CN112125653A - 一种基于3d打印制备的石墨烯陶瓷复合材料及其制备方法 - Google Patents
一种基于3d打印制备的石墨烯陶瓷复合材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于3D打印制备的石墨烯陶瓷复合材料及其制备方法,属于陶瓷复合材料制备领域。石墨烯陶瓷复合材料是由Al2O3、SiC颗粒以及石墨烯三种原料制备而成。制备流程主要包括:球磨混合,制作浆料,3D打印,烘干,微波烧结。本发明的主要优点有:采用3D打印技术与微波加压烧结相结合的方法,在烧结过后,氧化铝与碳化硅组成纳米陶瓷复合材料,石墨烯对碳化硅氧化铝陶瓷进行了改性,制备出的复合材料具有良好的断裂韧性、导电与导热性等。该方法制备的陶瓷复合材料工艺简单,通用性强,实现了陶瓷复合材料的无模增材制造,同时大大降低了生产成本,具有良好的经济效益。
Description
技术领域
本发明属于陶瓷复合材料技术领域,涉及3D打印技术,尤其是一种基于3D打印制备的石墨烯陶瓷复合材料、及其制备方法。
背景技术
现代陶瓷材料具有耐高温、硬度高、耐磨损、耐腐蚀及相对密度轻等许多优良的性能,使其具有接替金属作为高温结构材料的潜力。但是,陶瓷材料的脆性大、耐热震性能差,而且陶瓷材料对裂纹、气孔和夹杂物细微的缺陷很敏感等缺点阻碍其实用化。陶瓷复合材料是以纤维、晶须或颗粒为增强体,以陶瓷为基体的复合材料。增强陶瓷复合材料常用的晶须有碳化硅晶须、Si3N4晶须、氧化铝晶须等。碳化硅晶须补强氧化铝陶瓷时,可以起到强化晶界、细化晶粒的作用,并且在发生断裂时SiC晶须还有裂纹桥联、裂纹偏转与分叉、拔出效应等作用,所以抗弯强度和断裂韧性都有显著提高。目前陶瓷复合材料主要应用于航空、航天等领域。
近年来,由于石墨烯优异的光学、电学、力学特性,在材料学、微纳加工、能源、生物医学和药物传递等方面具有重要的应用前景,被认为是一种未来革命性的材料,以及其大规模量产的可行性,使其成为了研究热点。将石墨烯作为增强相添加到陶瓷复合材料中,可以提高复合材料的断裂韧性,又可以显著提升材料的导热/导电性,扩大陶瓷材料的应用范围。在陶瓷材料中加入石墨烯,石墨烯在陶瓷材料中可以实现自身增强增韧、拔出效应以及裂纹偏转等增韧机理,使得石墨烯/陶瓷基复合材料具有优异的力学性能。此外,石墨烯原子间作用力强,结构稳定,碳原子在受到外来缺陷和原子干扰的情况下不易发生散射,可以显著提高陶瓷基复合材料的导电性能。石墨烯具有极高的声子平均自由程,使得它具有优异的热导率,可以极大改善陶瓷基复合材料的导热性能。
3D打印是一种三维成型的方法,将设计和成型融为一体,借助计算机软件,将虚拟的结构变为真实的构件,可以打印多种多样的尺寸以及丰富多彩的形状。无模直写成型技术是3D打印的一种,使用计算机软件设计模型,将所制浆料通过气体动力挤出,按所设计模型层层打印,得到所需结构。无模直写成型技术具有以下优点:
(1)可以通过调配陶瓷浆料的添加剂等变量,使浆料的固相含量在一定范围内可以调控,保证构件的均匀性以及可以控制的致密度。
(2)点胶针头的直径从亚微米级到毫米级,精度可控度高,构件的大小及形状可灵活设计。
(3)设备简单,操作方便,成本低廉。
微波烧结是指材料以微波辐射作为外加热源,材料因其自身对于微波具有一定的吸收(介质损耗)进而得到能量而使材料致密化的过程。相对于传统烧结过程中,材料表面、内部和中心区域温度梯度大,晶粒大小不均匀,内部容易形成孔洞、偏析等较大缺陷,微波烧结依靠微波电磁场辐射透入材料内部,材料整体发生介质损耗而升温,各部分温差小,易得到均匀细晶结构。与传统烧结相比,微波烧结主要有整体加热、低温快烧、无加热惯性、选择性加热等显著特点。
发明内容
本发明的目的在于解决了目前陶瓷材料韧性、导电导热性差的问题,改善了陶瓷材料的力学性能,扩大了陶瓷材料除航空、航天的应用领域,发明的一种的石墨烯陶瓷复合材料、及其制备方法,结合3D打印和微波烧结技术,制备过程方便快捷、烧结速度快且烧结致密。
一种基于3D打印制备石墨烯陶瓷复合材料的方法,其特征在于,包括以下步骤:
(1)Al2O3粉、SiC粉、石墨烯三种原料的占比为:SiC粉的质量分数为20~30wt.%,石墨烯的质量分数为3~7wt.%,其余为Al2O3;将Al2O3粉、SiC粉、石墨烯与无水乙醇混合,超声分散12h,然后进行球磨,球磨过后的浆料在60℃干燥箱干燥4h,干燥结束后研磨、过80目筛,加入分散剂和粘结剂,在55~85℃的温度下溶于去离子水中,充分搅拌均匀制成水基浆料;
(2)将水基浆料放入挤压式打印注射筒内,根据要打印材料的形状和参数使用AutoCAD软件进行三维建模,使用AutoCAD将所建模型输出为STL格式文件,将STL格式文件导入切片软件中,该软件将STL文件切割成与挤出针头直径相似厚度的片层,再导入3D打印设备的控制电脑中进行3D打印;
(3)对打印结束后的产品进行烘干;
(4)把3D打印后的模型进行微波加压烧结,所用微波频率2.45GHz,采用SiC作为吸波层,采用双向微波烧结方法,抽真空后充氩保护,首先加热到330~380℃,保温1个小时,使得分散剂和粘结剂顺利排出,然后以30~100℃/min的升温速率升温到1200~1800℃,烧结50~70min。
进一步地,步骤(1)中所述的Al2O3粉的粒径为1um,纯度99.8%;SiC颗粒的粒径为10um,纯度为99.5%;石墨烯纯度为99.8%。
进一步地,所述分散剂为羧甲基纤维素钠。
进一步地,粘结剂为聚乙烯醇,粘结剂浓度为200mg/mL~300mg/mL。
进一步地,步骤(1)中球磨介质为氧化锆球,球料比为4︰1,球磨8h,转速为300r/min。
进一步地,步骤(3)对产品真空干燥至少12h。
进一步地,步骤(4)中第二次升温的升温速率为30~100℃/min。
进一步地,步骤(4)中抽真空的真空度<0.1Pa,充氩气所加压力>30MPa。
所述方法制得的石墨烯陶瓷复合材料,其特征在于:由Al2O3粉、SiC粉、石墨烯复合而成,Al2O3粉、SiC粉、石墨烯三种原料的占比为:SiC粉的质量分数为20~30wt.%,石墨烯的质量分数为3~7wt.%,其余为Al2O3。
本发明的有益效果体现如下:
(1)通过超声分散和球磨机球磨可以使三种材料分散均匀,使得在之后的制备过程中获得性能与组织均匀的材料。
(2)本发明使用SiC和石墨烯的粉末混合添加到Al2O3中,添加的SiC是微波的良好吸收体,所以改善了Al2O3粉体的微波烧结性能,降低陶瓷的烧成温度,且碳化硅晶须有强化晶界、细化晶粒、阻止裂纹拓展的作用。而由于石墨烯的添加,使得材料具有了良好的导热导电性能等,从而获得了新型的陶瓷复合材料。
(3)本发明采用3D打印和微波加压烧结工艺相结合的陶瓷制备方法,在打印过程中,可根据实际需要打印不同结构,用以满足不同工程条件下对于复合材料形状的不同要求,并且材料在氩气保护气氛下加压微波烧结,烧结速度快,防止了SiC的氧化,实现整体加热、可选择性加热、制得致密度高,组织缺陷少,经过加压可以使颗粒之间结合紧密,减少气孔率,增加致密化,可改善组织和性能优化。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
实施例1:
制备含量为25wt.%的SiC粉、含量为3wt.%的石墨烯,其余为Al2O3粉的3D打印石墨烯陶瓷复合材料:
选取粒径为10um、纯度为99.5%、含量为25wt.%的SiC粉,纯度为99.8%、含量为3wt.%的石墨烯,基体为粒径为1um、纯度99.8%的Al2O3粉,与一定量的无水乙醇混合,超声分散12h,然后进行球磨,球磨介质为氧化锆球,球料比为4︰1,球磨8h,转速为300r/min,球磨过后的浆料在60℃干燥箱干燥4h,干燥结束后研磨过80目筛,再加入分散剂羧甲基纤维素钠和粘结剂聚乙烯醇,在55~85℃的温度下溶于去离子水中,充分搅拌均匀制成水基浆料;接着将水基浆料放入挤压式打印注射筒内,根据要打印材料的形状和参数使用AutoCAD软件进行三维建模,使用AutoCAD将所建模型输出为STL格式文件,将STL格式文件导入切片软件中,该软件将STL文件切割成与挤出针头直径相似厚度的片层,再导入3D打印设备的控制电脑中进行3D打印;对打印结束后的产品进行真空干燥12h。把干燥后的模型进行微波加压烧结,所用微波频率2.45GHz,采用SiC作为吸波层,采用双向微波烧结方法,抽真空后充氩保护,真空度<0.1Pa,所加压力>30MPa,首先将温度加热到330~380℃,保温1个小时,使得分散剂和粘结剂顺利排出,然后温度升高到1200~1800℃,进行烧结,升温速率30~100℃/min,烧结时间50~70min,烧结后得到复合材料。
实施例2:
制备含量为30wt.%的SiC粉、含量为3wt.%的石墨烯,其余为Al2O3粉的3D打印石墨烯陶瓷复合材料:
选取粒径为10um、纯度为99.5%、含量为30wt.%的SiC粉,纯度为99.8%、含量为3wt.%的石墨烯,基体为粒径为1um、纯度99.8%的Al2O3粉,与一定量的无水乙醇混合,超声分散12h,然后进行球磨,球磨介质为氧化锆球,球料比为4︰1,球磨8h,转速为300r/min,球磨过后的浆料在60℃干燥箱干燥4h,干燥结束后研磨过80目筛,再加入分散剂羧甲基纤维素钠和粘结剂聚乙烯醇,在55~85℃的温度下溶于去离子水中,充分搅拌均匀制成水基浆料;接着将水基浆料放入挤压式打印注射筒内,根据要打印材料的形状和参数使用AutoCAD软件进行三维建模,使用AutoCAD将所建模型输出为STL格式文件,将STL格式文件导入切片软件中,该软件将STL文件切割成与挤出针头直径相似厚度的片层,再导入3D打印设备的控制电脑中进行3D打印;对打印结束后的产品进行真空干燥12h。把干燥过后的模型进行微波加压烧结,所用微波频率2.45GHz,采用SiC作为吸波层,采用双向微波烧结方法,抽真空后充氩保护,真空度<0.1Pa,所加压力>30MPa,首先将温度加热到330~380℃,保温1个小时,使得分散剂和粘结剂顺利排出,然后温度升高到1200~1800℃,进行烧结,升温速率30~100℃/min,烧结时间50~70min,烧结后得到复合材料。
实施例3:
制备含量为30wt.%的SiC粉、含量为5wt.%的石墨烯,其余为Al2O3粉的3D打印石墨烯陶瓷复合材料:
选取粒径为10um、纯度为99.5%、含量为30wt.%的SiC粉,纯度为99.8%、含量为5wt.%的石墨烯,基体为粒径为1um、纯度99.8%的Al2O3粉,与一定量的无水乙醇混合,超声分散12h,然后进行球磨,球磨介质为氧化锆球,球料比为4︰1,球磨8h,转速为300r/min,球磨过后的浆料在60℃干燥箱干燥4h,干燥结束后研磨过80目筛,再加入分散剂羧甲基纤维素钠和粘结剂聚乙烯醇,在55~85℃的温度下溶于去离子水中,充分搅拌均匀制成水基浆料;接着将水基浆料放入挤压式打印注射筒内,根据要打印材料的形状和参数使用AutoCAD软件进行三维建模,使用AutoCAD将所建模型输出为STL格式文件,将STL格式文件导入切片软件中,该软件将STL文件切割成与挤出针头直径相似厚度的片层,再导入3D打印设备的控制电脑中进行3D打印。对打印结束后的产品进行真空干燥12h。把干燥过后的模型进行微波加压烧结,所用微波频率2.45GHz,采用SiC作为吸波层,采用双向微波烧结方法,抽真空后充氩保护,真空度<0.1Pa,所加压力>30MPa,首先将温度加热到330~380℃,保温1个小时,使得分散剂和粘结剂顺利排出,然后温度升高到1200~1800℃,进行烧结,升温速率30~100℃/min,烧结时间50~70min,烧结后得到复合材料。
所述实施例为本发明的优选的实施方式,但本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (9)
1.一种基于3D打印制备石墨烯陶瓷复合材料的方法,其特征在于,包括以下步骤:
(1)Al2O3粉、SiC粉、石墨烯三种原料的占比为:SiC粉的质量分数为20~30wt.%,石墨烯的质量分数为3~7wt.%,其余为Al2O3;将Al2O3粉、SiC粉、石墨烯与无水乙醇混合,超声分散12h,然后进行球磨,球磨过后的浆料在60℃干燥箱干燥4h,干燥结束后研磨、过80目筛,加入分散剂和粘结剂,在55~85℃的温度下溶于去离子水中,充分搅拌均匀制成水基浆料;
(2)将水基浆料放入挤压式打印注射筒内,根据要打印材料的形状和参数使用AutoCAD软件进行三维建模,使用AutoCAD将所建模型输出为STL格式文件,将STL格式文件导入切片软件中,该软件将STL文件切割成与挤出针头直径相似厚度的片层,再导入3D打印设备的控制电脑中进行3D打印;
(3)对打印结束后的产品进行烘干;
(4)把3D打印后的模型进行微波加压烧结,所用微波频率2.45GHz,采用SiC作为吸波层,采用双向微波烧结方法,抽真空后充氩保护,首先加热到330~380℃,保温1个小时,使得分散剂和粘结剂顺利排出,然后以30~100℃/min的升温速率升温到1200~1800℃,烧结50~70min。
2.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:步骤(1)中所述的Al2O3粉的粒径为1um,纯度99.8%;SiC颗粒的粒径为10um,纯度为99.5%;石墨烯纯度为99.8%。
3.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:所述分散剂为羧甲基纤维素钠。
4.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:粘结剂为聚乙烯醇,粘结剂浓度为200mg/mL~300mg/mL。
5.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:步骤(1)中球磨介质为氧化锆球,球料比为4︰1,球磨8h,转速为300r/min。
6.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:步骤(3)对产品真空干燥至少12h。
7.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:步骤(4)中第二次升温的升温速率为30~100℃/min。
8.根据权利要求1所述的3D打印制备石墨烯陶瓷复合材料的方法,其特征在于:步骤(4)中抽真空的真空度<0.1Pa,充氩气所加压力>30MPa。
9.权利要求1-8任一项所述方法制得的石墨烯陶瓷复合材料,其特征在于:由Al2O3粉、SiC粉、石墨烯复合而成,Al2O3粉、SiC粉、石墨烯三种原料的占比为:SiC粉的质量分数为20~30wt.%,石墨烯的质量分数为3~7wt.%,其余为Al2O3。
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