CN112608163A - 一种钛酸钡掺杂改性碳基复合材料及其制备方法 - Google Patents

一种钛酸钡掺杂改性碳基复合材料及其制备方法 Download PDF

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CN112608163A
CN112608163A CN202011493122.0A CN202011493122A CN112608163A CN 112608163 A CN112608163 A CN 112608163A CN 202011493122 A CN202011493122 A CN 202011493122A CN 112608163 A CN112608163 A CN 112608163A
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barium titanate
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张福勤
王化中
吕波
杨宇
夏莉红
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Central South University
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Abstract

本发明公开了一种钛酸钡掺杂改性碳基复合材料及其制备方法，所述制备方法为将分散有钛酸钡粉末的混合液，喷洒在单层全网胎纤维的双表面，然后将单层含有钛酸钡粉末的全网胎纤维叠层针刺获得钛酸钡掺杂碳纤维预制体，然后将钛酸钡掺杂碳纤维预制体进行化学气相沉积致密即得钛酸钡掺杂改性碳基复合材料。所制得的钛酸钡掺杂改性碳基复合材料为中心有孔洞的圆柱体。本发明创新性的采用在预制体制备前期就可以达到钛酸钡均匀分散在预制体上的目的。该发明方法简单可控，复合材料中钛酸钡颗粒均匀分布，同时具有成本低廉，原料易得，对纤维无损等特性，适合于规模化生产及应用。

Description

一种钛酸钡掺杂改性碳基复合材料及其制备方法
技术领域
本发明属于碳基复合材料制备方法技术领域，特别涉及一种钛酸钡掺杂改性碳基复合材料及其制备方法。
背景技术
从目前碳/碳材料研究情况来看，主要还是应用在航空航天高强材料、摩擦材料和抗烧蚀材料领域，在电子功能材料领域的应用还需要探索。在对碳/碳材料进行应用时，常对其进行改性，如通过添加第二相介质对碳/碳材料进行改性，可以起到两个作用：一、添加第二相介质改善碳/碳复合材料的组织结构，提升其力学、抗烧蚀和摩擦磨损等性能，更好地满足原有领域对材料的需求。二、通过添加第二相介质改性碳/碳复合材料赋予其新的功能性，挖掘探究其在新领域的应用价值。
在用于电子发射领域时，材料需要具有耐高温、耐烧蚀和材料表面微点均匀分置的性质，然而碳碳材料虽然具有耐高温、抗烧蚀和优异的力学特性，然而其电子发射时需要借助材料表面发射微点实现均匀高密度发射的特性。
而钛酸钡不仅适合作为增强体改善碳/碳复合材料组织结构并提升其物理、力学性能，同时其还具有优异的高介电性能和低介电损耗；可能赋予碳/碳材料更好的功能特性，使改性碳碳复合材料应用在发射过程中，能够发射稳定，均匀性好。
目前常用的掺杂方法主要有原位生长法和电泳法，虽然能实现钛酸钡的均匀分散，但是工艺复杂，设备要求较高，引入量较少，同时对纤维也有一定的损伤。
发明内容
针对现有技术的不足，本发明的目的在于提供一种钛酸钡掺杂改性碳基复合材料及其制备方法。本发明的方法简单可控，复合材料中钛酸钡颗粒均匀分布，同时具有成本低廉，原料易得，对纤维无损等特性，适合于规模化生产及应用。
为了实现上述目的，本发明提供如下技术方案：
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，包括如下步骤：
将分散有钛酸钡粉末的混合液，喷洒在单层全网胎纤维的双表面，然后将单层含有钛酸钡粉末的全网胎纤维叠层针刺获得钛酸钡掺杂碳纤维预制体，然后将钛酸钡掺杂碳纤维预制体进行化学气相沉积致密即得钛酸钡掺杂改性碳基复合材料。
本发明的制备方法，先在单层全网胎纤维的表面喷洒分散有钛酸钡粉末的混合液，然后再通过针刺法获得钛酸钡掺杂碳纤维预制体，通过针刺纤维不仅可以把钛酸钡带入网胎层内部，同时增加了层间结合力。本发明通过编织过程中引入钛酸钡，工艺简单，既实现了钛酸钡在预制体制备过程中的均匀分散，增大了钛酸钡的掺杂量，同时又起到保护纤维结构完整性的作用，最后再利用化学气相沉积法制备得到钛酸钡掺杂改性碳基复合材料。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述钛酸钡粉末的粒径为100～500nm；优选为300～500nm。
在本发明中，钛酸钡粉末的粒径对最终材料的性能具有一定的影响，若粒径过小，钛酸钡粉末将被沉积形成的热解碳完全包覆，在电子发射中发射性能效果微弱，而若钛酸钡的粒径过大，则附在纤维上的分散性不好。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述分散有钛酸钡粉末混合液的获取方法为：将钛酸钡粉末加入无水乙醇中，在超声作用下分散，所述超声的功率为300～500w，超声的1～2h。
在实际操作过程中，超声作用下，获得充分分散有钛酸钡粉末的混合液，要立即喷洒于全网胎纤维层。
优选地，所述钛酸钡粉末和无水乙醇的固液质量体积比为1g:10～30mL。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述单层全网胎纤维的面密度20～30g/m2。
将单层全网胎纤维的面密度控制在上述范围可以使最终所得钛酸钡掺杂改性碳基复合材料的性能最佳，而若单层全网胎密度过高会使最终编制成型的预制体密度过高，相对热解碳含量少，电子发射的稳定性和均匀性就不理想。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述全网胎纤维中所用纤维为T700级碳纤维。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述全网胎纤维的制备方法为，将短切纤维用水喷湿、松散，然后铺设成网胎，再用长纤维在网胎上排列成径向纤维进行针刺形成单层全网胎纤维。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述单层含有钛酸钡粉末的全网胎纤维先经干燥，再层叠针刺，所述干燥的温度为100～200℃；时间为1～2h。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述钛酸钡掺杂碳纤维预制体为中心有孔洞的圆柱体，所述孔洞的直径20～30mm。
优选地，所述钛酸钡掺杂碳纤维预制体的外径为50～60mm，高度为40～50mm。
在本发明中，将钛酸钡掺杂碳纤维预制体制成有中心有孔洞的结构，可以使在气相沉积过程中，气体经压力差作用经过圆柱内部向外部扩散，可以加速致密，以及增加均匀性。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述钛酸钡掺杂碳纤维预制体的密度为0.2～0.3g/cm3。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述钛酸钡掺杂碳纤维预制体中，钛酸钡的质量分数为5％～25％；优选为15％～25％。
在本发明中，将钛酸钡的掺杂量控制在上述范围内，钛酸钡掺杂改性碳基复合材料的综合性能最佳，而若钛酸钡的掺杂量过小，则材料的电子发射性能提升不明显，掺杂量太大影响沉积碳的均匀性。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述化学气相沉积的工艺为：以N2为稀释气体，以丙烯为碳源气体，所述丙烯与N2的流量比为4～120:1；优选为60～100:1。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述化学气相沉积时，温度为1000～1100℃；炉内压力为1～8kpa。
本发明一种钛酸钡掺杂改性碳基复合材料的制备方法，所述钛酸钡掺杂改性碳基复合材料的密度≥1.8g/cm3。
在本发明中，经过多次CVD沉积直至钛酸钡掺杂改性碳基复合材料致密，在每次CVD前后用天平分别称量碳纤维预制体质量，计算每次沉积后的增重，并计算密度，同时在每次沉积完成后进行机加工，抛掉表层阻碍碳源气体扩散的通道，并清洗干净。
本发明还提供上述制备方法所制备的钛酸钡掺杂改性碳基复合材料。
本发明还提供上述制备方法制备的钛酸钡掺杂改性碳基复合材料的应用，将所述钛酸钡掺杂改性碳基复合材料应用于电子发射领域。
有益效果
本制备方法可以在编织过程中引入钛酸钡，以此制备得到钛酸钡改性碳基复合材料预制体，工艺简单，既实现了钛酸钡在预制体制备过程中的均匀分散，同时又起到保护纤维结构完整性的作用，利用化学气相沉积法制备得到钛酸钡掺杂改性碳基复合材料。
本发明在于提供一种钛酸钡掺杂改性碳基复合材料的制备方法，该发明方法简单可控，成本低廉，原料易得，对纤维无损等特性，适合于规模化生产及应用。同时所制得钛酸钡掺杂改性碳基复合材料中，钛酸钡颗粒均匀分布，钛酸钡掺杂量高，钛酸钡掺杂改性碳基复合材料不仅具有优异的力学性能，更重要的是大幅提了电子发射性能，使发射的稳定性、均匀性、电流密度等有了较大提升。
附图说明
图1为实施例1制备掺杂钛酸钡的扫描电镜图；
图2为实施例1制备钛酸钡掺杂改性碳基复合材料预制体扫描电镜图；
图3为实施例1制备钛酸钡掺杂改性碳基复合材料预制体实物图。
具体实施方式
实施例1
取20.59g粒径为500nm的钛酸钡粉末与300ml无水乙醇混合，在超声仪器中振荡、搅拌分散1.5h，待充分混合、分散，没有团聚之后，立即把配置好的钛酸钡分散液均匀喷洒在质量为391.11g的全网胎单层纤维的表面，所述全网胎单层纤维的表面密度为20g/cm3，将单层纤维烘干后叠层针刺，获得钛酸钡掺杂碳纤维预制体，所制得的钛酸钡掺杂碳纤维预制体中间具有孔洞，内径30mm，外径60mm，高度50mm；钛酸钡掺杂碳纤维预制体的密度为0.2g/cm3，钛酸钡在钛酸钡掺杂碳纤维预制体中的质量分数为5％。
再将钛酸钡掺杂碳纤维预制体置于化学气相沉积炉中进行沉积，以丙烯为沉积热解碳所需气体，N2为稀释气体，N2流量为0.5L/min，丙烯的流量为40L/min。沉积条件为：炉内温度为1000℃，炉内压力为1kpa，沉积时间以168h为一个沉积周期，沉积4个周期后制备得到钛酸钡掺杂改性碳基复合材料，所得复合材密度为1.8g/cm3。
将其所得钛酸钡掺杂改性碳基复合材料用于电子发射，发射稳定性好，电流密度达到12KA/cm3。
图1为实施例1中掺杂钛酸钡的扫描电镜图，钛酸钡颗粒相对均匀，在图2碳纤维预制体中分散也均匀。
图2为实施例1中所制备的钛酸钡掺杂改性碳基复合材料预制体形貌的扫描电镜图，从图中可以看到预制体结构内部形貌为一个个短纤维及其均匀附着在上面的钛酸钡小颗粒。
图3为实施例1中所制备的钛酸钡掺杂改性碳基复合材料的预制体形貌实物图，其为中心有孔洞的圆柱体，内径30mm，外径60mm，高度50mm。
实施例2
取粒径为500nm的钛酸钡粉末和无水乙醇，控制钛酸钡粉末质量和无水乙醇的固液质量比为1g:20mL，在超声仪器中振荡、搅拌分散1.5h，待充分混合、分散，没有团聚之后，立即把配置好的钛酸钡分散液均匀喷洒在全网胎单层纤维的表面，所述全网胎单层纤维的表面密度为0.2g/cm3，将单层纤维烘干后叠层针刺，获得钛酸钡掺杂碳纤维预制体，所制得的钛酸钡掺杂碳纤维预制体内径30mm，外径60mm，高度50mm。所得钛酸钡掺杂碳纤维预制体的密度为0.2g/cm3，钛酸钡粉末在钛酸钡掺杂碳纤维预制体中的质量分数为15％。
再将钛酸钡掺杂碳纤维预制体置于化学气相沉积炉中进行沉积，以丙烯为沉积热解碳所需气体，N2为稀释气体，N2流量为0.5L/min，丙烯的流量为40L/min。沉积条件为：炉内温度为1050℃，炉内压力为3kpa，沉积时间以150h为一个沉积周期，沉积3个周期后制备得到钛酸钡掺杂改性碳基复合材料，复合材密度为1.80g/cm3。
将其所得钛酸钡掺杂改性碳基复合材料用于电子发射，电流密度达到14KA/cm3。
实施例3
取粒径为500nm的钛酸钡粉末和无水乙醇，控制钛酸钡粉末质量和无水乙醇的固液质量比为1g:30mL，在超声仪器中振荡、搅拌分散1.5h，待充分混合、分散，没有团聚之后，立即把配置好的钛酸钡分散液均匀喷洒在全网胎单层纤维的表面，所述全网胎单层纤维的表面密度为20g/cm3，将单层纤维烘干后叠层针刺，获得钛酸钡掺杂碳纤维预制体，所制得的钛酸钡掺杂碳纤维预制体中间具有孔洞，内径30mm，外径60mm，高度50mm。所得钛酸钡掺杂碳纤维预制体的密度为0.2g/cm3，钛酸钡粉末在钛酸钡掺杂碳纤维预制体中的质量分数为25％。
以丙烯为沉积热解碳所需气体，N2为稀释气体，N2流量为0.5L/min，丙烯的流量为40L/min。沉积条件为：炉内温度为1100℃，炉内压力为8kpa，沉积时间以150h为一个沉积周期，沉积4个周期后制备得到钛酸钡掺杂改性碳基复合材料，复合材密度为1.81g/cm3。
将其所得钛酸钡掺杂改性碳基复合材料用于电子发射，电流密度达到16KA/cm3。
对比例1
其他条件与实施例1相同，仅是钛酸钡粉末粒径为50nm。
所得产品性能如下：钛酸钡粉末被沉积形成的热解碳完全包覆，在电子发射中发射性能效果极其微弱，与未掺杂的基本没有相同。
对比例2
其他条件与实施例2相同，仅是钛酸钡粉末在钛酸钡掺杂碳纤维预制体中的质量分数超过40％。钛酸钡粉末加入量过大，致使钛酸钡掺杂碳纤维预制体在沉积过程中增密效果减缓，效率低下，增加了时间和经济成本，未能达到1.8/cm3的密度要求。

Claims (9)

1.一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：包括如下步骤：
将分散有钛酸钡粉末的混合液，喷洒在单层全网胎纤维的双表面，然后将单层含有钛酸钡粉末的全网胎纤维叠层针刺获得钛酸钡掺杂碳纤维预制体，然后将钛酸钡掺杂碳纤维预制体进行化学气相沉积致密即得钛酸钡掺杂改性碳基复合材料。
2.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述钛酸钡粉末的粒径为100～500nm。
3.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述分散有钛酸钡粉末的混合液的获取方法为：将钛酸钡粉末加入无水乙醇中，在超声作用下分散，所述超声的功率为300～500w，超声的时间1～2h；所述钛酸钡粉末和无水乙醇的固液质量体积比为1g:10～30mL。
4.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述单层全网胎纤维的面密度20～30g/m2。
5.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述钛酸钡掺杂碳纤维预制体为中心有孔洞的圆柱体，所述孔洞的直径20～30mm；所述钛酸钡掺杂碳纤维预制体的外径为50～60mm，高度为40～50mm。
6.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述钛酸钡掺杂碳纤维预制体的密度为0.2～0.3g/cm3；所述钛酸钡掺杂碳纤维预制体中，钛酸钡的质量分数为5％～25％。
7.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述化学气相沉积的工艺为：以N2为稀释气体，以丙烯为碳源气体，所述丙烯与N2的流量比为4～120:1；温度为1000～1100℃；炉内压力为1～8kpa。
8.根据权利要求1所述的一种钛酸钡掺杂改性碳基复合材料的制备方法，其特征在于：所述钛酸钡掺杂改性碳基复合材料的密度≥1.8g/cm3。
9.根据权利要求1-8任意一项所述的制备方法所制备的钛酸钡掺杂改性碳基复合材料。
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