CN109545549A - 一种具有高介电性能的复合材料及其制备方法 - Google Patents
一种具有高介电性能的复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有高介电性能的复合材料及其制备方法,是将金属盐、有机配体2,5‑二羟基对苯二甲酸及模板助剂水杨酸在室温下反应获得金属有机框架材料;将金属有机框架材料分散于甲醇中进行水热反应,产物离心烘干后获得金属有机框架材料前驱体,该前驱体置于高温炉中惰性气体气氛下进行碳化处理后与碱性溶液混合,离心后在高温惰性气体气氛下煅烧处理;与酸性溶液混合,洗去残留的碱性物质,水洗后干燥,得到所需石墨烯碳纳米带材料;然后石墨烯碳纳米带材料与树脂、粉体混合制得三相复合材料。本方法所得复合体系介电损耗低,同时兼顾介电常数,达到提升复合材料介电性能的目的。
Description
技术领域
本发明涉及一种复合材料介电性能的提升方法,尤其适用于薄膜型聚合物基的复合材料。
背景技术
在电子科技领域,复合材料的介电性能对产品最终性能具有重大的影响。以应用于电容材料的复合体系来说,如何提升其介电常数,抑制其介电损耗对于提升电子产品信号完整性等意义重大。如果使用纯聚合物作为电容使用,其本身的介电常数非常低,一般只有3-4,而具有实际应用意义的材料,介电常数一般要在20以上,介电损耗控制在0.05左右,通过在其体系中添加第二相材料是一种很好的选择。最常用的是使用具有高介电常数的无机粉体,如钛酸钡、钛酸锶等,但是为了获得高的介电常数,无机粉体的添加量通常会很高,一般体积分数在50%以上,这会大大降低材料的机械性能。添加导电粒子,如纳米银、铜等,使其添加量达到渗流阈值附近可以大大提升复合材料的介电常数,但是由于纳米粒子容易团聚,内部形成了很长的导电回路,造成介电损耗大大上升。通过对纳米金属粒子,进行改性,提升材料的分散性,对改善介电损耗过大有一定帮助,但是效果仍不理想。添加碳材料如碳纳米管,由于其具有极大的比表面积,只需要很低的添加量就可以达到渗流阈值。同时,可以形成“微电容”结构,有效提升材料的介电性能。但是一般这类材料的尺寸都是微米级,在电子产品日趋薄形化,多功能化的今天,容易引起复合材料出现短路的问题。纳米级的石墨烯近年来得到了广泛的关注,但是由于其带隙为零,导电性能极强,造成较大的介电损耗,也不符合电子产品的发展趋势。因此,迫切需要一种具有高介电性能的复合材料。
发明内容
发明目的:为了克服现有技术的不足,本发明所要解决的技术问题是提供一种具有高介电性能的复合材料及其制备方法,添加具有结构可控的金属有机框架材料基纳米碳材料于介电粉体/聚合物复合体系中,利用纳米材料的结构控制,达到降低其导电性,降低介电损耗,同时兼顾复合体系的介电常数,达到提升复合材料介电性能的目的。
技术方案:为解决上述技术问题,本发明是这样实现的:
一种具有高介电性能的复合材料,包括电极基材,在电极基材的一侧涂覆有树脂/介电粉体/导电性可控碳纳米带的三相复合材料,涂层厚度控制在 5~30um,所得复合材料的介电常数大于20,介电损耗低于0.05。
所述的导电基材为铜箔或者铝箔;聚合物是环氧树脂、聚酰亚胺或者聚四氟乙烯;采用的溶剂为乙醇、丙酮、丁酮或者乙酸乙酯;介电粉体是钛酸钡、钛酸锶或者钛酸锶钡。
一种具有高介电性能的复合材料的制备方法,步骤如下:
(1)、金属有机框架材料的制备:金属盐、有机配体2,5-二羟基对苯二甲酸及模板助剂水杨酸在室温下反应0.5~1h,产物使用溶剂洗涤、离心,获得金属有机框架材料;
所述的金属盐为锌盐或者镁盐;溶剂为N,N-二甲基甲酰胺或者甲醇;
离心速度500~1000rpm,离心时间5~10min。
该步骤(1)中的金属盐、有机配体及模板助剂的比例调节可控最终产物石墨烯碳纳米带材料的结构与性质。
(2)、金属有机框架材料前驱体的制备:将步骤(1)获得的金属有机框架材料分散于甲醇中进行水热反应,水热反应温度在100~150℃,反应时间在24~48h,产物离心烘干后获得所需的金属有机框架材料前驱体。
(3)、碳化金属有机框架材料的制备:将步骤(2)获得的金属有机框架材料前驱体置于高温炉中惰性气体气氛下进行碳化处理。处理温度分为三个阶段,第一阶段从室温升温至1000~1200℃,持续时间为3~6h,第二阶段为保温阶段,温度为1000~1200℃,持续时间为0.5~4h,第三阶段为降温阶段,持续时间1~3h。
(4)、金属离子插层的碳化金属有机框架材料的制备:将获得的碳化金属有机框架材料,与碱性溶液混合,超声混合均匀,离心后继续在高温炉中惰性气体气氛下进行煅烧处理,处理温度也为三个阶段,第一阶段从室温升温至500~1000℃,持续时间为3~6h,第二阶段为保温阶段,温度为500~ 1000℃,持续时间为0.5~4h,第三阶段为降温阶段,持续时间1~3h,得到金属离子插层的碳化金属有机框架材料。
所述的碱性溶液为氢氧化钾或者氢氧化钠。惰性气体是氮气或者氩气。
(5)、石墨烯碳纳米带材料的制备:将获得的金属离子插层的碳化金属有机框架材料与酸性溶液混合,洗去残留的碱性物质,水洗后干燥,得到所需石墨烯碳纳米带材料;
(6)树脂/介电粉体/导电性可控碳纳米带三相复合材料的制备:将获得的导电性可控的石墨烯碳纳米带加入介电粉体/聚合物的复合溶液,混合均匀后涂布于导电基材上,经过固化后,得到一侧带有电极基材的复合薄膜材料。
涂层厚度控制在5~30um。固化温度为100~180℃,固化时间为0.5~ 4h。所得复合材料的介电常数大于20,介电损耗低于0.05。
导电基材为铜箔或者铝箔;
聚合物是环氧树脂、聚酰亚胺或者聚四氟乙烯;
采用的溶剂为乙醇、丙酮、丁酮或者乙酸乙酯;
介电粉体是钛酸钡、钛酸锶或者钛酸锶钡;
混合过程采用超声,超声时间控制在10~30min,温度为室温~50℃之间。
可以通过添加一些助剂,如润湿分散剂、防沉降剂来提升添加材料在聚合物溶液体系中的分散性。
本发明有以下积极的效果:通过控制碳化剥离的金属有机框架材料结构,进而控制其所得材料的导电性能。金属离子插层的碳化金属有机框架材料具有的层状结构保证了在低添加量下能够有效增强介电常数,而降低的导电性能,有利于抑制介电损耗的提升,将其作为添加材料加入介电粉体/聚合物基的复合材料中,可以达到有效提升介电性能的目的。
附图说明
图1是导电碳纳米带/介电粉体/聚合物复合体系示意图:其中:1-导电基材、2-聚合物基材、3-添加材料、4-无机介电粉体,5-银浆电极。
图2是实施例1所得钛酸钡/环氧树脂/导电纳米带的扫描电镜图:形貌描述其中:6-环氧树脂,7-钛酸钡粉体,8-导电碳纳米带。
图3是金属有机框架材料的电镜图;
图4是导电性可控的石墨烯碳纳米带。
具体实施方式
下面结合具体实施方式对本发明做进一步的详细说明。
实施例1钛酸钡/环氧树脂/导电纳米带的制备
选择硫酸锌为金属离子来源(0.4g),2,5-二羟基对苯二甲酸为有机配体(0.15g),水杨酸为助剂(0.05g),溶于N,N-二甲基甲酰胺溶液中进行反应,温度为室温,反应时间为30min。将反应后的金属有机框架材料静置 15min分层后,除去上层清液。将下层沉淀物用N,N-二甲基甲酰胺和无水甲醇各离心清洗三次。离心速度为500rpm,离心时间为5min。
将洗净的金属有机框架材料分散于无水甲醇中,置于谁热反应釜,于 120℃下反应36h。将获得的产品在烘箱中100℃烘干12h,再于真空烘箱中 150℃烘干24h,得到需要的金属有机框架材料前驱体。
将金属有机框架材料置于高温管式炉中,使用氩气进行气氛保护,加热的三段温度和时间分别设置为室温至1000℃5h,保温1000℃1h,降温至室温2h。
将获得的碳化金属有机框架材料与氢氧化钾水溶液进行超声混合,超声温度为40℃,超声时间30min。结束后,通过500rpm及5min的离心,再于100℃下烘干15h处理后,获得钾离子插层的碳化金属有机框架材料。
将获得的上述材料再次置于高温管式炉中,使用氩气进行保护,加热的三段温度和时间分别设置为室温至850℃3h,保温850℃1h,降温至室温 1.5h。
将上述高温处理过的材料与1N的HCl溶液混合,搅拌24h后,通过离心水洗干燥后获得最终用于添加的石墨烯碳纳米带材料。
按照上述反应步骤通过控制金属有机框架材料金属离子、有机配体和模板助剂的量,可以调控所得石墨烯碳纳米带的结构与尺寸。例如确定硫酸锌及2, 5-二羟基对苯二甲酸的比例后,通过逐渐增加水杨酸钠的添加量(0.1、0.2、0.3、 0.4g),来控制金属有机框架材料的形貌与尺寸(见图3),长度范围控制在0.5~ 2um,界面长宽控制在0~0.5um,再通过碳化剥离获得不同尺寸的石墨烯碳纳米带(长度控制在0.2~2um,宽度0~0.5um,见图4)。
将上述加入0.3g水杨酸获得的石墨烯碳纳米带材料(0.02g),加入到添加有超分散剂BYK-110的钛酸钡/环氧树脂丁酮溶液中,环氧树脂固化剂选择酸酐型固化剂,钛酸钡为2g,树脂质量为2g,丁酮为1g,超声30min混合均匀。
将上述配制的复合溶液涂布于规格为1oz的压延铜箔基材上,选择二段式旋涂,第一段速度为1000rpm,时间控制为30s。第二段速度为2000rpm,时间控制为30s,最终获得介电层厚度在15um左右。
将一侧涂布有介电涂料的铜箔直接进行烘干固化,烘干温度为110℃,时间控制在1h。
将导电银胶通过不锈钢掩膜,掩膜有固定尺寸的孔1×1mm,涂覆在铜箔基的复合薄膜材料上制作电极。取5个点进行测算电容值、介电损耗(检测频率设置为1KHz),通过切片测量相应的涂层厚度,得到的结果如表1所示:
表1
利用电容定义式计算获得的对应的介电常数:
C=εε0S/d 式(1)
其中C为电容值,ε为相对介电常数,ε0为真空介电常数,S为所测电容面积,d为介电层厚度。
获得的介电材料电容密度均值为4.66nF/cm2,而介电层厚度的平均值为 12.2um,因此计算获得的介电常数约为64.15,介电损耗约为0.0248。所得复合材料与商品化的材料相比(3M的C-Ply,其介电常数约20,介电损耗约0.05),介电常数有所提升,而介电损耗有所下降,达到了提升介电性能的目的。
上述具体实施方式不以任何形式限制本发明的技术方案,凡是采用等同替换或等效变换的方式所获得的技术方案均落在本发明的保护范围。
Claims (6)
1.一种具有高介电性能的复合材料,包括电极基材,其特征在于,在电极基材的一侧涂覆有树脂/介电粉体/导电性可控碳纳米带的三相复合材料,涂层厚度控制在5~30um,所得复合材料的介电常数大于20,介电损耗低于0.05;
所述的导电基材为铜箔或者铝箔;聚合物是环氧树脂、聚酰亚胺或者聚四氟乙烯;采用的溶剂为乙醇、丙酮、丁酮或者乙酸乙酯;介电粉体是钛酸钡、钛酸锶或者钛酸锶钡。
2.权利要求1所述的具有高介电性能的复合材料的制备方法,其特征在于,步骤如下:
(1)、金属有机框架材料的制备:金属盐、有机配体2,5-二羟基对苯二甲酸及模板助剂水杨酸在室温下反应0.5~1h,产物使用溶剂洗涤、离心,获得金属有机框架材料;
(2)、金属有机框架材料前驱体的制备:将步骤(1)获得的金属有机框架材料分散于甲醇中进行水热反应,水热反应温度在100~150℃,反应时间在24~48h,产物离心烘干后获得所需的金属有机框架材料前驱体;
(3)、碳化金属有机框架材料的制备:将步骤(2)获得的金属有机框架材料前驱体置于高温炉中惰性气体气氛下进行碳化处理;
(4)、金属离子插层的碳化金属有机框架材料的制备:将获得的碳化金属有机框架材料,与碱性溶液混合,超声混合均匀,离心后继续在高温炉中惰性气体气氛下进行煅烧处理;
(5)、石墨烯碳纳米带材料的制备:将获得的金属离子插层的碳化金属有机框架材料与酸性溶液混合,洗去残留的碱性物质,水洗后干燥,得到所需石墨烯碳纳米带材料;
(6)树脂/介电粉体/导电性可控碳纳米带三相复合材料的制备:将获得的导电性可控的石墨烯碳纳米带加入树脂粉体的溶液中,混合均匀后涂布于导电基材上,经过固化后,得到一侧涂覆有复合薄膜材料的电极基材。
3.权利要求2所述的具有高介电性能的复合材料的制备方法,其特征在于,步骤(1)中,所述的金属盐为锌盐或者镁盐;溶剂为N,N-二甲基甲酰胺或者甲醇。
4.权利要求2所述的具有高介电性能的复合材料的制备方法,其特征在于,步骤(3)中,碳化处理的处理温度分为三个阶段,第一阶段从室温升温至1000~1200℃,持续时间为3~6h,第二阶段为保温阶段,温度为1000~1200℃,持续时间为0.5~4h,第三阶段为降温阶段,持续时间1~3h。
5.权利要求2所述的具有高介电性能的复合材料的制备方法,其特征在于,步骤(4)中,煅烧处理的处理温度为三个阶段,第一阶段从室温升温至500~1000℃,持续时间为3~6h,第二阶段为保温阶段,温度为500~1000℃,持续时间为0.5~4h,第三阶段为降温阶段,持续时间1~3h。
6.权利要求2所述的具有高介电性能的复合材料的制备方法,其特征在于,步骤(4)中,所述的碱性溶液为氢氧化钾或者氢氧化钠。惰性气体是氮气或者氩气。
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