CN106630975A - 一种柔性复合陶瓷材料及其制备方法 - Google Patents

一种柔性复合陶瓷材料及其制备方法 Download PDF

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CN106630975A
CN106630975A CN201611235912.2A CN201611235912A CN106630975A CN 106630975 A CN106630975 A CN 106630975A CN 201611235912 A CN201611235912 A CN 201611235912A CN 106630975 A CN106630975 A CN 106630975A
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ceramic material
flexible compound
weight portions
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董睿智
丁天昊
丁萍
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GUANGDONG REAL FAITH LIGHTING TECHNOLOGY Co Ltd
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Abstract

本发明提供一种柔性复合陶瓷材料,包括下述组成材料:10‑50重量份的树脂,50‑85重量份的陶瓷粉体,0‑10重量份的溶剂,1‑2重量份的固化剂,1‑3重量份的助剂,其中:所述树脂为丙烯酸树脂、环氧树脂和有机硅树脂中的一种或几种,所述陶瓷粉体的粒径为1‑10um,所述溶剂为醇类、酯类、烷烃类、醚类、酮类和苯类中的一种或几种,所述固化剂为铂系催化剂、胺类、苯胺类、多元醇类、酚类、酸酐类、过氧化物类和咪唑类中的一种或几种,所述助剂为分散剂、消泡剂和抑制剂中的一种或几种。本发明具有传统陶瓷材料的耐磨性、耐蚀性、电性能,同时还具有优良的韧性、抗冲击性,以及相较于同类其它有机树脂改性的耐温性能。

Description

一种柔性复合陶瓷材料及其制备方法
技术领域
本发明属于复合陶瓷材料领域,具体涉及一种柔性复合陶瓷材料及其制备方法。
背景技术
陶瓷材料具有优异的耐磨性、杰出的耐热性、良好的耐蚀性。除此之外,功能性陶瓷还具有良好的电性能、光性能、热性能以及生物性能。陶瓷材料已经广泛应用于建筑、军事、交通、航空航天、汽车等通用领域。
传统的陶瓷材料的制备是先将特定的陶瓷粉体塑型,然后放入高温炉中进行烧结成型。然而,在制作期间不仅需要消耗大量的电能、热能,而且存在着对烧结设备的要求较高,综合投入较高等缺点。利用部分有机物改性陶瓷,不仅可以大大降低制作过程中使用的电、热能,减少设备的综合投入,还能赋予复合性陶瓷一些新性能特点。如传统陶瓷的最大不足就是材料的脆性,但通过部分有机成分可以大大降低陶瓷材料的脆性,从而可以获得结构性和功能性优良的柔性陶瓷材料。而柔性陶瓷材料相比于传统的硬性陶瓷具有更为广阔的应用前景。
发明内容
本发明的目的,即在于提供一种柔性复合陶瓷材料,具有传统陶瓷材料的耐磨性、耐蚀性、电性能,同时还具有优良的韧性、抗冲击性,以及相较于同类其它有机树脂改性的耐温性能。其抗拉强度≥30N/mm2,弯曲强度≥10N/mm2,且在300℃下不黄变。产品可以广泛地应用于3D电路、线圈防护、柔性基材等领域。另外,本发明还提供了一种柔性复合陶瓷材料的制备方法方法。
本发明是这样实现的:
一种柔性复合陶瓷材料,包括下述组成材料:
10-50重量份的树脂,
50-85重量份的陶瓷粉体,
0-10重量份的溶剂,
1-2重量份的固化剂,
1-3重量份的助剂,
其中:
所述树脂为丙烯酸树脂、环氧树脂和有机硅树脂中的一种或几种,
所述陶瓷粉体的粒径为1-10um,
所述溶剂为醇类、酯类、烷烃类、醚类、酮类和苯类中的一种或几种,
所述固化剂为铂系催化剂、胺类、苯胺类、多元醇类、酚类、酸酐类、过氧化物类和咪唑类中的一种或几种,
所述助剂为分散剂、消泡剂和抑制剂中的一种或几种。
优选地,所述丙烯酸树脂为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸缩水甘油酯、α-氰基丙烯酸甲酯、α-氰基丙烯酸乙酯和α-氰基丙烯酸丁酯中的一种或几种。
优选地,所述环氧树脂为酚醛类改性环氧树脂、有机硅改性环氧树脂和脂肪酸甘油酯环氧树脂中的一种或几种。
优选地,所述有机硅树脂为单组分缩合胶或双组分加成胶。
优选地,所述陶瓷粉体为氧化物陶瓷粉体、氮化物陶瓷粉体、硼化物陶瓷粉体和碳化物陶瓷粉体中的一种或几种。
优选地,所述氧化物陶瓷粉体为Al2O3
所述氮化物陶瓷粉体为AlN、BN、Si3N4和ZrN中的一种或几种,
所述碳化物陶瓷粉体为B4C、SiC、ZrC、TiC和WC中的一种或几种,
所述硼化物陶瓷粉体为ZrB2和TiB2中的一种或两种。
优选地,所述醇类溶剂为甲醇、乙醇、异丙醇、正丁醇、异丁醇和戊醇中的一种或几种,
所述酯类溶剂为甲酸乙酯、乙酸乙酯、醋酸正丁酯和醋酸异丁酯中的一种或几种,
所述烷烃类溶剂为正已烷、环已烷、正辛烷和异辛烷中的一种或几种,
所述醚类溶剂包括,乙醚、四氢呋喃、苯乙醚、乙二醇乙醚、乙二醇丁醚、丙二醇甲醚和丙二醇乙醚中的一种或几种,
所述酮类溶剂为丙酮、环已酮和甲乙酮中的一种或几种,
所述苯类溶剂为甲苯和二甲苯中的一种或两种。
优选地,所述分散剂为有机硅系分散剂或聚多元醇,所述消泡剂为有机硅系消泡剂,所述抑制剂为炔醇类。
根据本发明的另一方面,一种制备上述的柔性复合陶瓷材料的方法,包括以下步骤:
S1:称取树脂和溶剂于球磨罐中,搅拌均匀;
S2:加入陶瓷粉体,搅拌均匀,得到浆液;
S3:将固化剂和助剂加入到浆液中,并将浆液转移至球磨机中进行球磨;
S4:将球磨好的浆液进行过滤,得到磨好后的组分;
S5:将组分真空脱泡,后进行固化烧结,得到柔性复合陶瓷材料。
优选地,所述步骤S3中球磨机的转速为300-500转/分钟,球磨时间为30-60分钟;
所述步骤S4中过滤使用的纱网为300目;
所述步骤S5中的固化烧结温度为150-160度,时间为4-8小时。
与现有技术相比,本发明的柔性复合陶瓷材料具有传统陶瓷材料的耐磨性、耐蚀性、电性能,同时还具有优良的韧性、抗冲击性,以及相较于同类其它有机树脂改性的耐温性能。其抗拉强度≥30N/mm2,弯曲强度≥10N/mm2,且在300℃下不黄变。产品可以广泛地应用于3D电路、线圈防护、柔性基材等领域。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
实施例1
柔性复合陶瓷材料,包括下述组成材料:
20重量份的聚甲基丙烯酸缩水甘油酯,
75重量份粒径D50为1-5um的Al2O3陶瓷粉体,
2重量份的乙醇,2.5重量份的环已烷,
1重量份的异丙苯过氧化氢,
2重量份的聚乙二醇600分散剂。
按下述方法进行制备:
S1:称取20重量份的聚甲基丙烯酸缩水甘油酯、2重量份的乙醇和2.5重量份的环已烷于球磨罐中,机械搅拌均匀;
S2:加入75重量份、粒径D50为1-5um的Al2O3陶瓷粉体,机械搅拌均匀,得到浆液;
S3:将1重量份的异丙苯过氧化氢和2重量份的聚乙二醇600加入到浆液中,搅拌均匀后,将浆液转移至球磨机中进行球磨,设定转速300rpm,时间为30分钟;
S4:使用300目纱网对球磨好的浆液进行过滤,得到磨好后的组分,并装入单口瓶中充氮密封保存;
S5:将组分真空脱泡,后放入烘箱中并于150℃温度下固化烧结6小时,得到柔性复合陶瓷材料。
所得柔性复合陶瓷材料的抗拉强度35N/mm2,弯曲强度30N/mm2,其耐温可达250℃不黄变。
实施例2
柔性复合陶瓷材料,包括A和B两种组分,其中:
A组分包括下述组成材料:
10重量份的乙烯基质量分数为5.4%的甲基有机硅树脂,
80重量份粒径D50为5um的Al2O3陶瓷粉体,
5重量份的环已烷,
2重量份的Karstedt′s固化剂,
2重量份的有机硅分散剂,
2重量份的有机硅消泡剂。
B组分包括下述组成材料:
10重量份的氢基质量分数为0.05%的甲基有机硅树脂,
80重量份粒径D50为5um的Al2O3陶瓷粉体,
5重量份的环已烷,
1重量份的3,5-二甲基-1-己炔-3-醇,
2重量份的有机硅分散剂,
2重量份的有机硅消泡剂。
按下述方法进行制备:
S1:分别称量10重量份乙烯基质量分数为5.4%和10重量份氢基质量分数为0.05%的甲基有机硅树脂于不同球磨罐中,分别加入5份环已烷溶剂,机械搅拌均匀;
S2:分别加入D50粒径为5μm的氧化铝陶瓷粉体80重量份,机械搅拌均匀,得到浆液;
S3:分别将2重量份有机硅消泡剂和2重量份有机硅分散剂加入到浆液中,并在A组分中添入2重量份的Karstedt′s固化剂,而在B组分中加入1重量份3,5-二甲基-1-己炔-3-醇抑制剂,搅拌均匀后,将浆液转移至球磨机中进行球磨,设定转速300rpm,时间为30分钟;
S4:使用300目纱网分别对球磨好的浆液进行过滤,得到磨好后的A组分和B组分,并分别装入单口瓶中充氮密封保存;
S5:将A、B组分以重量份比为1:4进行混合后,将组分真空脱泡,后放入烘箱中并于150℃温度下固化烧结6小时,得到柔性复合陶瓷材料。
所得柔性复合陶瓷材料的抗拉强度30N/mm2,弯曲强度20N/mm2,其耐温可达300℃不黄变。
实施例3
柔性复合陶瓷材料,包括下述组成材料:
20重量份的有机硅改性环氧树脂,
75重量份粒径D50为5um的Al2O3陶瓷粉体,
2重量份的丙酮,
2重量份的间苯二胺,
1重量份的有机硅消泡剂。
按下述方法进行制备:
S1:称取20重量份的有机硅改性环氧树脂、2重量份的丙酮于球磨罐中,机械搅拌均匀;
S2:加入75重量份、粒径D50为5um的Al2O3陶瓷粉体,机械搅拌均匀,得到浆液;
S3:将2重量份的间苯二胺和1重量份的有机硅消泡剂加入到浆液中,搅拌均匀后,将浆液转移至球磨机中进行球磨,设定转速300rpm,时间为60分钟;
S4:使用300目纱网对球磨好的浆液进行过滤,得到磨好后的组分,并装入单口瓶中充氮密封保存;
S5:将组分真空脱泡,后放入烘箱中并于150℃温度下固化烧结6小时,得到柔性复合陶瓷材料。
所得柔性复合陶瓷材料的抗拉强度50N/mm2,弯曲强度35N/mm2,其耐温可达280℃不黄变。
实施例4
20重量份的有机硅改性环氧树脂,
75重量份粒径D50为5um的氮化铝陶瓷粉体,
2重量份的丙酮,
2重量份的间苯二胺,
1重量份的有机硅消泡剂。
按下述方法进行制备:
S1:称取20重量份的有机硅改性环氧树脂、2重量份的丙酮于球磨罐中,机械搅拌均匀;
S2:加入75重量份、粒径D50为5um的氮化铝陶瓷粉体,机械搅拌均匀,得到浆液;
S3:将2重量份的间苯二胺和1重量份的有机硅消泡剂加入到浆液中,搅拌均匀后,将浆液转移至球磨机中进行球磨,设定转速300rpm,时间为60分钟;
S4:使用300目纱网对球磨好的浆液进行过滤,得到磨好后的组分,并装入单口瓶中充氮密封保存;
S5:将组分真空脱泡,后放入烘箱中并于150℃温度下固化烧结6小时,得到柔性复合陶瓷材料。
所得柔性复合陶瓷材料的抗拉强度50N/mm2,弯曲强度35N/mm2,其耐温可达280℃不黄变。
实施例5
15重量份的有机硅改性环氧树脂,
80重量份粒径D50为5um的氮化硼陶瓷粉体,
2重量份的丙酮,
2重量份的间苯二胺,
1重量份的有机硅消泡剂。
按下述方法进行制备:
S1:称取15重量份的有机硅改性环氧树脂、2重量份的丙酮于球磨罐中,机械搅拌均匀;
S2:加入80重量份、粒径D50为5um的氮化硼陶瓷粉体,机械搅拌均匀,得到浆液;
S3:将2重量份的间苯二胺和1重量份的有机硅消泡剂加入到浆液中,搅拌均匀后,将浆液转移至球磨机中进行球磨,设定转速300rpm,时间为60分钟;
S4:使用300目纱网对球磨好的浆液进行过滤,得到磨好后的组分,并装入单口瓶中充氮密封保存;
S5:将组分真空脱泡,后放入烘箱中并于150℃温度下固化烧结6小时,得到柔性复合陶瓷材料。
所得柔性复合陶瓷材料的抗拉强度60N/mm2,弯曲强度80N/mm2,其耐温可达300℃不黄变。
与现有技术相比,本发明的柔性复合陶瓷材料具有传统陶瓷材料的耐磨性、耐蚀性、电性能,同时还具有优良的韧性、抗冲击性,以及相较于同类其它有机树脂改性的耐温性能。其抗拉强度≥30N/mm2,弯曲强度≥10N/mm2,且在300℃下不黄变。产品可以广泛地应用于3D电路、线圈防护、柔性基材等领域。
最后应说明的是:以上所述的各实施例仅用于说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分或全部技术特征进行等同替换;而这些修改或替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

1.一种柔性复合陶瓷材料,其特征在于:包括下述组成材料:
10-50重量份的树脂,
50-85重量份的陶瓷粉体,
0-10重量份的溶剂,
1-2重量份的固化剂,
1-3重量份的助剂,
其中:
所述树脂为丙烯酸树脂、环氧树脂和有机硅树脂中的一种或几种,
所述陶瓷粉体的粒径为1-10um,
所述溶剂为醇类、酯类、烷烃类、醚类、酮类和苯类中的一种或几种,
所述固化剂为铂系催化剂、胺类、苯胺类、多元醇类、酚类、酸酐类、过氧化物类和咪唑类中的一种或几种,
所述助剂为分散剂、消泡剂和抑制剂中的一种或几种。
2.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:所述丙烯酸树脂为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸缩水甘油酯、α-氰基丙烯酸甲酯、α-氰基丙烯酸乙酯和α-氰基丙烯酸丁酯中的一种或几种。
3.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:所述环氧树脂为酚醛类改性环氧树脂、有机硅改性环氧树脂和脂肪酸甘油酯环氧树脂中的一种或几种。
4.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:所述有机硅树脂为单组分缩合胶或双组分加成胶。
5.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:所述陶瓷粉体为氧化物陶瓷粉体、氮化物陶瓷粉体、硼化物陶瓷粉体和碳化物陶瓷粉体中的一种或几种。
6.根据权利要求5所述的柔性复合陶瓷材料,其特征在于:
所述氧化物陶瓷粉体为Al2O3
所述氮化物陶瓷粉体为AlN、BN、Si3N4和ZrN中的一种或几种,
所述碳化物陶瓷粉体为B4C、SiC、ZrC、TiC和WC中的一种或几种,
所述硼化物陶瓷粉体为ZrB2和TiB2中的一种或两种。
7.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:
所述醇类溶剂为甲醇、乙醇、异丙醇、正丁醇、异丁醇和戊醇中的一种或几种,
所述酯类溶剂为甲酸乙酯、乙酸乙酯、醋酸正丁酯和醋酸异丁酯中的一种或几种,
所述烷烃类溶剂为正已烷、环已烷、正辛烷和异辛烷中的一种或几种,
所述醚类溶剂包括,乙醚、四氢呋喃、苯乙醚、乙二醇乙醚、乙二醇丁醚、丙二醇甲醚和丙二醇乙醚中的一种或几种,
所述酮类溶剂为丙酮、环已酮和甲乙酮中的一种或几种,
所述苯类溶剂为甲苯和二甲苯中的一种或两种。
8.根据权利要求1所述的柔性复合陶瓷材料,其特征在于:所述分散剂为有机硅系分散剂或聚多元醇,所述消泡剂为有机硅系消泡剂,所述抑制剂为炔醇类。
9.一种制备权利要求1-8任一项所述的柔性复合陶瓷材料的方法,其特征在于:包括以下步骤:
S1:称取树脂和溶剂于球磨罐中,搅拌均匀;
S2:加入陶瓷粉体,搅拌均匀,得到浆液;
S3:将固化剂和助剂加入到浆液中,并将浆液转移至球磨机中进行球磨;
S4:将球磨好的浆液进行过滤,得到磨好后的组分;
S5:将组分真空脱泡,后进行固化烧结,得到柔性复合陶瓷材料。
10.根据权利要求9所述的制备柔性复合陶瓷材料的方法,其特征在于:
所述步骤S3中球磨机的转速为300-500转/分钟,球磨时间为30-60分钟;
所述步骤S4中过滤使用的纱网为300目;
所述步骤S5中的固化烧结温度为150-160度,时间为4-8小时。
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