CN107746283B - 一种碳纳米管均匀分散增强氧化铝复合材料的制备方法 - Google Patents

一种碳纳米管均匀分散增强氧化铝复合材料的制备方法 Download PDF

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CN107746283B
CN107746283B CN201711062537.0A CN201711062537A CN107746283B CN 107746283 B CN107746283 B CN 107746283B CN 201711062537 A CN201711062537 A CN 201711062537A CN 107746283 B CN107746283 B CN 107746283B
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贾建刚
刘第强
季根顺
郝相忠
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Lanzhou University of Technology
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Abstract

本发明公开了一种碳纳米管(CNTs)均匀分散增强氧化铝复合材料的制备方法，包括如下步骤：将TiO2与CuO的按一定重量比进行球磨混合后，取出备用；用烧杯量取200ml蒸馏水水浴加热至90℃，加入15g异丙醇铝，90℃水解4h后，加入1mlHNO3，90℃保温10h，得AlOOH溶胶；将CNTs按CNTs占CNTs/α‑Al2O3复合材料质量百分比为0.2％‑0.6％的比例均匀分散在所得的AlOOH溶胶内，加热至凝胶状后，按重量百分比1∶50加入所得的TiO2‑CuO烧结助剂，进行成型、干燥、煅烧和热压烧结处理，即得。本发明实现了碳纳米管在α‑Al2O3基体中的均匀分散，取得极佳的强韧化效果。

Description

一种碳纳米管均匀分散增强氧化铝复合材料的制备方法
技术领域
本发明涉及复合材料制备领域，具体涉及一种碳纳米管均匀分散增强氧化铝复合材料的制备方法。
背景技术
α-Al2O3陶瓷具有高强度、高模量、高硬度、耐磨损、耐腐蚀、抗氧化、热膨胀系数小、尺寸稳定等诸多优点，因此成为能源、航空航天、化工、电子等特别是高温下应用的结构部件的候选材料，故又称为高温结构陶瓷或工程陶瓷。但氧化铝陶瓷脆性大，抗热冲击性能差等这就限制了它的发展。通过加入增强材料后，可以在保留原有特点的基础上获得韧性较高的陶瓷基复合材料。碳纳米管(CNTs)是一种有碳-碳共价键结合的一维中空管状结构的纳米材料，具有强度高、长径比大、管径小等特点，其杨氏模量和剪切模量与金刚石相当，理论强度是钢的100倍，而密度仅为刚的1/7，碳纳米管可通过Stone-Wales变形不仅可以发生弹性变形而且可以发生一定的塑性变形具有很高的韧性。CNTs以其独特的力学性能被认为是最理想的晶须增韧材料，是纤维增韧的终极形式，碳纳米管广泛应用于陶瓷、聚合物和金属基复合材料的强化相.通过CNTs拔出桥联等机制能阻碍裂纹扩展，使复相陶瓷的断裂韧性提高。CNTs增强α-Al2O3优越性主要体现在：首先，CNTs的独特结构通过体积变化使其呈现高弹性，可承受40％的张力应变，且CNTs的破坏是通过其中空部分的塌陷来完成的，当基体断裂时，CNTs的拨出和断裂可吸收更多的能量，使复合材料呈现韧性断裂。然而，如何实现CNTs在基体中的均匀分布仍是CNTs增强陶瓷基复合材料的重大难题。
发明内容
为解决上述问题，本发明提供了一种碳纳米管均匀分散增强氧化铝复合材料的制备方法，实现了碳纳米管在α-Al2O3基体中的均匀分散，不仅对于CNTs增强氧化铝基复合材料的开发具有显然具有重大的现实意义，也为其他CNTs增强的复合材料提供有益的借鉴，推动CNTs增强复合材料快速发展。
为实现上述目的，本发明采取的技术方案为：
一种碳纳米管均匀分散增强氧化铝复合材料的制备方法，包括如下步骤：
S1、将TiO2与CuO的按一定的重量比进行球磨混合，球料比15∶1，转速为250r/min，球磨20h后，得TiO2-CuO烧结助剂，取出备用；所述TiO2与CuO的质量比为4∶1；
S2、用烧杯量取200ml蒸馏水水浴加热至90℃，加入15g异丙醇铝，90℃水解4h后，加入1ml质量分数为65％的HNO390℃保温10h，得AlOOH溶胶；
S3、将CNTs按CNTs占CNTs/α-Al2O3复合材料质量百分比为0.2％-0.6％的比例均匀分散在所得的AlOOH溶胶内，90℃恒温加热至凝胶状后，按重量百分比1∶50加入所得的TiO2-CuO烧结助剂，进行成型、100℃干燥10h煅烧(460℃煅烧4h后，进行热压烧结处理，即得CNTs/α-Al2O3复合材料；所述热压烧结的工艺条件为1500℃，20MPa，保温1h热压烧结。
本发明具有以下有益效果：
采用溶胶-凝胶法制备氧化铝前驱体，并将CNTs分散在AlOOH溶胶中，实现了CNTs均匀分散的CNTs/α-Al2O3复合材料，取得极佳的强韧化效果，不仅对于CNTs增强氧化铝基复合材料的开发具有显然具有重大的现实意义，也为其他CNTs增强的复合材料提供有益的借鉴，推动CNTs增强复合材料快速发展。
附图说明
图1为本发明实施例中所用到的CNTs的SEM形貌含。
图2为本发明实施例中添加烧结助剂CNTs/α-Al2O3复合材料的抗弯强度。
图3为本发明实施例中含烧结助剂CNTs/α-Al2O3复合材料三点弯曲载荷-位移曲线；
图中：(a)CNTs含量0.2％，(b)CNTs含量0.4％，(c)CNTs含量0.6％
图4为CNTs均匀分散到α-Al2O3基体中的SEM形貌。
具体实施方式
为了使本发明的目的及优点更加清楚明白，以下结合实施例对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例
一种碳纳米管均匀分散增强氧化铝复合材料的制备方法，包括如下步骤：
S1、采用南京大学生产的SP-3型行星式球磨机将TiO2与CuO的按重量比4∶1进行球磨混合，球料比15∶1，转速为250r/min，球磨20h后，得TiO2-CuO烧结助剂，取出备用；
S2、用烧杯量取200ml蒸馏水水浴加热至90℃，加入15g异丙醇铝，90℃水解4h后，加入1mlHNO3，90℃保温10h，得AlOOH溶胶；
S3、将CNTs按CNTs占CNTs/α-Al2O3复合材料质量百分比为0.2％-0.6％的比例均匀分散在所得的AlOOH溶胶内，加热至凝胶状后，按重量百分比1∶50加入所得的TiO2-CuO烧结助剂，进行成型、干燥、煅烧和热压烧结处理，即得CNTs/α-Al2O3复合材料。
图1为所用到的CNTs的SEM形貌，可以看到碳纳米管的管径从40-140nm大小不等，表面也不光滑。通过观察CNTs和TiO2-CuO烧结助剂分散到AlOOH溶胶的预制体，可以看到CNTs在AlOOH溶胶中是均匀分散的。
不同CNTs含量的复合材料抗弯强度如图2所示，可以看出，随着CNTs含量的增加，复合材料的抗弯强度也增加，其中CNTs含量为0.6％的复合材料平均强度为325Mpa，明显高于CNTs含量为0时的氧化铝陶瓷材料平均强度(167MPa)；可见，碳纤维含量为0.6％时复合材料的抗弯强度最大，最大强值高达325Mpa，比相同条件下制备的不含碳纤维的试样平均强度提高了95％。
图3(a)、(b)、(c)分别为CNTs含量分别为0.2％、0.4％和0.6％的复合材料材料三点弯曲实验时的载荷-位移曲线，CNTs含量为0.2％的复合材料载荷位移曲线具有脆性断裂特征。而0.4％和0.6％的复合材料，在载荷-位移曲线的非线性断出现棘齿状波动，随着载荷的增加发出轻微的响声，具有非线性特征的载荷-位移曲线，表明材料在断裂时吸收了断裂功，表明复合材料的韧性提高。
图4为CNTs含量为0.6％的CNTs/α-Al2O3复合材料SEM形貌。可以看到CNTs在基体中的分布非常均匀，复合材料在断裂的过程中CNTs在裂纹前端有纤维的桥接，可能从基体中拔出或者通过CNTs在基体的界面结合中脱粘，从而使复合材料在断裂时裂纹发生偏转，这样就使裂纹的扩展途径延长，在氧化铝基复合材料中形成了新的能量吸收机制，从而使材料的韧性提高。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (2)

1.一种碳纳米管均匀分散增强氧化铝复合材料的制备方法，其特征在于，包括如下步骤：
S1、将TiO2与CuO的按4∶1的重量比进行球磨混合，球料比15∶1，转速为250r/min，球磨20h后，得TiO2-CuO烧结助剂，取出备用；
S2、用烧杯量取200ml蒸馏水水浴加热至90℃，加入15g异丙醇铝，90℃水解4h后，加入1ml质量分数为65％的HNO390℃保温10h，得AlOOH溶胶；
S3、将CNTs按CNTs占CNTs/α-Al2O3复合材料质量百分比为0.2％-0.6％的比例均匀分散在所得的AlOOH溶胶内，90℃恒温加热至凝胶状后，按重量百分比1∶50加入所得的TiO2-CuO烧结助剂，进行成型、100℃干燥10h460℃煅烧4h后，进行热压烧结处理，即得CNTs/α-Al2O3复合材料。
2.根据权利要求1所述的一种碳纳米管均匀分散增强氧化铝复合材料的制备方法，其特征在于，所述热压烧结的工艺条件为1500℃，20MPa，保温1h热压烧结。
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