CN102027054A - 热固性环氧树脂,复合材料,形成复合材料制品的方法,模具和制造模具的方法 - Google Patents
热固性环氧树脂,复合材料,形成复合材料制品的方法,模具和制造模具的方法 Download PDFInfo
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Abstract
一种热固性环氧树脂,所述热固性环氧树脂含有磁铁矿颗粒和导电性碳颗粒来起到微波受体的作用。一种复合材料,所述复合材料包含具有磁铁矿颗粒的热固性环氧树脂基质相和碳纤维增强相。一种复合物制品用模具,所述模具包含具有含有微波辐射吸收材料的表面或后表面层的由基本上可被微波辐射透过的材料制成的模具主体。
Description
技术领域
本发明涉及热固性复合材料的领域。具体而言,本发明涉及热固性复合材料的微波固化领域。
背景技术
纤维/环氧树脂复合物在单面模具中的热固化是一项已建立的工业技术。通过施加热能,通常以烘箱或高压釜中的热空气对流进行热固化。这种方法进行缓慢而且使用了大量能量来加热空气和设备。随后必须将热空气排出并冷却热的设备。另外,因为设备要花费时间来达到相关的温度,所以工具面有更多时间由于热膨胀而延展。那样可以给最终制品的形状带来误差。
使用电磁能在较短时间中固化环氧树脂是已知的。使用电磁能例如无线电能或微波能固化环氧树脂的优点在于只对环氧树脂本身加热,因而可显著地节省能量。另外,因为模具本身不会变得过热,由于固化时间较短,由热膨胀引起的容许误差因而得到减小。
微波固化的一个实例为申请人为General Motors Corporation的美国专利第4626642号中所示的热固性聚合物。在该情况下,热固性聚合物用作将汽车塑料部件固定在一起的粘合剂。该热固性聚合物含有环氧树脂和附加的钢或铝纤维或粉末。石墨纤维被描述为替代性的添加剂。
日本专利第5-79208号公报中描述了含有环氧树脂和Kevlar纤维的增强塑料的微波固化方法。美国专利第6566414号描述了微波放热促进剂的添加。该文献本身关注的是将所述树脂组合物应用至沥青、混凝土和石板瓦中。
发明内容
本发明的一个目的在于提供一种改进的热固性环氧树脂。
本发明的第一方面提供了一种热固性环氧树脂,所述热固性环氧树脂含有磁铁矿颗粒和导电性碳材料颗粒。
导电性碳材料如石墨粉末和磁铁矿的组合具有现有技术中的单一物质添加剂环氧树脂未显现出的有益效果和增效作用。具体而言,磁铁矿在高于临界温度时起到有效微波受体的作用,而碳受体则从较低温度开始起作用。通过将所述两种物质组合进入热固性环氧树脂,提供了从低温开始直至热固温度均对微波加热有良好的敏感性的树脂材料。
本发明的一个目的在于提供一种改进的复合材料。
本发明的第二方面提供了一种复合材料,所述复合材料包含含有磁铁矿颗粒的热固性环氧树脂基质和铺敷好的碳纤维增强体。
碳纤维增强材料提供了低温微波敏感性而热固性环氧树脂中包含磁铁矿颗粒则提供了较高温度下的微波敏感性。必要时可向环氧树脂中加入额外的导电性碳材料。
本发明的一个目的在于提供一种改进的形成复合材料制品的方法。
本发明的第三方面提供了一种形成复合材料制品的方法,所述方法包括以下步骤:提供包含至少一种含有磁铁矿颗粒的热固性环氧树脂的基质材料,提供基本为微波透射材料的模具,提供碳纤维增强材料,在模具中铺敷基质材料和增强材料,并对铺敷好的材料施加微波辐射,从而进行树脂的热固化。
以该方式,树脂的微波加热引起了热固化,而且磁铁矿颗粒的存在与碳纤维增强材料的存在一起提供了上述碳和磁铁矿的组合的增效微波受体作用。
本发明的第四方面提供了一种用于模制复合材料制品的模具,所述模具包含由基本上可被微波辐射透过的材料形成的模具主体和在其工作表面上或邻近其工作表面处具有微波受体的工具面。
以该方式,在将复合材料铺敷在模具上并施加微波能时,模具本身吸收了极少的微波能,而通过在模具表面上或邻近模具表面处提供微波受体,将局部地吸收微波能,并且将引发促使至少在复合材料外侧模线处进行热固化的局部加热。
本发明的第五方面提供了一种制造用于模制复合材料制品的模具的方法,所述方法包括以下步骤:提供基本为微波透射材料的模具主体,提供工具面和将微波辐射吸收材料纳入工具面中,或者将微波辐射吸收材料施加在工具面的工作表面上。
本发明的其它优点将在所附的权利要求书中加以阐述。
附图说明
现将通过实施例并参照附图具体描述本发明各方面的实施方式,其中:
图1a和图1b是纤维增强复合材料的基质相和增强相的示意图;
图2是复合材料的示意图;
图3是本发明的模具的示意性截面图;
图4是本发明的另一模具的示意性截面图;和
图5是图4所示的模具的示意性截面图,其中显示了在该模具上铺敷有复合材料。
具体实施方式
图1a和图1b分别示出了碳纤维复合材料的基质相和增强相。基质相10包含具有以1体积%~5体积%分散在其中的磁铁矿颗粒12的热固性环氧树脂。磁铁矿颗粒的尺寸优选为5纳米~100纳米。
树脂和磁铁矿混合物可以如下形成:提供具有高浓度磁铁矿粉末的初始树脂母料,随后将该初始树脂母料混合至较大体积的树脂中,以提供树脂中优选的磁铁矿体积比例。
图1b示出了所述复合碳纤维材料的碳纤维增强相14。所述碳纤维增强相通常由形成为纱线并接着以多种不同方式纺制的石墨纤维制成。
在碳纤维增强相14与环氧树脂基质相组合时形成复合碳纤维/环氧树脂材料。可在模制前进行这两种物质的组合,例如在所谓的“预浸渍”过程中组合。作为替代,可以在模具中铺敷材料时进行环氧树脂和碳纤维的组合。
注意到,通过对前述碳纤维/环氧树脂/磁铁矿材料施加微波辐射,碳纤维中的石墨丝从低温开始起到微波受体的作用,这意味着所述碳纤维吸收微波能并将该能量转化为热,并加热所述碳纤维周围的环氧树脂基质材料。该碳纤维继而对磁铁矿粉末进行加热,在一定量的加热后,所述磁铁矿颗粒也会起到微波受体的作用。在相当接近的热接近性中磁铁矿和碳纤维的增效剂组合在通过施加微波能热固化环氧树脂的应用中特别有用。通过在复合材料中提供微波受体,需要施加在特定复合材料模具上的微波能的量得以降低。
虽然据预计复合材料中存在的碳纤维将足以从低温开始起到微波受体的作用,但是可能必要的是以石墨粉末或碳纳米管形式加入额外的碳。在该情况下,加入至热固性环氧树脂中的额外的碳材料应包含0.5%~2%的体积分数。可以使用10nm~60nm炭黑形式的石墨粉末。可以使用直径为5nm~20nm、长度为1nm~100nm的碳纳米管。
优选的是,微波受体添加剂总量相对于环氧树脂应小于或等于5体积%。
转向图3,模具18包含模具基体20和装在该模具基体20上的模具工具面22。该模具工具面22具有外表面24,倚靠该外表面24将放置复合碳纤维增强材料的外侧模线。
在图3的实施方式中,模具基体20由微波可相对透射的材料形成,这意味着微波能不会轻易地被模具基体20的材料所吸收。通常,微波透射材料将包含陶瓷材料。最具体的是,陶瓷纤维材料将形成所述模具基体20。如上所述,模具工具面22最优选在表面24上或在邻近表面24处由含有一定比例微波受体的材料形成。
在图3所示的实施例中,模具工具面22由添加有微波受体的硅酸盐/玄武岩纤维材料形成。所述微波受体可以是石墨或铁氧体材料,如磁铁矿。在生成模具工具面22时可以通过混合将该受体引入硅酸盐纤维中。
图4示出了与图3中的模具基本相似的模具18,其中与图3中的部件相对应的部件使用了相同的参引数字。
正如图3的模具18那样,图4的模具18包含由微波透射材料形成的模具基体20,如对图3的描述所述。在图4中,模具18具有装在模具基体20上的模具工具面22。在这种情况下,模具工具面22也由基本上可被微波透射的材料形成。在图4的模具18中,模具表面24具有含有一定比例微波受体材料的涂层26。通过在模具表面24涂粉、通过粉末涂覆模具表面24或通过刷涂载体和微波受体材料的乳液可以涂覆涂层26。图4配置的优点在于施加在模具18上的微波能仅仅引起涂覆有微波受体材料26处的局部加热,即在最需要热量进行热固化的工具面22的表面24上引起局部加热。该工具的其余区域不吸收微波能。在现有的模制配置中,将模具18配置在高压釜中,而且整个高压釜和模具需要受热以达到环氧树脂的热固化温度。而本发明的情况中,将模具配置在大型微波系统的内部且微波能并不被模具其余部分所吸收。大部分微波能被涂敷在模具表面的微波敏感性材料和碳纤维增强复合材料中的微波受体所吸收。
图5示出了带有复合材料的图4的模具,所述复合材料含有碳纤维增强材料和其中具有磁铁矿颗粒的环氧树脂基质。
在将碳纤维复合物铺敷在所述模具上时施加微波能,并且模具基体20和模具工具面22吸收了极少量的微波辐射。微波受体如涂敷在工具面22表面上的层26中的磁铁矿和/或石墨和碳纤维增强基质中的石墨和磁铁矿颗粒吸收了微波能并将其转化成使环氧树脂基质材料热固化的热量。
对所述模具施加的微波辐射的频率优选为约2.45GHz,其为家用微波炉的常用频率。
Claims (25)
1.一种热固性环氧树脂,所述热固性环氧树脂含有磁铁矿颗粒和导电性碳材料颗粒。
2.如权利要求1所述的热固性环氧树脂,其中,所述磁铁矿颗粒的尺寸为5纳米~100纳米。
3.如权利要求1或2所述的热固性环氧树脂,其中,所述导电性碳材料包含石墨粉末。
4.如权利要求1或2所述的热固性环氧树脂,其中,所述导电性碳材料包含碳纳米管。
5.如前述权利要求中任一项所述的热固性环氧树脂,其中,所述导电性碳材料包含石墨粉末与碳纳米管的混合物。
6.如前述权利要求中任一项所述的热固性环氧树脂,其中,所述磁铁矿颗粒以所述树脂的1体积%~5体积%,最优选为3体积%~5体积%的量提供。
7.如前述权利要求中任一项所述的热固性环氧树脂,其中,所述导电性碳材料颗粒以所述树脂的0.5体积%~5体积%,最优选为0.5体积%~2体积%的量提供。
8.如前述权利要求中任一项所述的热固性环氧树脂,其中,所述磁铁矿和导电性碳材料的颗粒一起形成所述树脂的小于或等于5体积%。
9.一种复合材料,所述复合材料包含含有磁铁矿颗粒的热固性环氧树脂基质和碳纤维增强体。
10.如权利要求9所述的复合材料,所述复合材料作为预浸渍材料形成。
11.如权利要求9或10所述的复合材料,所述复合材料还含有导电性碳材料颗粒。
12.如权利要求9、10或11所述的复合材料,其中,所述磁铁矿颗粒的尺寸为5纳米~100纳米。
13.如权利要求11所述的复合材料,其中,所述导电性碳材料包含石墨粉末。
14.如权利要求11所述的复合材料,其中,所述导电性碳材料包含碳纳米管。
15.如权利要求11所述的复合材料,其中,所述导电性碳材料包含石墨粉末与碳纳米管的混合物。
16.如前述权利要求中任一项所述的复合材料,其中,所述磁铁矿颗粒以所述树脂的1体积%~5体积%,最优选为3体积%~5体积%的量提供。
17.如权利要求11或13~15中任一项所述的复合材料,其中,所述导电性碳材料颗粒以所述树脂的0.5体积%~5体积%,最优选为0.5体积%~2体积%的量提供。
18.如权利要求11或13~15中任一项所述的复合材料,其中,所述磁铁矿和导电性碳材料的颗粒一起形成所述树脂的小于或等于5体积%。
19.一种形成复合材料制品的方法,所述方法包括以下步骤:
提供包含至少一种热固性环氧树脂和磁铁矿颗粒的基质材料,提供基本为微波透射材料的模具,提供碳纤维增强材料,在所述模具中铺敷所述基质材料和增强材料,并对铺敷好的材料施加微波辐射,从而进行树脂的热固化。
20.一种用于模制复合材料制品的模具,所述模具包含:
由基本上可被微波辐射透过的材料形成的模具主体,和
在其工作表面上或邻近其工作表面处具有微波辐射吸收材料的工具面。
21.一种用于模制复合材料制品的模具的制造方法,所述方法包括以下步骤:
提供基本为微波透射材料的模具主体,提供工具面和将微波辐射吸收材料纳入所述工具面中,或者将所述微波辐射吸收材料涂覆在所述工具面的工作表面上。
22.如权利要求21所述的模具的制造方法,其中,将所述微波辐射吸收材料涂覆在所述工具面的工作表面上的步骤包括:在模制前通过刷涂法、粉末涂覆法或集尘法用所述微波辐射吸收材料涂覆所述工具面的工作表面。
23.如权利要求22所述的用于模制复合物制品的模具的制造方法,其中,将所述微波辐射吸收材料纳入所述工具面中的步骤包括:将所述微波辐射吸收材料加入至用于形成所述工具面的陶瓷中。
24.如权利要求19~23中任一项所述的形成复合材料制品的方法、用于模制复合材料制品的模具和用于模制复合材料制品的模具的制造方法,其中,所述基本为微波透射材料的模具主体包含硅酸盐陶瓷。
25.如权利要求20~23中任一项所述的模具或用于模制复合材料制品的模具的制造方法,其中,所述微波辐射吸收材料包含磁性和/或导电性碳材料的颗粒。
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GBGB0808636.5A GB0808636D0 (en) | 2008-05-13 | 2008-05-13 | A thermosetting epoxy resin,a composite material,a method of forming a composite material article,a mould and a method of making a mould |
PCT/GB2009/050499 WO2009138782A2 (en) | 2008-05-13 | 2009-05-11 | A thermosetting epoxy resin, a composite material, a method of forming a composite material article, a mould and a method of making a mould |
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2008
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2009
- 2009-05-11 CN CN2009801169103A patent/CN102027054B/zh not_active Expired - Fee Related
- 2009-05-11 BR BRPI0912508A patent/BRPI0912508A2/pt not_active IP Right Cessation
- 2009-05-11 EP EP09746099A patent/EP2285880A2/en not_active Withdrawn
- 2009-05-11 RU RU2010149142/05A patent/RU2499013C2/ru not_active IP Right Cessation
- 2009-05-11 US US12/936,928 patent/US20110031433A1/en not_active Abandoned
- 2009-05-11 KR KR1020107027922A patent/KR20110020809A/ko not_active Application Discontinuation
- 2009-05-11 CA CA2721237A patent/CA2721237A1/en not_active Abandoned
- 2009-05-11 JP JP2011509009A patent/JP2011521044A/ja active Pending
- 2009-05-11 WO PCT/GB2009/050499 patent/WO2009138782A2/en active Application Filing
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103946936A (zh) * | 2011-09-20 | 2014-07-23 | 大同特殊钢株式会社 | 电抗器及用于电抗器的复合物 |
CN103372985A (zh) * | 2012-04-25 | 2013-10-30 | 空中客车营运有限公司 | 复合材料的微波固化 |
CN105283513A (zh) * | 2013-06-03 | 2016-01-27 | 昭和电工株式会社 | 微波加热用导电性树脂组合物 |
CN103525013A (zh) * | 2013-10-17 | 2014-01-22 | 嘉兴市隆鑫碳纤维制品有限公司 | 一种导电碳纤维复合材料及其制备方法 |
CN104552989A (zh) * | 2015-01-23 | 2015-04-29 | 南京航空航天大学 | 微波加热快速拉挤制备玻璃纤维复合材料Z-Pin的设备及方法 |
CN104760304A (zh) * | 2015-03-19 | 2015-07-08 | 南京航空航天大学 | 一种紫外固化快速拉挤制备玻璃纤维复合材料Z-pin的设备及其制备方法 |
CN107428961A (zh) * | 2015-06-03 | 2017-12-01 | 三菱重工业株式会社 | 树脂复合材料、其固化方法及树脂成型品 |
CN104946108A (zh) * | 2015-06-26 | 2015-09-30 | 广东元星工业新材料有限公司 | 喷涂聚脲弹性体模具及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2721237A1 (en) | 2009-11-19 |
US20110031433A1 (en) | 2011-02-10 |
KR20110020809A (ko) | 2011-03-03 |
JP2011521044A (ja) | 2011-07-21 |
CN102027054B (zh) | 2013-08-14 |
WO2009138782A2 (en) | 2009-11-19 |
RU2010149142A (ru) | 2012-06-20 |
RU2499013C2 (ru) | 2013-11-20 |
EP2285880A2 (en) | 2011-02-23 |
BRPI0912508A2 (pt) | 2015-10-13 |
WO2009138782A3 (en) | 2010-03-04 |
GB0808636D0 (en) | 2008-06-18 |
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