CN113024259B - 一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其制备方法 - Google Patents

一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其制备方法 Download PDF

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CN113024259B
CN113024259B CN202110291042.5A CN202110291042A CN113024259B CN 113024259 B CN113024259 B CN 113024259B CN 202110291042 A CN202110291042 A CN 202110291042A CN 113024259 B CN113024259 B CN 113024259B
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刘应军
沙建军
祖宇飞
苏成
代吉祥
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Dalian University of Technology
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Abstract

本发明属于超高温陶瓷基复合材料领域，具体涉及一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其制备方法。在碳纤维的截面方向上，具有n层以碳纤维为中心从内到外热膨胀系数逐渐变大的梯度陶瓷基体，陶瓷基体原料包括：二硼化物超高温陶瓷、碳化硅和二硅化锆；所述的二硼化物超高温陶瓷包括二硼化锆或二硼化铪；制备方法是在碳纤维上电泳沉积n层径向梯度陶瓷涂层，然后热压烧结得到复合材料。本发明的效果和益处：解决了碳纤维与基体热不匹配的问题，提升了复合材料的机械性能，避免了复合材料抗氧化、抗烧蚀性能的下降；设计的梯度陶瓷基体，提高了复合材料的抗断裂性能和抗热冲击性能；优化了基体组分，提升了复合材料的耐超高温性能。

Description

一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其 制备方法
技术领域
本发明属于超高温陶瓷基复合材料领域，具体涉及一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其制备方法。
背景技术
高超声速导弹、跨大气层飞行器、空天飞机等在飞行过程中将遭受强烈的气动加热效应，其尖锐部件(如头锥、机翼前缘)的温度将会高达2000℃以上。这对服役的材料提出了苛刻要求。碳纤维增韧碳基复合材料具有优良的抗断裂性能、较低的密度(～2g/cm3)、较高的强度，广泛应用在航天结构材料中。但在有氧的超高温环境(>1600℃)下，碳纤维增韧碳基复合材料将迅速被氧化、烧蚀，导致结构失效。因此，开发出了新一代的超高温陶瓷(如二硼化锆、二硼化铪)，它们 具有高熔点(～3000℃)、高模量(～500GPa)、高硬度(～26GPa)、优异的高温稳定性、以及优异的抗氧化、抗烧蚀性能。
然而，超高温陶瓷的脆性较大、对裂纹很敏感，容易发生灾难性破坏。为了提高超高温陶瓷的抗断裂韧性，考虑使用具有优异性能(较低的密度～1.8 g/cm3，优异的刚度和强度)的碳纤维来增韧。碳纤维可以通过纤维脱粘、纤维拔出、纤维桥接等机制来偏转裂纹，吸收大量的断裂能，大幅提升了复合材料的抗断裂韧性。碳纤维增韧超高温陶瓷基复合材料综合了碳纤维和超高温陶瓷的优良性质，兼具优异的抗氧化性能和优良的抗断裂性能，还具有较低的密度，是极端环境下热防护材料的备选者。
通常，采用热压烧结或放电等离子体烧结技术在1300-2000℃下制备碳纤维增韧超高温陶瓷基复合材料。在材料制备过程中，往往由于碳纤维与超高温陶瓷的热膨胀系数不匹配而产生微裂纹、甚至开裂，这严重削弱了复合材料的机械性能。文献1[Luca Zoli,Antonio Vinci,Pietro Galizia,Cesare Melandri， DilettaSciti，“On the thermalshock resistance and mechanical properties of novel unidirectional UHTCMCsfor extreme environments”，Sci Rep 8,9148(2018)]中第二段，Zoli等人在制备的碳纤维增韧超高温陶瓷基复合材料的基体中发现了微裂纹。文献2[P.Galizia，L.Zoli，D.Sciti，“Impact of residual stress on thermal damage accumulation,and Young'smodulus of fiber-reinforced ultra-high temperature ceramics”，Materials&Design，Volume 160,15December 2018,Pages 803-809] 中3.1节，Galizia等人对碳纤维增韧超高温陶瓷基复合材料进行了热循环处理，明显的观察到了垂直于纤维轴向的微裂纹，复合材料的弹性模量从195GPa降低到24GPa。
具体的，碳纤维的纵向热膨胀系数为1.6-2.1×10-6/℃，横向热膨胀系数为 (-1.5)-(-0.6)×10-6/℃；二硼化锆的热膨胀系数为5.99-8.3×10-6/℃，二硼化铪的热膨胀系数为6.3-8.15×10-6/℃。在降温过程中，热膨胀系数的差异将导致残余热应力的产生。碳纤维易受压残余热应力，超高温陶瓷基体易受拉残余热应力。因此，在基体中易形成垂直于纤维轴向的微裂纹网络，甚至还会造成基体开裂。在复合材料的使用过程中，这种残余热应力将叠加于外加拉伸载荷，大大降低了复合材料的机械性能。此外，存在的微裂纹网络将成为含氧气氛的通道，降低了复合材料的抗氧化、抗烧蚀性能。
因此，为了提升碳纤维增韧超高温陶瓷基复合材料的机械性能，避免抗氧化、抗烧蚀性能的下降，确保其在服役过程中的可靠性，迫切需要解决碳纤维与基体热不匹配的问题。
发明内容
本发明的目的在于提供一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料及其制备方法，拟解决因热不匹配造成复合材料性能下降的问题，提升复合材料在服役过程中的可靠性。
为了实现本发明的目的，通过以下技术方案：
一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，在碳纤维的截面方向上，具有n层以碳纤维为中心从内到外热膨胀系数逐渐变大的梯度陶瓷基体，最内层陶瓷基体原料包括碳化硅和二硅化锆；最外层陶瓷基体原料包括二硼化物超高温陶瓷和二硅化锆；中间层的陶瓷基体原料包括：二硼化物超高温陶瓷、碳化硅和二硅化锆；所述的二硼化物超高温陶瓷包括二硼化锆或二硼化铪；以碳纤维增韧超高温陶瓷基复合材料的体积为100份计，碳纤维的体积份为10-60；对于第i层陶瓷基体，以这一层的体积为100份计，二硅化锆的体积份设为m，二硼化物超高温陶瓷的体积份为
Figure BDA0002982694730000031
碳化硅的体积份为
Figure BDA0002982694730000032
其中，m＝10-40；n＝2，3，4，5，…；i＝1，2，3，4，…，n。
一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，是利用电泳沉积技术在碳纤维上涂覆n层径向梯度陶瓷涂层，然后通过热压烧结得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，具体步骤包括：
1)对碳纤维进行预氧化处理，以便分开纤维丝：将原始碳纤维置于高温炉中，在300-550℃下氧化处理5-40min；
2)在碳纤维上涂覆热解碳涂层，用于保护碳纤维：首先以多巴胺为原料，利用电泳沉积技术在碳纤维上涂覆聚多巴胺涂层，然后在600-1400℃下热解 30-120min得到热解炭涂层纤维；
3)配制第i层陶瓷涂层的浆料：首先将聚乙烯亚胺溶于无水乙醇中配成浓度为1-20mg/ml的聚乙烯亚胺乙醇溶液；然后根据第i层陶瓷基体的体积比换算成质量比，称取二硼化物超高温陶瓷纳米级粉末、碳化硅纳米级粉末、二硅化锆纳米级粉末，加入到聚乙烯亚胺乙醇溶液中；其中，陶瓷基体原料粉末与聚乙烯亚胺的质量比为0.9-50:1；在持续超声震荡下机械搅拌20-60min，得到分散均匀的第i层陶瓷涂层的浆料；同样的操作，可配置第i+1，i+2，…，n层陶瓷涂层的浆料；
4)在碳纤维上涂覆n层径向梯度陶瓷涂层：将步骤2)所得热解炭涂层纤维置于步骤3)配制的第i层陶瓷涂层的浆料中，电泳沉积2-120min，然后在 60-100℃下真空干燥10-60min，得到第i层陶瓷涂层纤维；然后将第i层陶瓷涂层纤维置于步骤3)配制的第i+1层陶瓷涂层的浆料中，电泳沉积2-120min，在真空条件下60-100℃干燥10-60min，得到第i+1层陶瓷涂层纤维；如此重复操作，直到获得第n层陶瓷涂层纤维；
5)将步骤4)得到的第n层陶瓷涂层纤维置于高温热压炉中，施加20-50 MPa的压力，在1400-1700℃下烧结10-120分钟，最终得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料。
本发明的有益效果：
1)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，在碳纤维的截面方向上，具有n层以碳纤维为中心的梯度陶瓷基体；从内到外，陶瓷基体的热膨胀系数逐渐变大；通过控制碳化硅(热膨胀系数较低)和二硼化物超高温陶瓷(热膨胀系数较高)的含量和来调节梯度陶瓷基体的热膨胀系数；解决了碳纤维与基体热不匹配的问题，提升了复合材料的机械性能，避免了复合材料抗氧化、抗烧蚀性能的下降，提高了复合材料在服役过程中的可靠性。
2)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，在热冲击过程中，具有的n层热膨胀系数逐渐变大的梯度陶瓷基体减小了复合材料遭受的的热应力，减轻了复合材料的热损伤，提高了复合材料的抗热冲击性能。
3)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，具有的n层陶瓷基体在外加载荷作用下可以发生层间脱粘，从而捕获并偏转裂纹，吸收大量的断裂能，提升了复合材料的抗断裂韧性。
4)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，利用电泳沉积技术在碳纤维上均匀涂覆n层径向梯度陶瓷涂层，可以通过调节沉积时间来优化涂层的涂覆情况，获得了性能优良的复合材料。
5)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，在热压烧结过程中，来源于聚合物的热解碳，避免了碳纤维受基体相的化学侵蚀，充分发挥了纤维拔出、纤维桥接、纤维脱粘等增韧机制的效果，提升了复合材料的抗断裂性能。
6)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，来源于聚合物的热解碳与二硅化锆发生化学反应，原位生成了纳米级超高温相，优化了基体组分，提升了复合材料的耐高温性能。
7)本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，利用电泳沉积技术，拥有绿色安全、成本较低、效率高等优点，可以在纤维纺丝工艺过程中实现。
附图说明
图1为本发明的实施例1中利用电泳沉积技术得到的3层陶瓷涂层纤维示意图。
图2为本发明的实施例2中利用电泳沉积技术得到的5层陶瓷涂层纤维示意图。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1
一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，在碳纤维的截面方向上，具有n层以碳纤维为中心从内到外热膨胀系数逐渐变大的梯度陶瓷基体，最内层陶瓷基体原料包括碳化硅和二硅化锆；最外层陶瓷基体原料包括二硼化物超高温陶瓷和二硅化锆；中间层的陶瓷基体原料包括：二硼化物超高温陶瓷，碳化硅，二硅化锆；所述的二硼化物超高温陶瓷为二硼化锆；以碳纤维增韧超高温陶瓷基复合材料的体积为100份计，碳纤维的体积份为40；对于第 i层陶瓷基体，以这一层的体积为100份计，二硅化锆的体积份设为m，二硼化物超高温陶瓷的体积份为
Figure BDA0002982694730000061
碳化硅的体积份为
Figure BDA0002982694730000062
在本实施例中，m＝20；n＝3；i＝1，2，3；
所述的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，其制备方法是利用电泳沉积技术在碳纤维上涂覆n层径向梯度陶瓷涂层，然后通过热压烧结得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，具体步骤包括：
1)对碳纤维进行预氧化处理，以便分开纤维丝：将原始碳纤维置于高温炉中，在400℃下氧化处理20min；
2)在碳纤维上涂覆热解碳涂层，用于保护碳纤维：首先以多巴胺为原料，利用电泳沉积技术在碳纤维上涂覆聚多巴胺涂层，然后在1200℃下热解60min 得到热解炭涂层纤维；
3)配制第i层陶瓷涂层的浆料：首先将聚乙烯亚胺溶于无水乙醇中配成浓度为10mg/ml的聚乙烯亚胺乙醇溶液；然后根据第i层陶瓷基体的体积比换算成质量比，称取二硼化物超高温陶瓷纳米级粉末，碳化硅纳米级粉末，二硅化锆纳米级粉末，加入到聚乙烯亚胺乙醇溶液中；其中，陶瓷基体原料粉末与聚乙烯亚胺的质量比为1；在持续超声震荡下机械搅拌60min，得到分散均匀的第 i层陶瓷涂层的浆料；同样的操作，可配置第i+1，i+2，…，3层陶瓷涂层的浆料；
4)在碳纤维上涂覆n层径向梯度陶瓷涂层：将步骤2)所得热解炭涂层纤维置于步骤3)配制的第i层陶瓷涂层的浆料中，电泳沉积20min，然后在80℃下真空干燥20min，得到第i层陶瓷涂层纤维；然后将第i层陶瓷涂层纤维置于步骤3)配制的第i+1层陶瓷涂层的浆料中，电泳沉积20min，在真空条件下 80℃干燥20min，得到第i+1层陶瓷涂层纤维；如此重复操作，直到获得第n 层陶瓷涂层纤维；得到的3层陶瓷涂层纤维如图1所示。
5)将步骤4)得到的第n层陶瓷涂层纤维置于高温热压炉中，施加40MPa 的压力，在1600℃下烧结60分钟，最终得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料。
实施例2
本实施例和实施例1不同的是，n＝5；i＝1，2，3，4，5；在步骤4)中，电泳沉积时间为12min。如图2所示，利用电泳沉积技术在碳纤维上涂覆5层径向梯度陶瓷涂层。
实施例3
本实施例和实施例1不同的是，二硼化物超高温陶瓷为二硼化铪；以碳纤维增韧超高温陶瓷基复合材料的体积为100份计，碳纤维的体积份为30；m＝30； n＝5；i＝1，2，3，4，5；在步骤4)中，电泳沉积时间为14min。
综上，本发明的一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，解决了碳纤维与基体热不匹配的问题，提升了复合材料的机械性能，避免了复合材料抗氧化、抗烧蚀性能的下降；设计的梯度陶瓷基体，提高了复合材料的抗断裂性能和抗热冲击性能；来源于聚合物的热解碳与二硅化锆发生化学反应，原位生成了纳米级超高温相，提升了复合材料的耐超高温性能；此外，可以在纤维纺丝工艺过程中实现。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (2)

1.一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，其特征在于，在碳纤维的截面方向上，具有n层以碳纤维为中心从内到外热膨胀系数逐渐变大的梯度陶瓷基体，最内层陶瓷基体原料包括碳化硅和二硅化锆；最外层陶瓷基体原料包括二硼化物超高温陶瓷和二硅化锆；中间层的陶瓷基体原料包括：二硼化物超高温陶瓷、碳化硅和二硅化锆；所述的二硼化物超高温陶瓷包括二硼化锆或二硼化铪；以碳纤维增韧超高温陶瓷基复合材料的体积为100份计，碳纤维的体积份为10-60；对于第i层陶瓷基体，以这一层的体积为100份计，二硅化锆的体积份设为m，二硼化物超高温陶瓷的体积份为
Figure FDA0002982694720000011
碳化硅的体积份为
Figure FDA0002982694720000012
其中，m＝10-40；n＝2，3，4，5，…；i＝1，2，3，4，…，n。
2.一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料的制备方法，其特征在于：是利用电泳沉积技术在碳纤维上涂覆n层径向梯度陶瓷涂层，然后通过热压烧结得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料，具体步骤包括：
1)对碳纤维进行预氧化处理，以便分开纤维丝：将原始碳纤维置于高温炉中，在300-550℃下氧化处理5-40min；
2)在碳纤维上涂覆热解碳涂层，用于保护碳纤维：首先以多巴胺为原料，利用电泳沉积技术在碳纤维上涂覆聚多巴胺涂层，然后在600-1400℃下热解30-120min得到热解炭涂层纤维；
3)配制第i层陶瓷涂层的浆料：首先将聚乙烯亚胺溶于无水乙醇中配成浓度为1-20mg/ml的聚乙烯亚胺乙醇溶液；然后根据第i层陶瓷基体的体积比换算成质量比，称取二硼化物超高温陶瓷纳米级粉末、碳化硅纳米级粉末、二硅化锆纳米级粉末，加入到聚乙烯亚胺乙醇溶液中；其中，陶瓷基体原料粉末与聚乙烯亚胺的质量比为0.9-50:1；在持续超声震荡下机械搅拌20-60min，得到分散均匀的第i层陶瓷涂层的浆料；同样的操作，可配置第i+1，i+2，…，n层陶瓷涂层的浆料；
4)在碳纤维上涂覆n层径向梯度陶瓷涂层：将步骤2)所得热解炭涂层纤维置于步骤3)配制的第i层陶瓷涂层的浆料中，电泳沉积2-120min，然后在60-100℃下真空干燥10-60min，得到第i层陶瓷涂层纤维；然后将第i层陶瓷涂层纤维置于步骤3)配制的第i+1层陶瓷涂层的浆料中，电泳沉积2-120min，在真空条件下60-100℃干燥10-60min，得到第i+1层陶瓷涂层纤维；如此重复操作，直到获得第n层陶瓷涂层纤维；
5)将步骤4)得到的第n层陶瓷涂层纤维置于高温热压炉中，施加20-50MPa的压力，在1400-1700℃下烧结10-120分钟，最终得到一种避免热不匹配的碳纤维增韧超高温陶瓷基复合材料。
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CN112341230B (zh) * 2020-11-10 2022-02-15 大连理工大学 一种受树叶启发的分级增韧超高温陶瓷基复合材料及其制备方法

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