CN112793252A - 一种耐高温导热橡胶磁及其制备方法 - Google Patents
一种耐高温导热橡胶磁及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温导热橡胶磁及其制备方法。本发明的耐高温导热橡胶磁由若干耐热磁胶片层叠而成;所述耐热磁胶片由磁胶层和涂覆在磁胶层两面的导热层组成;所述磁胶层由磁粉、橡胶和助剂组成;所述导热层由导热填料和橡胶组成。本发明的耐高温导热橡胶磁的制备方法包括以下步骤:1)导热填料的表面预处理;2)导热浆料的制备;3)磁胶片的制备;4)将导热浆料涂覆在磁胶片两面,干燥固化,得到耐热磁胶片;5)将若干耐热磁胶片叠加后进行双向压制,再进行硫化,即得耐高温导热橡胶磁。本发明的橡胶磁的耐高温性能优异、导热性能优异,磁性能和物理性能与现有的橡胶磁相当,且制备工艺简单,便于实现大规模工业化生产。
Description
技术领域
本发明涉及粘结磁体材料技术领域,具体涉及一种耐高温导热橡胶磁及其制备方法。
背景技术
橡胶磁是一种由磁粉与合成橡胶复合,经挤出成型、压延成型、注射成型等工艺制成的具有柔软性、弹性及可扭曲的磁体,其既具有磁性,又保持了部分橡胶特性,可加工成条状、卷状、片状、块状、圆环及各种复杂形状。橡胶磁可以自由弯曲不开裂,尺寸形状可任意裁切,且制成的各向异性产品便于辐射多机充磁,有利于自动化生产。橡胶磁已经广泛应用于汽车、家电、办公自动化、驱动器等领域,而随着设备往集成化、微型化、高性能化的方向快速发展,对橡胶磁的散热性和耐高温性的要求也越来越高。然而,目前市面上常见的橡胶磁的最高使用温度只有100℃左右,在要求高温环境的汽车、高温密封箱、电机等行业使用受到限制。
因此,亟需开发一种更耐高温、导热性能优异的橡胶磁。
发明内容
本发明的目的在于提供一种耐高温导热橡胶磁及其制备方法。
本发明所采取的技术方案是:
一种耐高温导热橡胶磁,由若干耐热磁胶片层叠而成;所述耐热磁胶片由磁胶层和涂覆在磁胶层两面的导热层组成;所述磁胶层由磁粉、橡胶和助剂组成;所述导热层由导热填料和橡胶组成。
优选的,所述耐高温导热橡胶磁由以下质量百分比的组分组成:
磁粉:80%~90%;
橡胶:4%~8%;
导热填料:5%~10%;
助剂:1%~4%。
优选的,所述磁粉为锶铁氧体磁粉、钡铁氧体磁粉、钕铁硼磁粉、钐铁氮磁粉中的至少一种。
优选的,所述橡胶为丁腈橡胶、氢化丁腈橡胶、硅橡胶、丁苯橡胶、乙烯-乙酸乙烯酯橡胶、三元乙丙橡胶、丁基橡胶、乙华平橡胶中的至少一种。
进一步优选的,所述橡胶为丁腈橡胶、氢化丁腈橡胶中的至少一种。氢化丁腈橡胶的耐高温性能好,搭配防老剂、耐热剂和抗氧剂,可以在实现导热性的前提下,使橡胶磁的长期最高使用温度可达170℃。
优选的,所述导热填料为石墨、氮化硅、氮化硼、碳化硅、铁粉、氮化铝、二氧化硅、氧化铝中的至少一种。
优选的,所述导热填料由纳米级导热粉末和微米级导热粉末复配组成,微米级导热粉末之间相互堆积会存在较大的堆积空隙,而纳米级导热粉末可以填充这些堆积空隙,进而有利于增加导热粒子间的接触和形成导热通路,可以显著提高材料的导热性。
优选的,所述纳米级导热粉末、微米级导热粉末的质量比为1:4~1:6。
优选的,所述助剂为偶联剂、增塑剂、防老剂、硫化剂、耐热剂、润滑剂中的至少一种。
优选的,所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的至少一种。
优选的,所述增塑剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、偏苯三酸三辛酯中的至少一种。
优选的,所述防老剂为防老剂MB、防老剂D、防老剂RD、防老剂445、微晶蜡中的至少一种。
优选的,所述硫化剂为硫磺、金属氧化物、过氧化物中的至少一种。
优选的,所述耐热剂为氧化铁、氧化镁、甲基丙烯酸锌、甲基丙烯酸镁中的至少一种。
优选的,所述润滑剂为硬脂酸锌、硬脂酸钙、硬脂酸中的至少一种。
上述耐高温导热橡胶磁的制备方法包括以下步骤:
1)用偶联剂对导热填料进行表面处理,得到改性处理的导热填料;
2)将改性处理的导热填料、橡胶和有机溶剂混合均匀,得到导热浆料;
3)将磁粉、橡胶和助剂混合,进行混炼和破碎后压成磁胶片;
4)将导热浆料涂覆在磁胶片两面,干燥固化,得到耐热磁胶片;
5)将若干耐热磁胶片叠加后进行双向压制,再进行硫化,即得耐高温导热橡胶磁。
优选的,步骤1)所述偶联剂的用量为导热填料质量的0.8%~1.2%。
优选的,步骤2)所述有机溶剂为丙酮、乙酸乙酯、二丁酯、二甲苯中的至少一种。
优选的,步骤3)所述混炼的温度为135℃~145℃,混炼为12min~15min。
优选的,步骤4)中导热浆料在磁胶片两面的涂覆厚度为0.2mm~0.4mm。
本发明的有益效果是:本发明的橡胶磁的耐高温性能优异、导热性能优异,磁性能和物理性能与现有的橡胶磁相当,且制备工艺简单,便于实现大规模工业化生产。
具体来说:
1)本发明对导热填料进行了表面改性处理,提高了润湿性能,减少了团聚,确保了导热填料可以充分均匀分散在橡胶基材中,形成更多更密的接触导热链;
2)本发明将导热填料制成导热浆料涂覆在磁胶片的两面(常规的往橡胶基材中添加导热填料的方式对于提高材料的导热性效果很差,因为橡胶磁为保持高磁特性,已经填充了大量的磁粉,添加少量的导热填料对橡胶磁的导热性无提高,而大量添加导热填料又必然会降低橡胶磁的磁性能),既解决了橡胶磁导热性差的问题,又基本不影响橡胶磁的磁特性;
3)本发明将常规的单向叠压调整为倍数叠压与双向压制的方式,成型压延压力传递更加均匀,压力损失也比较小,橡胶磁经过压延取向后实现了高导热性,同时磁性能和物理性能与现有的橡胶磁相当。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1:
一种耐高温导热橡胶磁,其组成如下表所示:
表1一种耐高温导热橡胶磁的组成表
上述耐高温导热橡胶磁的制备方法包括以下步骤:
1)将纳米级氮化铝、微米级氧化铝和铝酸酯偶联剂(占纳米级氮化铝和微米级氧化铝总质量的1%)加入搅拌槽,密闭后在70Hz频率下搅拌30min,得到改性处理的导热填料;
2)将改性处理的导热填料、液体丁腈橡胶和丙酮按照质量比5:1:2混合加入搅拌机,超声搅拌30min,得到导热浆料;
3)将锶铁氧体磁粉、氢化丁腈橡胶、剩余的铝酸酯偶联剂、防老剂445、过氧化二苯甲酰、三烯丙基异氰脲酸酯(TAIC)、甲基丙烯酸锌和硬脂酸锌加入密炼机,混炼至140℃,混炼14min,再破碎后用压延机压成厚度1.0mm~1.1mm的磁胶片;
4)将导热浆料涂覆在磁胶片两面,涂覆厚度为0.3mm,再120℃干燥8min,得到耐热磁胶片;
5)将7片耐热磁胶片叠加后放入压延机,60℃双向叠压6次至最终厚度2.0mm,再将压好的片放入硫化炉,180℃硫化8min,即得耐高温导热橡胶磁。
实施例2:
一种耐高温导热橡胶磁,其组成如下表所示:
表2一种耐高温导热橡胶磁的组成表
上述耐高温导热橡胶磁的制备方法包括以下步骤:
1)将纳米级氮化铝、微米级氧化铝和铝酸酯偶联剂(占纳米级氮化铝和微米级氧化铝总质量的1%)加入搅拌槽,密闭后在70Hz频率下搅拌30min,得到改性处理的导热填料;
2)将改性处理的导热填料、液体丁腈橡胶和丙酮按照质量比5:1:2混合加入搅拌机,超声搅拌30min,得到导热浆料;
3)将锶铁氧体磁粉、氢化丁腈橡胶、剩余的铝酸酯偶联剂、防老剂445、过氧化二苯甲酰、三烯丙基异氰脲酸酯(TAIC)、甲基丙烯酸锌和硬脂酸锌加入密炼机,混炼至140℃,混炼14min,再破碎后用压延机压成厚度1.0mm~1.1mm的磁胶片;
4)将导热浆料涂覆在磁胶片两面,涂覆厚度为0.3mm,再120℃干燥8min,得到耐热磁胶片;
5)将7片耐热磁胶片叠加后放入压延机,60℃双向叠压6次至最终厚度2.0mm,再将压好的片放入硫化炉,180℃硫化8min,即得耐高温导热橡胶磁。
对比例1:
一种橡胶磁,除了用“6%的微米级氧化铝”替代“1%的纳米级氧化铝和5%的微米级氧化铝”以外,其余组成和制备方法与实施例1完全一样。
对比例2:
一种橡胶磁,除了用“6%的纳米级氮化铝”替代“1%的纳米级氧化铝和5%的微米级氧化铝”以外,其余组成和制备方法与实施例1完全一样。
对比例3:
一种橡胶磁,除了用“固体丁腈橡胶”替代“氢化丁腈橡胶”以外,其余组成和制备方法与实施例1完全一样。
对比例4:
市售无卤橡胶磁(广州金南磁性材料有限公司,未添加导热填料,粘结基材为固体丁腈橡胶)。
对比例5:
一种橡胶磁,其原料组成和原料配比与实施例1完全相同,其制备方法包括以下步骤:
1)将纳米级氮化铝、微米级氧化铝和铝酸酯偶联剂(占纳米级氮化铝和微米级氧化铝总质量的1%)加入搅拌槽,密闭后在70Hz频率下搅拌30min,得到改性处理的导热填料;
2)将改性处理的导热填料、液体丁腈橡胶和丙酮按照质量比5:1:2混合加入搅拌机,超声搅拌30min,得到导热浆料;
3)将锶铁氧体磁粉、氢化丁腈橡胶、导热浆料、剩余的铝酸酯偶联剂、防老剂445、过氧化二苯甲酰、三烯丙基异氰脲酸酯(TAIC)、甲基丙烯酸锌和硬脂酸锌加入密炼机,混炼至140℃,混炼14min,再破碎后用压延机压成厚度1.0mm~1.1mm的磁胶片;
4)将7片磁胶片叠加后放入压延机,60℃双向叠压6次至最终厚度2.0mm,再将压好的片放入硫化炉,180℃硫化8min,即得橡胶磁。
性能测试:
1)对实施例1~2和对比例1~5的橡胶磁进行不同温度下的老化测试(测试样条的大小规格为100mm×10mm×2mm),测试样品的硬度(Shore D)变化,测试结果如下表所示:
表3不同温度下老化样品的硬度变化测试结果
编号 | 100℃,96h | 120℃,96h | 140℃,96h | 160℃,96h | 180℃,96h |
实施例1 | +1 | +2 | +7 | +12 | +22 |
实施例2 | +1 | +2 | +7 | +12 | +22 |
对比例1 | +1 | +3 | +7 | +12 | +22 |
对比例2 | +1 | +3 | +7 | +11 | +22 |
对比例3 | +3 | +9 | +18 | +25 | +35 |
对比例4 | +4 | +9 | +17 | +27 | +34 |
对比例5 | +1 | +2 | +8 | +12 | +23 |
由表3可知:本发明的耐高温导热橡胶磁的耐老化性能更好。
2)对实施例1~2和对比例1~5的橡胶磁在长时间高温条件下的尺寸变化率进行测试(测试样条的大小规格为100mm×10mm×2mm),测试结果如下表所示:
表4长时间高温条件下的尺寸变化率测试结果
由表4可知:本发明的耐高温导热橡胶磁的尺寸变化率明显更小,说明其更加耐高温。
3)对实施例1~2和对比例1~5的橡胶磁的磁性能和物理性能进行测试(测试样条的大小规格为100mm×10mm×2mm),测试结果如下表所示:
表5磁性能和物理性能测试结果
注:磁性能采用ATM-4磁化特性自动测量仪进行测试。
由表5可知:本发明的耐高温导热橡胶磁的磁性能和物理性能与现有的橡胶磁相当,即本发明添加导热填料基本不影响橡胶磁的磁性能和物理性能。
4)对实施例1~2和对比例1~5的橡胶磁的导热系数进行测试(测试样条的大小规格为100mm×10mm×2mm),测试结果如下表所示:
表6导热系数测试结果
由表6可知:本发明将导热填料涂覆在磁胶片两面可以大幅提高胶磁片的导热系数。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种耐高温导热橡胶磁,其特征在于:所述耐高温导热橡胶磁由若干耐热磁胶片层叠而成;所述耐热磁胶片由磁胶层和涂覆在磁胶层两面的导热层组成;所述磁胶层由磁粉、橡胶和助剂组成;所述导热层由导热填料和橡胶组成。
2.根据权利要求1所述的耐高温导热橡胶磁,其特征在于:所述耐高温导热橡胶磁由以下质量百分比的组分组成:
磁粉:80%~90%;
橡胶:4%~8%;
导热填料:5%~10%;
助剂:1%~4%。
3.根据权利要求1或2所述的耐高温导热橡胶磁,其特征在于:所述磁粉为锶铁氧体磁粉、钡铁氧体磁粉、钕铁硼磁粉、钐铁氮磁粉中的至少一种。
4.根据权利要求1或2所述的耐高温导热橡胶磁,其特征在于:所述橡胶为丁腈橡胶、氢化丁腈橡胶、硅橡胶、丁苯橡胶、乙烯-乙酸乙烯酯橡胶、三元乙丙橡胶、丁基橡胶、乙华平橡胶中的至少一种。
5.根据权利要求1或2所述的耐高温导热橡胶磁,其特征在于:所述导热填料为石墨、氮化硅、氮化硼、碳化硅、铁粉、氮化铝、二氧化硅、氧化铝中的至少一种。
6.根据权利要求5所述的耐高温导热橡胶磁,其特征在于:所述导热填料由纳米级导热粉末和微米级导热粉末复配组成。
7.根据权利要求6所述的耐高温导热橡胶磁,其特征在于:所述纳米级导热粉末、微米级导热粉末的质量比为1:4~1:6。
8.根据权利要求1或2所述的耐高温导热橡胶磁,其特征在于:所述助剂为偶联剂、增塑剂、防老剂、硫化剂、耐热剂、润滑剂中的至少一种。
9.根据权利要求8所述的耐高温导热橡胶磁,其特征在于:所述偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的至少一种;所述增塑剂为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、偏苯三酸三辛酯中的至少一种;所述防老剂为防老剂MB、防老剂D、防老剂RD、防老剂445、微晶蜡中的至少一种;所述硫化剂为硫磺、金属氧化物、过氧化物中的至少一种;所述耐热剂为氧化铁、氧化镁、甲基丙烯酸锌、甲基丙烯酸镁中的至少一种;所述润滑剂为硬脂酸锌、硬脂酸钙、硬脂酸中的至少一种。
10.权利要求1~9中任意一项所述的耐高温导热橡胶磁的制备方法,其特征在于,包括以下步骤:
1)用偶联剂对导热填料进行表面处理,得到改性处理的导热填料;
2)将改性处理的导热填料、橡胶和有机溶剂混合均匀,得到导热浆料;
3)将磁粉、橡胶和助剂混合,进行混炼和破碎后压成磁胶片;
4)将导热浆料涂覆在磁胶片两面,干燥固化,得到耐热磁胶片;
5)将若干耐热磁胶片叠加后进行双向压制,再进行硫化,即得耐高温导热橡胶磁。
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