CN117430837A - 一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 - Google Patents
一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 Download PDFInfo
- Publication number
- CN117430837A CN117430837A CN202210818725.6A CN202210818725A CN117430837A CN 117430837 A CN117430837 A CN 117430837A CN 202210818725 A CN202210818725 A CN 202210818725A CN 117430837 A CN117430837 A CN 117430837A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyimide fiber
- preparation
- aerogel
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 62
- 229920001721 polyimide Polymers 0.000 title claims abstract description 62
- 239000000835 fiber Substances 0.000 title claims abstract description 57
- 239000004964 aerogel Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000377 silicon dioxide Substances 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- 238000007710 freezing Methods 0.000 claims abstract description 13
- 230000008014 freezing Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- 229920005839 ecoflex® Polymers 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000805 composite resin Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 7
- 239000000806 elastomer Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种垂直石墨烯‑聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法。本发明将氧化石墨烯纳米片与聚酰亚胺纤维通过冰模版法通过定向冷冻、高温煅烧制备结构高度有序的杂化气凝胶,并通过与橡胶弹性体通过真空辅助浸渍法制备了兼具导热与柔弹性的热界面材料。垂直有序的石墨烯气凝胶网络提高了轴向的导热率,减少填料聚集对聚合物基体弹性柔弹度的负面影响,实现了仅需少量填料便即可获得良好的导热性能。
Description
技术领域
本发明属于柔弹性导热复合材料技术领域,具体来书涉及一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法。
背景技术
随着5G时代及人工智能领域的不断进步,微电子器件、航天航天、能源化工等领域对热界面材料(TIMs),特别是弹性热界面材料有着迫切的需求。目前商用的TIMs主要是聚合物基复合材料,具有质量轻、成本适宜、加工方便等优点。传统聚合物基导热材料通过大量添加导热填料已获得高热导率,然而随着导热填料的增加,复合材料的弹性模量也会随之大幅增加,从而牺牲聚合物基质的柔弹性。对于热界面材料而言,材料的柔弹性能可以降低热接触电阻,缓解应力集中引起的翘曲失效。
石墨烯具有超高的导热性(5000W/(m·K))和优越的力学性能,广泛应用于导热散热领域。石墨烯气凝胶的三维碳网络可以有效接触面积,实现碳填料的均匀分布,显著降低碳材料之间的界面热阻。目前制备的石墨烯气凝胶多以氧化石墨烯水溶液为前驱体,片层间容易存在各种缺陷堆叠等,使得石墨烯的各项优异性能(如导热性能、力学性能)显著降低,传统石墨烯网络在垂直方向的导热路径较少,与树脂弹性体复合后在垂直方向上达不到理想的传热效果。
发明内容
为了克服现有技术的不足,本发明的目的在于提供以一种构建垂直取向的三维网络石墨烯-聚酰亚胺纤维气凝胶,提高垂直方向的导热率,减少填料聚集对聚合物基体弹性柔度的负面影响。本发明采用以下技术方案:
本发明关于石墨烯-聚酰亚胺纤维气凝胶及其复合材料的合成方法,其特征步骤如下:
1)氧化石墨烯的制备:在冰水浴的条件下向1L的烧杯中加入360ml浓硫酸和40mL浓磷酸,缓慢加入4g鳞片石墨。3h后,分批加入20g高锰酸钾。加料完毕后,油浴50℃加热18h。反应结束后,将反应液缓慢倒入碎冰中,待温度降为室温时,向反应液加入5%双氧水,直至液体变为亮黄色。用1mol/L稀盐酸洗涤2次,去离子水洗涤1次,高速离心。将凝胶状氧化石墨收集,加入50mL去离子水,倒入透析袋中,透析一周。
2)垂直取向氧化石墨烯-聚酰亚胺纤维气凝胶的制备:制备一定浓度的的氧化石墨烯分散液和的聚酰亚胺纤维分散液。将适量体积的氧化石墨烯分散液与聚酰亚胺纤维分散液混合后,用超声细胞破碎机超声3min。将所制备的凝胶倒入培养皿中,液面高度大概在8~10mm左右。将盛有不同浓度氧化石墨烯/聚酰亚胺分散液的培养皿放在定向冷冻装置(在杜瓦瓶中搭建铜台,灌注液氮至铜台表面)。冰冻完成后,将其放入冷冻干燥机中,设置温度-20℃,冰冻2天。冷冻结束后利用管式炉对制备的石墨烯-聚酰亚胺纤维骨架进行高温煅烧,以5℃/min的升温速率,从50℃升至500℃后,在500℃保温20min,自然冷却至室温后取出。
3)石墨烯-聚酰亚胺纤维/树脂复合材料:石墨烯-聚酰亚胺纤维/聚二甲基硅氧烷的制备:通过真空辅助浸渍的方法将树脂溶液充入到石墨烯/石墨烯聚酰亚胺纤维气凝胶混杂复合体,至完全饱和状态,成型后制备石墨烯-聚酰亚胺纤维气凝胶/树脂复合材料。
优选地,步骤2)氧化石墨烯与聚酰亚胺纤维的质量比为10∶(1~3);
优先地,步骤2)氧化石墨烯的浓度为2.5~10mg/mL;聚酰亚胺纤维分散液的浓度为10~20mg/mL;
优选地,步骤3)所述的树脂基体为所用的树脂基体为道康宁184、Ecoflex、聚氨酯、TPEE、Latex以及VHB(3M);
优选地,步骤3)所述的道康宁184中主剂与固化剂的比例为(10~50)∶1。
本发明将氧化石墨烯纳米片与聚酰亚胺纤维通过冰模版法通过定向冷冻、高温煅烧制备结构高度有序的杂化气凝胶,并通过与橡胶弹性体通过溶液浸渍制备了兼具导热与柔弹性的热界面材料。垂直取向的导热网络与低模量的橡胶弹性体实现了仅需少量填料便即可实现良好的导热性能。
附图说明
图1为氧化石墨烯与石墨烯气-聚酰亚胺纤维气凝胶的XPS谱图;
图2为石墨烯-聚酰亚胺纤维气凝胶的扫描电镜图片;
图3为石墨烯-聚酰亚胺纤维/Ecoflex导热率随石墨烯浓度的变化规律;
图4为石墨烯浓度为2.5、5、10mg/mL的石墨烯-聚酰亚胺纤维/PDMS的应力-应变曲线。
具体实施方式
下面给出本发明的3个实施例,是对本发明的进一步说明,而不是限制本发明的范围。
实施例1
1)氧化石墨烯的制备:在冰水浴的条件下向1L的烧杯中加入360ml浓硫酸和40mL浓磷酸,缓慢加入4g鳞片石墨。3h后,分批加入20g高锰酸钾。加料完毕后,油浴50℃加热18h。反应结束后,将反应液缓慢倒入碎冰中,待温度降为室温时,向反应液加入5%双氧水,直至液体变为亮黄色。用1mol/L稀盐酸洗涤2次,去离子水洗涤1次,高速离心。将凝胶状氧化石墨收集,加入50mL去离子水,倒入透析袋中,透析一周。
2)垂直取向氧化石墨烯-聚酰亚胺纤维气凝胶的制备:制备2.5mg/mL的氧化石墨烯分散液和20mg/mL聚酰亚胺纤维分散液。将适量体积的氧化石墨烯分散液与聚酰亚胺纤维分散液混合(氧化石墨烯与聚酰亚胺纤维的质量比为10∶3)后,用超声细胞破碎机超声3min。将所制备的凝胶倒入培养皿中,液面高度大概在8mm左右。将氧化石墨烯/聚酰亚胺分散液的培养皿放在定向冷冻装置(杜瓦瓶中搭建铜台,灌注液氮至铜台表面)。冰冻完成后,将其放入冷冻干燥机中,设置温度-20℃,冰冻2天。冷冻结束后利用管式炉对制备的石墨烯-聚酰亚胺纤维骨架进行高温煅烧,以5℃/min的升温速率,从50℃升至500℃后,在500℃保温20min,自然冷却至室温后取出。
3)石墨烯-聚酰亚胺纤维/聚二甲基硅氧烷的制备:取30mL的PDMS主剂加入少量二氯甲烷,振荡至完全溶解;加入3mL的交联剂,超声15min。静置脱泡后,将制备的垂直石墨烯-聚酰亚胺纤维骨架中在真空条件下进行溶液浸渍,静置30min。将复合材料置于60℃的恒温箱中预固化30min,再升温至120℃固化180min,得到垂直取向的石墨烯-聚酰亚胺纤维/PDMS复合材料。
实施例2
1)氧化石墨烯的制备:在冰水浴的条件下向1L的烧杯中加入360ml浓硫酸和40mL浓磷酸,缓慢加入4g鳞片石墨。3h后,分批加入20g高锰酸钾。加料完毕后,油浴50℃加热18h。反应结束后,将反应液缓慢倒入碎冰中,待温度降为室温时,向反应液加入5%双氧水,直至液体变为亮黄色。用1mol/L稀盐酸洗涤2次,去离子水洗涤1次,高速离心。将凝胶状氧化石墨收集,加入50mL去离子水,倒入透析袋中,透析一周。
2)垂直取向氧化石墨烯-聚酰亚胺纤维气凝胶的制备:制备5mg/mL的氧化石墨烯分散液和10mg/mL聚酰亚胺纤维分散液。将适量体积的氧化石墨烯分散液与聚酰亚胺纤维分散液混合(氧化石墨烯与聚酰亚胺纤维的质量比为10∶1)后,用超声细胞破碎机超声3min。将所制备的凝胶倒入培养皿中,液面高度大概在8mm左右。将氧化石墨烯/聚酰亚胺分散液的培养皿放在定向冷冻装置(杜瓦瓶中搭建铜台,灌注液氮至铜台表面)。冰冻完成后,将其放入冷冻干燥机中,设置温度-20℃,冰冻2天。冷冻结束后利用管式炉对制备的石墨烯-聚酰亚胺纤维骨架进行高温煅烧,以5℃/min的升温速率,从50℃升至500℃后,在500℃保温20min,自然冷却至室温后取出。
3)石墨烯-聚酰亚胺纤维/聚二甲基硅氧烷的制备:取30mL的PDMS主剂加入少量二氯甲烷,振荡至完全溶解;加入1.5mL的交联剂,超声15min。静置脱泡后,将制备的垂直石墨烯-聚酰亚胺纤维骨架中在真空条件下进行溶液浸渍,静置30min。将复合材料置于60℃的恒温箱中预固化30min,再升温至120℃固化180min,得到垂直取向的石墨烯-聚酰亚胺纤维/PDMS复合材料。
实施例3
1)氧化石墨烯的制备:在冰水浴的条件下向1L的烧杯中加入360ml浓硫酸和40mL浓磷酸,缓慢加入4g鳞片石墨。3h后,分批加入20g高锰酸钾。加料完毕后,油浴50℃加热18h。反应结束后,将反应液缓慢倒入碎冰中,待温度降为室温时,向反应液加入5%双氧水,直至液体变为亮黄色。用1mol/L稀盐酸洗涤2次,去离子水洗涤1次,高速离心。将凝胶状氧化石墨收集,加入50mL去离子水,倒入透析袋中,透析一周。
2)垂直取向氧化石墨烯-聚酰亚胺纤维气凝胶的制备:制备10mg/mL的氧化石墨烯分散液和20mg/mL聚酰亚胺纤维分散液。将适量体积的氧化石墨烯分散液与聚酰亚胺纤维分散液混合(氧化石墨烯与聚酰亚胺纤维的质量比为10∶3)后,用超声细胞破碎机超声3min。将所制备的凝胶倒入培养皿中,液面高度大概在8mm左右。将氧化石墨烯/聚酰亚胺分散液的培养皿放在定向冷冻装置(杜瓦瓶中搭建铜台,灌注液氮至铜台表面)。冰冻完成后,将其放入冷冻干燥机中,设置温度-20℃,冰冻2天。冷冻结束后利用管式炉对制备的石墨烯-聚酰亚胺纤维骨架进行高温煅烧,以5℃/min的升温速率,从50℃升至500℃后,在500℃保温20min,自然冷却至室温后取出。
3)石墨烯-聚酰亚胺纤维/Ecoflex的制备:将15mL Ecoflex A和B分配到混合容器后,彻底混合3分钟。静置脱泡后,将制备的垂直石墨烯-聚酰亚胺纤维骨架中在真空条件下进行溶液浸渍,静置30min。将复合材料置于60℃的恒温箱中预固化30min,再升温至120℃固化180min,得到垂直取向的石墨烯-聚酰亚胺纤维/PDMS复合材料。
导热系数(W/m·K) | |
实施例1 | 0.20 |
实施例2 | 0.53 |
实施例3 | 0.74 |
以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (4)
1.一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法,其特征在于包括以下步骤如下:
步骤一:氧化石墨烯的制备:在冰水浴的条件下向1L的烧杯中加入360ml浓硫酸和40mL浓磷酸,缓慢加入4g鳞片石墨。3h后,分批加入20g高锰酸钾。加料完毕后,油浴50℃加热18h。反应结束后,将反应液缓慢倒入碎冰中,待温度降为室温时,向反应液加入5%双氧水,直至液体变为亮黄色。用1mol/L稀盐酸洗涤2次,去离子水洗涤1次,高速离心。将凝胶状氧化石墨收集,加入50mL去离子水,倒入透析袋中,透析一周。
步骤二:垂直取向石墨烯-聚酰亚胺纤维气凝胶的制备:制备一定浓度的氧化石墨烯/水分散液和的聚酰亚胺纤维/水分散液。将适量体积的氧化石墨烯分散液与聚酰亚胺纤维分散液混合后,用超声细胞破碎机超声3min。将所制备的凝胶倒入培养皿中,液面高度大概在8~10mm左右。将盛有不同浓度氧化石墨烯/聚酰亚胺分散液的培养皿放在定向冷冻装置(在杜瓦瓶中搭建铜台,添加液氮至铜台表面)。冰冻完成后,将其放入冷冻干燥机中,设置温度-20℃,冰冻2天。其中:所述的氧化石墨烯-气凝胶为由2.5-10mg/ml的氧化石墨烯分散液经液氮定向冷冻制得,具有垂直取向的三维石墨烯结构。冷冻结束后利用管式炉对制备的石墨烯-聚酰亚胺纤维骨架进行高温煅烧。
步骤三:石墨烯-聚酰亚胺纤维/聚二甲基硅氧烷的制备:通过真空辅助浸渍的方法将树脂溶液充入到石墨烯/石墨烯聚酰亚胺纤维气凝胶混杂复合体,至完全饱和状态,成型后制备石墨烯-聚酰亚胺纤维气凝胶/树脂复合材料。
2.根据权利要求1步骤二所述的制备方法,其特征在于,按质量比,氧化石墨烯与聚酰亚胺纤维的比例为10∶(1-3)。
3.根据权利要求1步骤二中所述的制备方法,煅烧条件:5℃/min的升温速率,从50℃升至500℃后,在500℃保温20min,自然冷却至室温后取出。
4.根据权利要求1中步骤三所述的制备方法,其特征在于,所述的树脂基体为所用的树脂基体为道康宁184,Ecoflex、聚氨酯、TPEE、Latexy以及VHB(3M)。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210818725.6A CN117430837A (zh) | 2022-07-13 | 2022-07-13 | 一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210818725.6A CN117430837A (zh) | 2022-07-13 | 2022-07-13 | 一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117430837A true CN117430837A (zh) | 2024-01-23 |
Family
ID=89548474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210818725.6A Pending CN117430837A (zh) | 2022-07-13 | 2022-07-13 | 一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117430837A (zh) |
-
2022
- 2022-07-13 CN CN202210818725.6A patent/CN117430837A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112094625A (zh) | 一种氮化硼纳米管气凝胶/相变导热复合材料及其制备方法 | |
CN113881228A (zh) | 一种高导热碳素纤维复合材料及其制备方法 | |
CN107651662B (zh) | 一种制备硼、氮双掺杂炭气凝胶的方法 | |
CN114854087B (zh) | 一种具备双导热网络的聚酰亚胺复合材料及其制备方法 | |
CN113831587A (zh) | 光热转换胶乳海绵及其制备方法和应用 | |
CN112759788B (zh) | 一种具有固液互穿网络结构的导热复合水凝胶及制备方法 | |
CN117430837A (zh) | 一种垂直石墨烯-聚酰亚胺纤维气凝胶/聚甲基硅氧复合材料的制备方法 | |
CN112812528B (zh) | 一种生物质基片状活性炭增强smc复合材料的制备方法 | |
Chen et al. | Properties and morphologies of epoxy resin based composites reinforced by polyurethane and graphene oxide | |
CN109161195A (zh) | 一种导电型碳纳米管/氰酸酯复合材料及其制备方法 | |
CN110918010A (zh) | 一种海泡石石墨烯复合气凝胶的制备方法 | |
CN111334028B (zh) | 一种抗紫外的高导热改性聚氨酯复合薄膜材料及其制法 | |
Li et al. | Polyurethane foam-supported three-dimensional interconnected graphene nanosheets network encapsulated in polydimethylsiloxane to achieve significant thermal conductivity enhancement | |
CN113549296A (zh) | 一种环氧树脂高导热复合材料及制备方法 | |
CN110468591B (zh) | 一种石墨烯纤维用上浆剂及其制备方法 | |
CN112029247A (zh) | 一种高导热的改性聚乳酸薄膜及其制法 | |
CN107159067B (zh) | 一种柔性氧化硅气凝胶材料及其制备方法 | |
CN111423163A (zh) | 一种再生石墨-水泥砂浆复合材料及其制备方法 | |
CN115558241B (zh) | 一种高导热碳纤维织物复合材料及其制备方法 | |
CN112745478B (zh) | 高导热性热塑性聚氨酯复合材料及其制备方法 | |
Wang et al. | Multifunctional nanocomposites reinforced by aligned graphene network via a low-cost lyophilization-free method | |
CN114085530B (zh) | 一种低热阻高导热石墨烯硅橡胶复合材料及其制备方法 | |
CN113150498B (zh) | 一种高强度、导热绝缘环氧树脂复合材料及其制备方法 | |
CN116003097B (zh) | 一种聚酰亚胺基复合碳气凝胶及其制备方法和用途 | |
CN112778752B (zh) | 一种新型石墨烯热界面材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication |