CN109608664A - 一种高导热氧化铝/环氧树脂纳米复合材料的制备方法 - Google Patents
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法 Download PDFInfo
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Abstract
本发明一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,属于高分子复合材料领域。该方法首先采用一定的压力对不同粒径的Al2O3粉体进行模压成型,在不同温度和保温时间条件下,通过常压烧结获得气孔率和孔径可调的多孔Al2O3骨架。经过表面改性后,将预热的多孔Al2O3骨架置入环氧树脂、促进剂、固化剂和纳米氧化铝颗粒形成的混合溶液中,并保持一定时间,最后经加热固化获得微、纳米氧化铝共掺杂的环氧树脂复合材料。本发明可通过调整纳米氧化铝的掺入量来控制有机复合材料的热导率;另一方面,有机复合材料中的氧化铝骨架呈连续状,可大幅度提高氧化铝/环氧树脂复合材料的热导率、抗高温蠕变能力。本发明可为研制和开发高性能环氧复合材料提供新思路。
Description
技术领域
本发明属于高分子复合材料领域,具体涉及一种高导热氧化铝/环氧树脂纳米复合材料的制备方法。
背景技术
电子封装材料是用于承载电子元器件及其相互连线,并具有良好电绝缘性的基体材料,主要起机械支持、密封保护、散失电子元件所产生的热量等作用,是高功率集成电路的重要组成部分。
环氧复合材料由于其优良的力学和绝缘性能被广泛应用于电子封装领域。但环氧树脂本体的导热率很低(0.17~0.21W·m-1·k-1),越来越不能满足现代电子封装领域对材料高导热性能的要求。出于导热和经济成本的考虑,通常使用添加大量无机填料的环氧树脂,其中无机填料Al2O3具有高纯度、高分散性、高导热性、价格低廉等优点,其作为无机填料的环氧复合材料可以利用Al2O3颗粒致密的原子晶体结构,以及作为载流子的声子实现复合材料的高导热性。且与纯环氧树脂相比,掺入Al2O3颗粒的环氧树脂既能克服纯环氧树脂耐热性差,力学强度不高等缺点,又可充分发挥无机颗粒的高导热性,耐腐蚀性等优点。
目前学界多采用溶液混合法制备环氧复合材料,但采用溶液混合法制备复合材料时,氧化铝/环氧树脂复合材料中Al2O3颗粒孤立地存在于环氧树脂基体内,孤立的氧化铝颗粒难以形成有效的导热通道,氧化铝/环氧树脂复合材料的导热率难以大幅度提高。
发明内容
本发明所要解决的技术问题是针对现有环氧复合材料中Al2O3颗粒孤立分布导致热导率不高,提供了一种高导热氧化铝/环氧树脂纳米复合材料的制备方法。
本发明采用如下技术方案来实现的:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,该氧化铝/环氧树脂纳米复合材料通过将环氧树脂、固化剂、促进剂和纳米氧化铝颗粒的混合液体浸渍至多孔氧化铝陶瓷骨架中,经过高温固化得到;其中,多孔氧化铝陶瓷的气孔率为40%~70%,对应其在复合材料中的体积分数为70vol.%~40vol.%,均匀弥散分布在环氧树脂基体中的纳米氧化铝颗粒的体积分数为0.5vol.%~3vol.%,包括以下步骤:
1)将不同粒径的Al2O3粉、黏结助剂PVA、发泡剂淀粉混合均匀,混合粉体过筛,将筛分得到模压所用粉体置于模具中,在轴向压力作用下模压成型,将压好的生坯放入空气炉中进行高温烧结,保温后冷却至室温,得到气孔率为40%~70%、不同孔径的多孔Al2O3骨架,其中,烧结温度为1150~1550℃,保温时间为1~3h,将得到的多孔Al2O3骨架表面研磨平整后,置于含有2~5wt.%硅烷偶联剂的乙醇水溶液中进行表面改性,60~80℃保温2~5h,乙醇水溶液中按体积比:乙醇:水=95:5;
2)将步骤1)得到的表面改性后的多孔Al2O3骨架预热到50~80℃,将环氧树脂、固化剂、促进剂与纳米氧化铝按质量比为1:(0.6~0.9):(0.01~0.05):(0.0313~0.163)混合后,在50~80℃下搅拌2~4h,混合均匀后,真空脱泡2~4h,真空度为-0.095MPa;将预热的多孔Al2O3骨架置于环氧树脂、促进剂、固化剂和纳米氧化铝颗粒的混合溶液中,在50~80℃下真空脱泡2~4h,真空度为-0.095MPa,将真空浸渍后的样品放置在真空烘箱中进行固化,得到高导热热氧化铝/环氧树脂纳米复合材料。
本发明进一步的改进在于,步骤1)中,Al2O3粉的平均粒径为0.2~30μm。
本发明进一步的改进在于,步骤1)中,平均粒径为0.2μm、0.5μm的Al2O3粉的模压压力为25~45MPa,保压时间为1min;平均粒径为2μm、5μm的Al2O3粉的模压压力为45~65MPa,保压时间1min;平均粒径为10μm、30μm的Al2O3粉的模压压力为65~85MPa,保压时间1min。
本发明进一步的改进在于,步骤1)中,混合粉体的过筛目数为150目或200目。
本发明进一步的改进在于,步骤1)中,黏结助剂PVA的固相含量为8~15wt.%,黏结助剂PVA的质量分数为5wt.%,发泡剂淀粉的质量分数为10~25wt.%。
本发明进一步的改进在于,步骤1)中,烧结温度的升温速率在600℃以下为3℃/min,600℃及以上为5℃/min。
本发明进一步的改进在于,步骤2)中,环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂或者双酚S型环氧树脂中的任意一种,固化剂为甲基四氢邻苯二甲酸酐,促进剂为三苯酚。
本发明进一步的改进在于,步骤2)中,纳米氧化铝颗粒倒入盛有去离子水的容器中,在室温条件下用磁力搅拌器进行1h的搅拌,在超声仪器中100℃超声分散1h,之后在烘箱中烘干。
本发明进一步的改进在于,步骤2)中,纳米氧化铝颗粒置于含有2~5wt.%硅烷偶联剂的无水乙醇中进行表面改性,60~80℃保温2~5h。
本发明进一步的改进在于,步骤2)中,真空浸渍后的样品的固化制度为:95℃保温2h,升温至140℃保温3h,升温至170℃,保温4h,每个阶段的升温速率均为5℃/min。
本发明具有如下有益的技术效果:
本发明摒弃传统上的溶液混合法制备氧化铝/环氧树脂复合材料的方法,首先采用无压烧结制备多孔Al2O3陶瓷,通过控制起始Al2O3粒径大小和淀粉造孔剂的含量,可控制多孔Al2O3陶瓷的孔径尺寸(0.5~10μm)和气孔率(40~70%);再采用真空浸渍法将纳米氧化铝-环氧树脂混合溶液填充到经过表面改性的多孔Al2O3陶瓷骨架中,获得高导热氧化铝/环氧树脂纳米复合材料。环氧复合材料内部的Al2O3相为连续相,且环氧树脂基体中掺杂有纳米氧化铝颗粒,可大幅度提高氧化铝/环氧树脂材料的热导率,热导率最高可达6.423W·m-1·k-1。
本发明的制备工艺简单,易于操作,可通过调控多孔材料的气孔率来改变复合材料中Al2O3增强相的含量;通过调控纳米氧化铝的添加量可改变掺杂氧化铝的含量。本发明可用于电子元器件封装领域。
附图说明
图1为本发明实施例1所得的多孔Al2O3骨架的显微结构照片。
图2为本发明实施例1所得的氧化铝/环氧树脂复合材料的显微结构照片。
具体实施方式
现结合实施例和附图,对本发明作进一步描述,但本发明的实施并不仅限于此。
实施例1:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将70wt.%的Al2O3粉(2μm)、25wt.%的淀粉和5wt.%的PVA(固相含量8wt.%)混合均匀,并过200目筛网筛分得到模压所用粉体;在45MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1350℃常压烧结,保温1h,得到气孔率为65%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有3.5wt.%硅烷偶联剂的无水乙醇中进行表面改性,65℃保温4.5h;
2)将双酚A型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.86:0.03:0.0626的比例在80℃下高速搅拌2h,混合均匀后,真空脱泡2h。将80℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.2%,抗弯强度为125.4MPa,热导率为5.323W·m-1·k-1。
实施例2:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将75wt.%的Al2O3粉(5μm)、20wt.%的淀粉和5wt.%的PVA(固相含量10wt.%)混合均匀,并过200目筛网筛分得到模压所用粉体;在55MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1250℃常压烧结,保温2h,得到气孔率为60%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有3wt.%硅烷偶联剂的无水乙醇中进行表面改性,60℃保温5h;
2)将双酚F型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.6:0.02:0.102的比例在50℃下高速搅拌3h,混合均匀后,真空脱泡3h。将50℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.0%,抗弯强度为122.7MPa,热导率为5.5214W·m-1·k-1。
实施例3:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将65wt.%的Al2O3粉(0.5μm)、30wt.%的淀粉和5wt.%的PVA(固相含量15wt.%)混合均匀,并过200目筛网筛分得到模压所用粉体;在25MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1150℃常压烧结,保温2h,得到气孔率为70%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有2wt.%硅烷偶联剂的无水乙醇中进行表面改性,70℃保温3h;
2)将双酚S型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.9:0.04:0.0313的比例在60℃下高速搅拌4h,混合均匀后,真空脱泡4h。将60℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.4%,抗弯强度为110.8MPa,热导率为5.084W·m-1·k-1。
实施例4:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将80wt.%的Al2O3粉(10μm)、15wt.%的淀粉和5wt.%的PVA(固相含量10wt.%)混合均匀,并过150目筛网筛分得到模压所用粉体;在75MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1550℃常压烧结,保温1h,得到气孔率为48%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有4wt.%硅烷偶联剂的无水乙醇中进行表面改性,60℃保温3h;
2)将双酚A型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.86:0.03:0.128的比例在65℃下高速搅拌2h,混合均匀后,真空脱泡2h。将65℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.8%,抗弯强度为190.4MPa,热导率为6.212W·m-1·k-1。
实施例5:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将85wt.%的Al2O3粉(0.2μm)、10wt.%的淀粉和5wt.%的PVA(固相含量8wt.%)混合均匀,并过200目筛网筛分得到模压所用粉体;在85MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1400℃常压烧结,保温2h,得到气孔率为40%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有5wt.%硅烷偶联剂的无水乙醇中进行表面改性,65℃保温3h;
2)将双酚A型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.9:0.04:0.163的比例在55℃下高速搅拌3h,混合均匀后,真空脱泡3h。将55℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.3%,抗弯强度为195.5MPa,热导率为6.4231W·m-1·k-1。
实施例6:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)在研钵中将79wt.%的Al2O3粉(30μm)、16wt.%的淀粉和5wt.%的PVA(固相含量8wt.%)混合均匀,并过150目筛网筛分得到模压所用粉体;在60MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1200℃常压烧结,保温3h,得到气孔率为50%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有4wt.%硅烷偶联剂的无水乙醇中进行表面改性,80℃保温2h;
2)将双酚A型环氧树脂、固化剂、促进剂与纳米氧化铝颗粒按1:0.86:0.01:0.102的比例在50℃下高速搅拌2h,混合均匀后,混合均匀后,真空脱泡2h。将50℃预热的多孔Al2O3骨架置于环氧树脂、促进剂、固化剂和纳米氧化铝的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为0.6%,抗弯强度为147.1MPa,热导率为6.162W·m-1·k-1。
实施例7:
一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,包括下列步骤:
1)将重量比为75:20的Al2O3粉(10μm)和淀粉在酒精中球磨24h,烘干后,在研钵中将75wt.%的Al2O3粉(10μm)、20wt.%的淀粉和5wt.%的PVA(固相含量8wt.%)混合均匀,并过150目筛网筛分得到模压所用粉体;在80MPa压力下双向加压成型后获得氧化铝坯体。将压好的生坯放入高温空气炉中,于1400℃常压烧结,保温2h,得到气孔率为55%的多孔氧化铝陶瓷,在600℃以下为3℃/min,600℃~烧结温度为5℃/min,将得到的多孔Al2O3骨架表面研磨平整后,置于含有3wt.%硅烷偶联剂的无水乙醇中进行表面改性,80℃保温6h;
2)将双酚F型环氧树脂、固化剂、促进剂和纳米氧化铝按1:0.8:0.03:0.0864的比例在70℃下高速搅拌2h,混合均匀后,混合均匀后,真空脱泡3h。将80℃预热的多孔Al2O3骨架置于环氧树脂、促进剂和固化剂的混合溶液中浸渍1h,在烘箱中固化得到双连续相复合材料。复合材料的气孔率为1.1%,抗弯强度为139.8MPa,热导率为5.774W·m-1·k-1。
图1为本发明实施例1所得的多孔Al2O3骨架的显微结构照片。如图所示,经过1350℃高温烧结后,氧化铝颗粒直接形成烧结颈,颗粒直径相互连通。晶粒尺寸明显长大,孔径均匀分布,大部分孔径为0.1~3μm,同时试样中存在少量的大尺寸气孔。
图2为本发明实施例1所得的氧化铝/环氧树脂纳米复合材料的显微结构照片。如图所示,环氧树脂已基本均匀地浸渍入多孔Al2O3骨架中,氧化铝/环氧树脂界面结合状态良好,断口存在一定数量的孔,这是由于断裂过程颗粒拔出导致的。
Claims (10)
1.一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,该氧化铝/环氧树脂纳米复合材料通过将环氧树脂、固化剂、促进剂和纳米氧化铝颗粒的混合液体浸渍至多孔氧化铝陶瓷骨架中,经过高温固化得到;其中,多孔氧化铝陶瓷的气孔率为40%~70%,对应其在复合材料中的体积分数为70vol.%~40vol.%,均匀弥散分布在环氧树脂基体中的纳米氧化铝颗粒的体积分数为0.5vol.%~3vol.%,包括以下步骤:
1)将不同粒径的Al2O3粉、黏结助剂PVA、发泡剂淀粉混合均匀,混合粉体过筛,将筛分得到模压所用粉体置于模具中,在轴向压力作用下模压成型,将压好的生坯放入空气炉中进行高温烧结,保温后冷却至室温,得到气孔率为40%~70%、不同孔径的多孔Al2O3骨架,其中,烧结温度为1150~1550℃,保温时间为1~3h,将得到的多孔Al2O3骨架表面研磨平整后,置于含有2~5wt.%硅烷偶联剂的乙醇水溶液中进行表面改性,60~80℃保温2~5h,乙醇水溶液中按体积比:乙醇:水=95:5;
2)将步骤1)得到的表面改性后的多孔Al2O3骨架预热到50~80℃,将环氧树脂、固化剂、促进剂与纳米氧化铝按质量比为1:(0.6~0.9):(0.01~0.05):(0.0313~0.163)混合后,在50~80℃下搅拌2~4h,混合均匀后,真空脱泡2~4h,真空度为-0.095MPa;将预热的多孔Al2O3骨架置于环氧树脂、促进剂、固化剂和纳米氧化铝颗粒的混合溶液中,在50~80℃下真空脱泡2~4h,真空度为-0.095MPa,将真空浸渍后的样品放置在真空烘箱中进行固化,得到高导热热氧化铝/环氧树脂纳米复合材料。
2.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤1)中,Al2O3粉的平均粒径为0.2~30μm。
3.根据权利要求2所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤1)中,平均粒径为0.2μm、0.5μm的Al2O3粉的模压压力为25~45MPa,保压时间为1min;平均粒径为2μm、5μm的Al2O3粉的模压压力为45~65MPa,保压时间1min;平均粒径为10μm、30μm的Al2O3粉的模压压力为65~85MPa,保压时间1min。
4.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤1)中,混合粉体的过筛目数为150目或200目。
5.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤1)中,黏结助剂PVA的固相含量为8~15wt.%,黏结助剂PVA的质量分数为5wt.%,发泡剂淀粉的质量分数为10~25wt.%。
6.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤1)中,烧结温度的升温速率在600℃以下为3℃/min,600℃及以上为5℃/min。
7.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤2)中,环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂或者双酚S型环氧树脂中的任意一种,固化剂为甲基四氢邻苯二甲酸酐,促进剂为三苯酚。
8.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤2)中,纳米氧化铝颗粒倒入盛有去离子水的容器中,在室温条件下用磁力搅拌器进行1h的搅拌,在超声仪器中100℃超声分散1h,之后在烘箱中烘干。
9.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤2)中,纳米氧化铝颗粒置于含有2~5wt.%硅烷偶联剂的无水乙醇中进行表面改性,60~80℃保温2~5h。
10.根据权利要求1所述的一种高导热氧化铝/环氧树脂纳米复合材料的制备方法,其特征在于,步骤2)中,真空浸渍后的样品的固化制度为:95℃保温2h,升温至140℃保温3h,升温至170℃,保温4h,每个阶段的升温速率均为5℃/min。
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CN110358255A (zh) * | 2019-07-26 | 2019-10-22 | 南方科技大学 | 一种三维复合材料及其制备方法、应用和基板与电子装置 |
CN111574967A (zh) * | 2020-05-06 | 2020-08-25 | 苏州通富超威半导体有限公司 | 散热材料、应用该散热材料的芯片封装组件及制备方法 |
CN113667272A (zh) * | 2021-07-02 | 2021-11-19 | 华南理工大学 | 一种聚合物基高导热材料及其制备工艺 |
CN114025472A (zh) * | 2021-11-12 | 2022-02-08 | 百强电子(深圳)有限公司 | 高散热金属基印刷电路板及其制作方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08283538A (ja) * | 1995-04-14 | 1996-10-29 | Toshiba Chem Corp | 注形用エポキシ樹脂組成物 |
CN102234410A (zh) * | 2010-04-28 | 2011-11-09 | 上海合复新材料科技有限公司 | 导热型热固性模塑复合材料及其用途 |
CN102234187A (zh) * | 2010-04-29 | 2011-11-09 | 比亚迪股份有限公司 | 一种陶瓷复合材料及其制备方法 |
CN104788911A (zh) * | 2015-04-29 | 2015-07-22 | 华中科技大学 | 一种环氧树脂复合材料、其制备方法及应用 |
CN106633652A (zh) * | 2016-12-14 | 2017-05-10 | 国家电网公司 | 一种双连续相氧化铝/环氧树脂复合材料的制备方法 |
-
2018
- 2018-11-30 CN CN201811456671.3A patent/CN109608664A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08283538A (ja) * | 1995-04-14 | 1996-10-29 | Toshiba Chem Corp | 注形用エポキシ樹脂組成物 |
CN102234410A (zh) * | 2010-04-28 | 2011-11-09 | 上海合复新材料科技有限公司 | 导热型热固性模塑复合材料及其用途 |
CN102234187A (zh) * | 2010-04-29 | 2011-11-09 | 比亚迪股份有限公司 | 一种陶瓷复合材料及其制备方法 |
CN104788911A (zh) * | 2015-04-29 | 2015-07-22 | 华中科技大学 | 一种环氧树脂复合材料、其制备方法及应用 |
CN106633652A (zh) * | 2016-12-14 | 2017-05-10 | 国家电网公司 | 一种双连续相氧化铝/环氧树脂复合材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
王旗等: ""微/纳米氧化铝/环氧树脂复合材料热导率和击穿强度的研究"", 《绝缘材料》 * |
王聪: ""环氧树脂/氧化铝导热复合材料的结构设计和制备"", 《绝缘材料》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110358255A (zh) * | 2019-07-26 | 2019-10-22 | 南方科技大学 | 一种三维复合材料及其制备方法、应用和基板与电子装置 |
CN110358255B (zh) * | 2019-07-26 | 2022-07-05 | 南方科技大学 | 一种三维复合材料及其制备方法、应用和基板与电子装置 |
CN111574967A (zh) * | 2020-05-06 | 2020-08-25 | 苏州通富超威半导体有限公司 | 散热材料、应用该散热材料的芯片封装组件及制备方法 |
CN113667272A (zh) * | 2021-07-02 | 2021-11-19 | 华南理工大学 | 一种聚合物基高导热材料及其制备工艺 |
CN113667272B (zh) * | 2021-07-02 | 2022-06-14 | 华南理工大学 | 一种聚合物基高导热材料及其制备工艺 |
CN114025472A (zh) * | 2021-11-12 | 2022-02-08 | 百强电子(深圳)有限公司 | 高散热金属基印刷电路板及其制作方法 |
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