CN111716853B - 一种耐磨绝热复合材料及其制备方法 - Google Patents

一种耐磨绝热复合材料及其制备方法 Download PDF

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CN111716853B
CN111716853B CN202010575616.7A CN202010575616A CN111716853B CN 111716853 B CN111716853 B CN 111716853B CN 202010575616 A CN202010575616 A CN 202010575616A CN 111716853 B CN111716853 B CN 111716853B
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wear
resistant
fiber
composite material
resistant layer
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CN111716853A (zh
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王一靓
刘婷
左景奇
王明星
杨名波
杨军
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Zhuzhou Times New Material Technology Co Ltd
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Abstract

本发明公开了一种耐磨绝热复合材料及其制备方法，将耐磨层原料放入模具中加压并保压，在卸压、脱模后进行烧结制成耐磨层板材，然后将耐磨层板材经过萘‑钠处理液活化处理；将纤维或纤维‑织物浸渍胶黏剂，形成在纤维或纤维‑织物上有半固化物的增强层预浸料；将一层及以上重叠的增强层预浸料和耐磨层板材复合进行热压成型，制得耐磨绝热复合材料。本发明将耐磨材料和增强材料复合一体成型，在保证耐磨层和增强层的结合强度的情况下，免去粘接工序，保证了复合材料表面低温下具有耐磨性能和良好的机械强度高、绝缘、绝热性能。本发明复合材料应用于室温到绝对零度的低温环境下能同时满足绝缘、耐磨、绝热和结构支撑作用。

Description

一种耐磨绝热复合材料及其制备方法
技术领域
本发明涉及一种复合材料，尤其涉及一种耐磨绝热复合材料及其制备方法。
背景技术
随着低温运输、储存和运行设备的快速发展，对材料提出了在极低温下保持良好机械强度、绝热、绝缘并兼具耐磨性的要求，因此需要一种新型耐磨绝热复合材料可以在室温到绝对零度(-273℃)的低温环境下能同时满足绝缘、耐磨、绝热和结构支撑作用。
增强材料是由纤维增强材料为基材，以树脂作为粘合剂经热压而成的层压制品，低温下具有良好的机械强度高、绝缘、绝热性能，但耐磨性较差。耐磨材料具有良好的耐磨性，但是在机械强度不足，蠕变性能较大，易变形，不能起到支撑作用。
将耐磨材料和增强材料复合在一起通常是采用粘接的方法，借助胶粘剂在需要粘接的固体表面上所产生的粘合力，将不同种材料牢固地连接在一起的方法，但是存在粘接效果不好、结合强度不高、低温摩擦性能下降等不足。
发明内容
本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种耐磨绝热复合材料及其制备方法，以提升耐磨性能、机械强度和绝热性能。
为解决上述技术问题，本发明提出的技术方案为：
一种耐磨绝热复合材料的制备方法，包括下述的步骤：
S1.将耐磨层原料放入模具中加压并保压，在卸压、脱模后进行烧结制成耐磨层板材，然后将耐磨层板材经过萘-钠处理液活化处理；所述耐磨层原料包括按重量份计的下述组分：聚四氟乙烯微粉60～90份、二硫化钼2～10份、聚苯酯2～10份和空心玻璃微珠0～10份；
S2.将纤维或纤维-织物浸渍胶黏剂，形成在纤维或纤维-织物上有半固化物的增强层预浸料；
S3.将S2制备的一层及以上重叠的增强层预浸料和S1制备的耐磨层板材复合进行热压成型，制得耐磨绝热复合材料。
进一步的，S1所述加压压力为10～80MPa、保压1～10min。
进一步的，S1所述烧结温度320～420℃、保温2.5～6小时。
进一步的，S1所述萘-钠处理液是由等摩尔比的钠和萘溶解在四氢呋喃溶剂中形成的溶液。
进一步的，S2所述增强层预浸料包括按重量份计的下述组分：纤维或纤维-织物50～70份、半固化物30～50份和空心玻璃微珠0～10份，首先将空心玻璃微珠混合入胶黏剂。
进一步的，S2所述纤维包括玻璃纤维、玄武岩纤维、聚酯纤维、芳纶纤维或碳纤维中的一种或两种以上纤维的混合物，所述纤维-织物包括纤维丝、纤维短切毡、纤维缝编毡、纤维表面毡、纤维连续毡或纤维复合毡中的一种或两种以上的混合物。
进一步的，S2所述胶黏剂包括不饱和聚酯、酚醛胶黏剂、二苯醚胶黏剂、聚酰亚胺胶黏剂、聚胺酰亚胺胶黏剂、氨基树脂胶黏剂或环氧树脂胶黏剂中的一种或两种以上。
进一步的，S3所述复合是将裁剪后的一层及以上重叠的增强层预浸料摆放在模具上，再在上面放入耐磨层板材；或将耐磨层板材摆放在模具上再在上面放入一层及以上重叠的增强层预浸料；或将耐磨层板材摆放在模具上再在上面放入一层及以上重叠的增强层预浸料，再在上面放入耐磨层板材。
进一步的，S3所述热压成型温度在125℃～350℃、压力在4MPa～50Mpa。
本发明提供的一种耐磨绝热复合材料，采用上述方法制备而成。
与现有技术相比，本发明的有益效果为：
本发明将耐磨材料和增强材料复合一体成型，在保证耐磨层和增强层的结合强度的情况下，免去粘接工序，保证了复合材料表面低温下具有耐磨性能和良好的机械强度高、绝缘、绝热性能。本发明复合材料应用于室温到绝对零度(-273℃)的低温环境下能同时满足绝缘、耐磨、绝热和结构支撑作用。
具体实施方式
为了便于理解本发明，下文将结合较佳的实施例对本发明做更全面、细致地描述，但本发明的保护范围并不限于以下具体实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
本发明一个具体实施方式的耐磨绝热复合材料的制备方法，包括下述的步骤：
1.耐磨层的制备
耐磨层原料组成(质量份)：聚四氟乙烯微粉60～90份、二硫化钼2～10份、聚苯酯2～10份、空心玻璃微珠0～10份。其中聚四氟乙烯微粉是主体耐磨树脂，二硫化钼作为固体润滑剂、提升摩擦性能，聚苯酯改善机械强度和加工性能，空心玻璃微珠降低导热系数、提升树脂流动性。
耐磨层制备方法：将上述原料混合后，放入模具中加压，压力为10～80MPa、保压1～10min，然后卸压、脱模。之后进行烧结，使混合好的粉体聚合成板材，烧结温度320～420℃、保温2.5～6小时。烧结温度太大或太小都会降低材料的力学性能。最后将耐磨层经过萘-钠处理液的活化处理。萘-钠处理溶液是由等摩尔比的钠和萘溶解在四氢呋喃溶剂中形成的溶液。萘-钠活化可以改善聚四氟乙烯的表面粘接性能，提升粘接后的力学性能。
2.增强层预浸料的制备
将纤维或纤维-织物浸渍胶黏剂，然后根据需要进行烘焙，以便形成在纤维或纤维-织物上有半固化物的纤维预浸渍材料或纤维-织物预浸渍材料。可以将空心玻璃微珠混合入胶黏剂，然后再浸渍。增强层中增加起到隔热作用的空心玻璃微珠，导热系数大大降低。
增强层预浸料组成为(质量份)：纤维或纤维-织物50～70份、半固化物30～50份、空心玻璃微珠0～10份。
所述纤维可以为玻璃纤维、玄武岩纤维、聚酯纤维、芳纶纤维、碳纤维中的一种或一种以上纤维的混合物，所述纤维-织物可以为纤维丝、纤维短切毡、纤维缝编毡、纤维表面毡、纤维连续毡、以及纤维复合毡中的一种或两种以上的混合物。
所述胶黏剂包括不饱和聚酯、酚醛胶黏剂、二苯醚胶黏剂、聚酰亚胺胶黏剂、聚胺酰亚胺胶黏剂、氨基树脂胶黏剂或环氧树脂胶黏剂。
3.热压成型
将裁剪后的一层及以上重叠的纤维预浸渍或纤维-织物预浸料摆放在模具上，再在上面放入耐磨层；或耐磨层摆放在模具上再在上面放入一层及以上重叠的纤维预浸渍或纤维-织物预浸料；或将耐磨层板材摆放在模具上再在上面放入一层及以上重叠的增强层预浸料，再在上面放入耐磨层板材。优选设置成耐磨层-增强层-耐磨层夹心结构。模具与预浸料接触面涂有脱模剂或放置离型膜。
然后送入装有热板的普通热压机或真空热压机，控制温度在125℃～350℃、压力在4MPa～50MPa的条件下进行热压成型，然后出模制得耐磨绝热复合材料。通过热压保证了耐磨层和增强层的结合强度。
本发明在压制时通过预浸料中的胶黏剂粘结耐磨层，起到耐磨层与增强层的复合。由于在耐磨层中未加入起粘结作用的原料，耐磨层耐磨性能优异，摩擦系数可达到0.004。
以下通过实施例对本发明进行详细说明。
实施例1
1.耐磨层的制备：
原料组成：聚四氟乙烯微粉90份、二硫化钼5份、聚苯酯5份。放入模具中加压30MPa、保压5min，烧结温度370℃、保温5小时。耐磨层经过萘-钠处理液的活化处理，萘-钠处理溶液是由等摩尔比的钠和萘溶解在四氢呋喃溶剂中形成的溶液。
2.增强层预浸料的制备
将空心玻璃微珠混合入环氧树脂胶黏剂，然后将玻璃纤维浸渍胶黏剂，烘焙后形成在平纹玻璃布上有半固化物的玻璃纤维预浸渍材料，预浸料组成：玻璃纤维67份、半固化物30份、空心玻璃微珠3份。
3.热压成型
将上述制备的耐磨层摆放在模具上再在上面放入60层重叠的玻璃纤维预浸料，然后再在玻璃纤维预浸料放置耐磨层。然后送入装有热板的普通热压机或真空热压机，控制温度在165℃、压力在10MPa的条件下热压成型，然后出模制得耐磨绝热复合材料。经检测，各项性能如下表1。
表1
性能 检测方法 20℃ –160℃
压缩强度/MPa ISO 604:2002 511 685
层间剪切强度/MPa lEC60893ˉ2:2003 25 41
线性热膨胀系数/10-6K-1 ISO11359-2:1999 51 42
导热系数/W/m·K GB/T 10295-2008 0.15 0.14
摩擦系数 TB/T 2331-2013 0.004 0.004
实施例2
1.耐磨层的制备：
原料组成：聚四氟乙烯微粉85份、二硫化钼7份、聚苯酯2份、空心玻璃微珠6份。放入模具中加压20MPa、保压3min，烧结温度370℃、保温5小时。耐磨层经过萘-钠处理液的活化处理，萘-钠处理溶液是由等摩尔比的钠和萘溶解在四氢呋喃溶剂中形成的溶液。
2.增强层预浸料的制备
将空心玻璃微珠混合入聚胺酰亚胺胶黏剂，然后将玻璃纤维浸渍胶黏剂，烘焙后形成在平纹芳纶布上有半固化物的芳纶纤维预浸渍材料，预浸料组成：芳纶纤维65份、半固化物30份、空心玻璃微珠5份。
3.热压成型
将上述制备的耐磨层摆放在模具上再在上面放入150层重叠的芳纶纤维预浸料，然后送入装有热板的普通热压机或真空热压机，控制温度在320℃、压力在7MPa的条件下热压成型，然后出模制得耐磨绝热复合材料。经检测，各项性能如下表2。
表2
性能 检测方法 20℃ –160℃
压缩强度/MPa ISO 604:2002 720 781
层间剪切强度/MPa lEC60893ˉ2:2003 35 61
线性热膨胀系数/10-6K-1 ISO 11359-2:1999 45 38
导热系数/W/m·K GB/T 10295-2008 0.13 0.11
摩擦系数 TB/T 2331-2013 0.004 0.004
上述实施例表明，本发明在常温到低温环境下能同时满足耐磨、绝热和结构支撑作用。
上述只是本发明的较佳实施例，并非对本发明作任何形式上的限制。因此，凡是未脱离本发明技术方案的内容，依据本发明技术实质对以上实施例所做的任何简单修改、等同变化及修饰，均应落在本发明技术方案保护的范围内。

Claims (7)

1.一种耐磨绝热复合材料的制备方法，其特征在于，包括下述的步骤：
S1. 将耐磨层原料放入模具中加压并保压，在卸压、脱模后进行烧结制成耐磨层板材，然后将耐磨层板材经过萘-钠处理液活化处理；所述耐磨层原料包括按重量份计的下述组分：聚四氟乙烯微粉60~90份、二硫化钼2~10份、聚苯酯2~10份和空心玻璃微珠0~10份；
S2. 将纤维或纤维-织物浸渍胶黏剂，形成在纤维或纤维-织物上有半固化物的增强层预浸料；所述胶黏剂包括不饱和聚酯、酚醛胶黏剂、二苯醚胶黏剂、聚酰亚胺胶黏剂、聚胺酰亚胺胶黏剂、氨基树脂胶黏剂或环氧树脂胶黏剂中的一种或两种以上；所述增强层预浸料包括按重量份计的下述组分：纤维或纤维-织物50～70份、半固化物30~50份和空心玻璃微珠3~10份，首先将空心玻璃微珠混合入胶黏剂；
S3. 将S2制备的一层及以上重叠的增强层预浸料和S1制备的耐磨层板材复合进行热压成型，制得耐磨绝热复合材料；所述热压成型温度在125℃～350℃、压力在4MPa～50Mpa。
2.根据权利要求1所述的耐磨绝热复合材料的制备方法，其特征在于，S1所述加压压力为10~80MPa、保压1~10min。
3.根据权利要求1或2所述的耐磨绝热复合材料的制备方法，其特征在于，S1所述烧结温度320~420℃、保温2.5~6小时。
4.根据权利要求1或2所述的耐磨绝热复合材料的制备方法，其特征在于，S1所述萘-钠处理液是由等摩尔比的钠和萘溶解在四氢呋喃溶剂中形成的溶液。
5.根据权利要求1的耐磨绝热复合材料的制备方法，其特征在于，S2所述纤维包括玻璃纤维、玄武岩纤维、聚酯纤维、芳纶纤维或碳纤维中的一种或两种以上纤维的混合物，所述纤维-织物包括纤维丝、纤维短切毡、纤维缝编毡、纤维表面毡、纤维连续毡或纤维复合毡中的一种或两种以上的混合物。
6.根据权利要求1所述的耐磨绝热复合材料的制备方法，其特征在于，S3所述复合是将裁剪后的一层及以上重叠的增强层预浸料摆放在模具上，再在上面放入耐磨层板材；或将耐磨层板材摆放在模具上再在上面放入一层及以上重叠的增强层预浸料；或将耐磨层板材摆放在模具上再在上面放入一层及以上重叠的增强层预浸料，再在上面放入耐磨层板材。
7.一种耐磨绝热复合材料，其特征在于，采用权利要求1~6任一项所述方法制备而成。
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