过液氮冷却至-90~-60℃,并对冷却后的可溶性中间相沥青进行超声波粉碎、去静电,制得物质A1;
2)制备混合液体:将质量份为7~9份的物质A1与质量份为1份的短切及研磨碳纤维充分混合,形成混合物B1;
将质量份为1份的混合物B1加入到质量份为1.5~2份的60~70℃乙二醇溶剂中充分搅拌,并在搅拌状态下冷却至20~30℃,制得均匀浆状可流态的混合液体B2;
3)制备碳浆膜:将混合液体B2均匀倒入循环转动的碳纤维编织的覆带布面上,控制混合液体B2在碳纤维编织的覆带布面上维持长度0.5-0.8m,碳纤维编织的覆带布面下方设交变磁场,控制交变磁场的强度与方向来改变混合液体B2中碳颗粒晶体的排列结构,制得磁化排列规则的碳浆膜C;
4)高温蒸汽脱除溶剂:将载有碳浆膜C的碳纤维编织的履带布面穿过高温蒸汽箱,高温蒸汽箱箱内碳纤维编织的履带布面下方10-15cm处设有强力交变磁场,保持碳浆膜C内的乙二醇溶剂在渗流过程中晶体移动后取向不变;
5)制备辊压碳膜:对经过高温蒸汽箱后的载有碳浆膜C的碳纤维编织的履带布面进行第一道热轧辊和第二道热轧辊处理,制得碳源膜D1;
通过碳膜辊将碳源膜D1从碳纤维编织的履带布面上分离并卷绕在陶瓷卷辊上,制得新的碳膜D2;
对碳膜D2进行第三道热轧辊处理,制得辊压碳膜D3;
将辊压碳膜D3通过轴传送至氧化固化箱,辊压碳膜D3在氧化固化箱的停留时间不低于60-150min,并向所述氧化固化箱中通入净化空气,制得氧化固化后的碳膜D4;
将氧化固化后的碳膜D4通过轴传送至第四道热压辊进行处理,制得辊压碳膜D5,所述辊压碳膜D5卷绕在陶瓷卷辊上;
6)碳化处理:将卷绕在陶瓷卷辊上的辊压碳膜D5和陶瓷卷辊一起放入碳化箱中,碳化箱内部通过氮气完全置换保护,碳化箱以5℃/min的速率升温到1700-1800℃后保温30min,待自然降温至室温后取出辊压碳膜D5,将其反方向卷绕在另一个陶瓷卷辊上,制得碳化碳膜E1;
7)石墨化处理:将碳化碳膜E1放入高纯氩气保护的石墨箱中进行石墨处理,石墨箱以5-10℃/min的速率升温到2800-3200℃后保温30min,待自然降温至室温后取出,制得定向导热导电碳膜F1;
8)制备定向导热碳件:将质量份为1.5份的可溶性聚酰亚胺和质量份为0.05份的氧化石墨烯溶解于质量份为1份的二甲基乙酰胺溶剂中,通过超声波搅拌处理,制得粘接剂G1;
将定向导热导电碳膜F1放到卷辊上并粘粘接剂G1后,往复折叠若干次,制得碳膜件H1;
将碳膜件H1在温度260-450℃、压力2-2.5mpa下压紧成块,保持压紧件温度内外均匀,蒸发掉溶剂后,继续在温度350-400℃、压力2-2.5mpa下压紧10-30min,制得定向导热碳件I1。
2.根据权利要求1所述的一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:所述步骤1)中可溶性中间相沥青为各向异性体含量100%的AR沥青,超声波粉碎后的颗粒孔径为5-15um。
3.根据权利要求1所述的一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:所述步骤3)中碳纤维编织的覆带布面的转动速度为6-20m/min,交变磁场覆盖碳纤维编织的覆带布面长度为0.6-1.2m。
4.根据权利要求1所述的一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:所述步骤4)中高温蒸汽箱长度不低于2m,高温蒸汽箱内温度为116-135℃。
5.根据权利要求1所述的一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:所述步骤5)中第一道热轧辊的温度为150-180℃,压力维持在0.2-0.6mpa,辊压厚度为0.4-0.8mm;第二道热轧辊的温度为230-280℃,压力维持在0.8-1.2mpa,辊压厚度为0.2-0.4mm;第三道热压辊的温度为350-480℃,压力维持在1.5-2.5mpa,辊压厚度为0.05-0.1mm;氧化固化箱的温度维持在160-350℃,第四道热压辊的压力维持在2.5-4mpa,辊压厚度为0.02-0.05mm。
6.根据权利要求1所述的一种定向导热导电石墨碳膜及定向导热碳件的制备方法,其特征在于:所述步骤8)中的往复折叠次数Y=目标件厚度X/2×氧化固化后的碳膜D4厚度Z。
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Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001294676A (ja) * | 2000-04-13 | 2001-10-23 | Jsr Corp | 熱伝導性シート、熱伝導性シートの製造方法および熱伝導性シートを用いた放熱構造 |
JP2004002096A (ja) * | 2002-05-31 | 2004-01-08 | Toyo Tanso Kk | 炭素繊維強化炭素複合材料及びその製造方法並びにヒートシンク |
CN108504016A (zh) * | 2016-06-14 | 2018-09-07 | 络派模切(北京)有限公司 | 一种导热垫片及其制备方法 |
CN109790309A (zh) * | 2016-09-28 | 2019-05-21 | 帝人株式会社 | 散热片 |
CN109776103A (zh) * | 2019-01-17 | 2019-05-21 | 郑州中科新兴产业技术研究院 | 一种三维石墨烯/碳纳米管复合散热材料的制备方法 |
CN110124612A (zh) * | 2019-04-02 | 2019-08-16 | 江苏大学 | 一种空气处理用微米级厚度的透气碳膜及其制造方法 |
CN110872193A (zh) * | 2018-09-04 | 2020-03-10 | 天津大学 | 一种高导热石墨烯/短切碳纤维复合材料的制备方法 |
CN111978732A (zh) * | 2020-09-04 | 2020-11-24 | 广东思泉新材料股份有限公司 | 一种三维导热网络结构的热界面材料 |
CN112251026A (zh) * | 2020-09-25 | 2021-01-22 | 北京空间飞行器总体设计部 | 一种填料有序倾斜排列的导热垫片及其制备方法 |
CN112822917A (zh) * | 2021-01-05 | 2021-05-18 | 苏州熵流科技有限公司 | 一种碳素导热片的制备方法 |
CN113150558A (zh) * | 2021-05-12 | 2021-07-23 | 广东思泉新材料股份有限公司 | 一种定向导热片及其制备方法、及半导体散热装置 |
CN113321933A (zh) * | 2021-06-11 | 2021-08-31 | 常州富烯科技股份有限公司 | 纵向高导热垫片、制备方法及应用 |
CN113416420A (zh) * | 2021-06-25 | 2021-09-21 | 厦门大学 | 一种高定向排列石墨烯片热界面材料制备方法 |
CN114341273A (zh) * | 2019-09-30 | 2022-04-12 | 积水保力马科技株式会社 | 导热性片和其制造方法 |
CN114456603A (zh) * | 2022-01-27 | 2022-05-10 | 厦门大学 | 一种磁场诱导排列碳纤维导热材料及其制备方法 |
CN115029816A (zh) * | 2022-06-17 | 2022-09-09 | 武汉科技大学 | 超高导热中间相沥青基碳纤维、复合材料及其制备方法 |
-
2022
- 2022-09-21 CN CN202211153630.3A patent/CN115448745B/zh active Active
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001294676A (ja) * | 2000-04-13 | 2001-10-23 | Jsr Corp | 熱伝導性シート、熱伝導性シートの製造方法および熱伝導性シートを用いた放熱構造 |
JP2004002096A (ja) * | 2002-05-31 | 2004-01-08 | Toyo Tanso Kk | 炭素繊維強化炭素複合材料及びその製造方法並びにヒートシンク |
CN108504016A (zh) * | 2016-06-14 | 2018-09-07 | 络派模切(北京)有限公司 | 一种导热垫片及其制备方法 |
CN109790309A (zh) * | 2016-09-28 | 2019-05-21 | 帝人株式会社 | 散热片 |
CN110872193A (zh) * | 2018-09-04 | 2020-03-10 | 天津大学 | 一种高导热石墨烯/短切碳纤维复合材料的制备方法 |
CN109776103A (zh) * | 2019-01-17 | 2019-05-21 | 郑州中科新兴产业技术研究院 | 一种三维石墨烯/碳纳米管复合散热材料的制备方法 |
CN110124612A (zh) * | 2019-04-02 | 2019-08-16 | 江苏大学 | 一种空气处理用微米级厚度的透气碳膜及其制造方法 |
CN114341273A (zh) * | 2019-09-30 | 2022-04-12 | 积水保力马科技株式会社 | 导热性片和其制造方法 |
CN111978732A (zh) * | 2020-09-04 | 2020-11-24 | 广东思泉新材料股份有限公司 | 一种三维导热网络结构的热界面材料 |
CN112251026A (zh) * | 2020-09-25 | 2021-01-22 | 北京空间飞行器总体设计部 | 一种填料有序倾斜排列的导热垫片及其制备方法 |
CN112822917A (zh) * | 2021-01-05 | 2021-05-18 | 苏州熵流科技有限公司 | 一种碳素导热片的制备方法 |
CN113150558A (zh) * | 2021-05-12 | 2021-07-23 | 广东思泉新材料股份有限公司 | 一种定向导热片及其制备方法、及半导体散热装置 |
CN113321933A (zh) * | 2021-06-11 | 2021-08-31 | 常州富烯科技股份有限公司 | 纵向高导热垫片、制备方法及应用 |
CN113416420A (zh) * | 2021-06-25 | 2021-09-21 | 厦门大学 | 一种高定向排列石墨烯片热界面材料制备方法 |
CN114456603A (zh) * | 2022-01-27 | 2022-05-10 | 厦门大学 | 一种磁场诱导排列碳纤维导热材料及其制备方法 |
CN115029816A (zh) * | 2022-06-17 | 2022-09-09 | 武汉科技大学 | 超高导热中间相沥青基碳纤维、复合材料及其制备方法 |
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