CN109020508B - 一种三维石墨烯桥连氧化物陶瓷及其制备方法 - Google Patents

一种三维石墨烯桥连氧化物陶瓷及其制备方法 Download PDF

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CN109020508B
CN109020508B CN201810760305.0A CN201810760305A CN109020508B CN 109020508 B CN109020508 B CN 109020508B CN 201810760305 A CN201810760305 A CN 201810760305A CN 109020508 B CN109020508 B CN 109020508B
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王玉金
阮超
张翰超
谢芳
王诗阳
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Jilin Changyu Tetao New Material Technology Co ltd
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Abstract

本发明公开了一种三维石墨烯桥连氧化物陶瓷，包括基体陶瓷纳米粒子和三维石墨烯，所述三维石墨烯均匀包覆所述基体陶瓷纳米粒子外层，且所述三维石墨烯的质量百分比为0.5～4％，提高了复合陶瓷材料的介电性能。本发明还提供一种三维石墨烯桥连氧化物陶瓷的制备方法，将木质纤维素转化为三维石墨烯网络，并均匀包覆于基体陶瓷粒子外层，既可增加复合陶瓷材料的介电性能，又可将导电和导热性能退耦形成良好的热电性能。

Description

一种三维石墨烯桥连氧化物陶瓷及其制备方法
技术领域
本发明涉及氧化物陶瓷材料设计及制备技术领域，更具体的是，本发明涉及一种三维石墨烯桥连氧化物陶瓷及其制备方法。
背景技术
氧化物陶瓷具有高熔融温度、高机械强度，电绝缘性能和化学稳定性，且对氧化气氛的耐受度极强。除氧化铍陶瓷外，氧化物陶瓷的导热性均较低。为改善氧化物陶瓷的导电导热性能、力学性能以及热电性能，研究人员已将多种碳纳米材料用做填料，通常采用物理掺杂方法来增强氧化物陶瓷，其中碳纳米材料的选择包括单壁碳纳米管(SWNTs)、多壁碳纳米管(MWNTs)、石墨烯(Graphene)以及还原型氧化石墨烯(r-GO)等；但由于碳纳米材料的强疏水性通常会使其在氧化物陶瓷中分散不均匀，进而导致所制备复合陶瓷的导电性和力学性能提升效果并不明显。另一方面，石墨烯作为一种新型碳纳米材料具有独特的理化性质，如优良的导电导热性、化学稳定性、低密度等；但石墨烯横向(片层尺寸)的导电性远高于纵向(片层厚度)，因此选择适当基体使其横向可以延展并控制纵向厚度更易于发挥石墨烯的导电性能。
发明内容
本发明的一个目的是提供一种三维石墨烯桥连氧化物陶瓷，将木质纤维素转化成的三维石墨烯网络均匀包覆于基体陶瓷粒子外层，提高复合陶瓷材料的介电性能。
本发明的另一个目的是提供一种三维石墨烯桥连氧化物陶瓷的制备方法，将木质纤维素转化为三维石墨烯网络，并均匀包覆于基体陶瓷粒子外层，既可增加复合陶瓷材料的介电性能，又可将导电和导热性能退耦形成良好的热电性能。
本发明提供的技术方案为：
一种三维石墨烯桥连氧化物陶瓷，包括基体陶瓷纳米粒子和三维石墨烯，所述三维石墨烯均匀包覆所述基体陶瓷纳米粒子外层，且所述三维石墨烯的质量百分比为0.5～4％。
优选的是，所述三维石墨烯为卷曲的多层石墨烯。
优选的是，所述石墨烯的层数为5～25层。
优选的是，所述基体陶瓷为氧化铝、氧化锆、氧化铍、尖晶石、莫来石、氧化钇稳定的氧化锆或锆钛酸铅陶瓷中的一种。
一种三维石墨烯桥连氧化物陶瓷的制备方法，包括如下步骤：
步骤1：配制体积分数为35％的基体陶瓷粉体浆料，调节pH值后与木质纤维素浆料混合得到混合浆料；
步骤2：将所述混合浆料湿磨后快速冷却并冷冻干燥得到木质纤维素和基体陶瓷型纳米复合陶瓷粉体；
步骤3：将所述纳米复合陶瓷粉体置于石墨模具中，并进行真空放电等离子体烧结，控制升温速率为80～100℃·min-1，最终烧结温度为1250～1500℃，接触压力由5～15MPa升至60～100MPa，烧结时间为30～60min，制得三维石墨烯桥连氧化物陶瓷。
优选的是，所述步骤1中的木质纤维素浆料中木质纤维素的体积分数为1.5～6％。
优选的是，所述步骤1中的pH调节值为8～10。
优选的是，在所述步骤2中，所述混合浆料湿磨采用：2～5mm的二氧化锆磨球，并以球磨机临界转速的55％旋转，球磨时间为3～6h。
优选的是，在所述步骤3中，接触压力在2min内由起始的8～10MPa升至最终的70～90MPa。
优选的是，所述基体陶瓷为氧化铝、氧化锆、氧化铍、尖晶石、莫来石、氧化钇稳定的氧化锆或锆钛酸铅陶瓷中的一种。
本发明所述的有益效果为：
(1)本发明提供的三维石墨烯桥连氧化物陶瓷，将三维石墨烯网络均匀包覆于基体陶瓷粒子外层，提高复合陶瓷材料的介电性能。
(2)本发明提供的三维石墨烯桥连氧化物陶瓷的制备方法，能够将木质纤维素转化为三维石墨烯网络，均匀包覆于基体陶瓷粒子外层，形成连续的电子传输通道，既可增加复合陶瓷材料的介电性能，又可将导电和导热性能退耦形成良好的热电性能。
(3)本发明获得的三维石墨烯桥连氧化物陶瓷结构适用于后续放电加工或烧结成型，进而制成复杂形状的陶瓷制品。
附图说明
图1为本发明实施例1得到的3D-Graphene@YSZ陶瓷的明场与暗场透射电镜图像。
图2为本发明实施例2得到的3D-Graphene@Al2O3陶瓷的暗场透射电镜图像以及能谱元素分析图。
具体实施方式
下面结合附图对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
本发明提供一种三维石墨烯桥连氧化物陶瓷(3D-Graphene@MxOy)，包括基体陶瓷MxOy纳米粒子和三维石墨烯，所述三维石墨烯均匀包覆所述基体陶瓷MxOy纳米粒子外层，且所述三维石墨烯的质量百分比为0.5～4％。
所述三维石墨烯为卷曲的多层石墨烯，其层数为5～25层。所述基体陶瓷MxOy为氧化铝(Al2O3)、氧化锆(ZrO2)、氧化铍(BeO2)、尖晶石(MgO·Al2O3)、莫来石(3Al2O3·2SiO2)、氧化钇稳定的氧化锆(YSZ)、锆钛酸铅(PZT)陶瓷中的一种。
本发明提供的三维石墨烯桥连氧化物陶瓷，将三维石墨烯网络均匀包覆于基体陶瓷粒子外层，提高复合陶瓷材料的介电性能。
本发明还提供一种三维石墨烯桥连氧化物陶瓷的制备方法，包括如下步骤：
步骤1：配制体积分数为35％的基体陶瓷MxOy粉体浆料，所述基体陶瓷MxOy为氧化铝(Al2O3)、氧化锆(ZrO2)、氧化铍(BeO2)、尖晶石(MgO·Al2O3)、莫来石(3Al2O3·2SiO2)、氧化钇稳定的氧化锆(YSZ)、锆钛酸铅(PZT)陶瓷中的一种；
调节pH值后与木质纤维素浆料混合得到混合浆料，所述木质纤维素浆料中木质纤维素的体积分数为1.5～6％，所述pH值控制在8～10之间。
步骤2：将步骤1得到的混合浆料湿磨后采用液氮快速冷却并冷冻干燥得到木质纤维素/基体陶瓷MxOy型纳米复合陶瓷粉体；
所述混合浆料的湿磨采用球磨机进行，向球磨机中装载混合浆料的装载量为球磨机筒体有效容积的50％，并且所述球磨机采用2～5mm的二氧化锆(ZrO2)磨球，湿磨过程中，以球磨机临界转速的55％旋转，球磨时间为3～6h。
步骤3：将所述纳米复合陶瓷粉体置于石墨模具中，并置于放电等离子体烧结炉中进行真空烧结，控制升温速率为80-100℃·min-1，最终烧结温度为1250-1500℃(根据所选基体陶瓷材料进行选取)，接触压力由5～15MPa升至60～100MPa，优选的是，接触压力在2min内由起始的8～10MPa升至最终的70～90MPa，烧结时间为30～60min，制得三维石墨烯桥连氧化物(3D-Graphene@MxOy)陶瓷。
实施例1
配制体积分数为35％的氧化钇稳定的氧化锆(YSZ)陶瓷粉体浆料，调节pH值在8～10之间后，依次与体积分数为1.5％、3％、4.5％、5％的木质纤维素浆料混合，将混合浆料湿磨，采用3mm的ZrO2的磨球，向球磨机中装载混合浆料的装载量为球磨机筒体有效容积的50％，并以球磨机临界转速的55％旋转，球磨时间为3h。然后用液氮快速冷却并冷冻干燥制得纳米木质纤维素/YSZ复合陶瓷粉体，最后将制备好的纳米复合陶瓷粉体装入石墨磨具，置于放电等离子体烧结炉中进行真空烧结，升温速率为80℃·min-1，最终烧结温度为1250℃，接触压力在2min内由起始的8MPa升至最终的70MPa，烧结时间为45min，最终制得三维石墨烯桥连氧化钇稳定的氧化锆(3D-Graphene@YSZ)陶瓷，其中石墨烯的质量百分比依次为0.5％、1％、2％、3％，含3％石墨烯的3D-Graphene@YSZ陶瓷的明场与暗场透射电镜图像如图1所示，从图中可以看出YSZ粒子外层覆盖有连续的三维碳结构。该复合陶瓷的导电性随三维石墨烯质量百分比含量变化如表1所示。
表1 3D-Graphene@YSZ陶瓷的电导率与三维石墨烯含量的关系
3D-Graphene含量(wt％) 0.5 1 2 3
电导率(S·m<sup>-1</sup>) 620 490 380 250
实施例2
配制体积分数为35％的氧化铝(Al2O3)陶瓷粉体浆料，调节pH值在8～10之间后，依次与体积分数为1.5％、3％、4.5％、6％的木质纤维素浆料混合，将混合浆料湿磨，采用2mmZrO2的磨球，向球磨机中装载混合浆料的装载量为球磨机筒体有效容积的50％，并以球磨机临界转速的55％旋转，球磨时间为4h。然后用液氮快速冷却并冷冻干燥制得纳米木质纤维素/Al2O3复合陶瓷粉体，最后将制备好的纳米复合陶瓷粉体装入石墨磨具，置于放电等离子体烧结炉中进行真空烧结，升温速率为80℃·min-1，最终烧结温度为1350℃，接触压力在2min内由起始的9MPa升至最终的80MPa，烧结时间为30min，最终制得三维石墨烯桥连氧化铝(3D-Graphene@Al2O3)陶瓷，其中石墨烯的质量百分比依次为1％、2％、3％、4％，含3％石墨烯的3D-Graphene@Al2O3陶瓷的暗场透射电镜图像以及能谱元素分析图如图2所示。该复合陶瓷的导电性随三维石墨烯质量百分比含量变化如表2所示。
表2 3D-Graphene@Al2O3陶瓷的电导率与三维石墨烯含量的关系
3D-Graphene含量(wt％) 1 2 3 4
电导率(S·m<sup>-1</sup>) 750 630 520 400
实施例3
配制体积分数为35％的氧化锆(ZrO2)陶瓷粉体浆料，调节pH值在8～10之间后，依次与体积分数为1.5％、3％、4.5％、6％的木质纤维素浆料混合，将混合浆料湿磨，采用2mmZrO2的磨球，向球磨机中装载混合浆料的装载量为球磨机筒体有效容积的50％，并以球磨机临界转速的55％旋转，球磨时间为6h。然后用液氮快速冷却并冷冻干燥制得纳米木质纤维素/ZrO2复合陶瓷粉体，最后将制备好的纳米复合陶瓷粉体装入石墨磨具，置于放电等离子体烧结炉中进行真空烧结，升温速率为100℃·min-1，最终烧结温度为1500℃，接触压力在2min内由起始的10MPa升至最终的90MPa，烧结时间为60min，最终制得三维石墨烯桥连氧化锆(3D-Graphene@ZrO2)陶瓷，其中石墨烯的质量百分比依次为1％、2％、3％、4％。该复合陶瓷的导电性随三维石墨烯质量百分比含量变化如表3所示。
表3 3D-Graphene@ZrO2陶瓷的电导率与三维石墨烯含量的关系
3D-Graphene含量(wt％) 1 2 3 4
电导率(S·m<sup>-1</sup>) 890 780 640 510
本发明提供的三维石墨烯桥连氧化物陶瓷的制备方法，能够将木质纤维素转化为三维石墨烯网络，均匀包覆于基体陶瓷粒子外层，形成连续的电子传输通道，既可增加复合陶瓷材料的介电性能，又可将导电和导热性能退耦形成良好的热电性能。并且本发明获得的三维石墨烯桥连氧化物陶瓷结构适用于后续放电加工或烧结成型，进而制成复杂形状的陶瓷制品。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。

Claims (5)

1.一种三维石墨烯桥连氧化物陶瓷的制备方法，其特征在于，包括如下步骤：
步骤1：配制体积分数为35％的基体陶瓷粉体浆料，调节pH值后与木质纤维素浆料混合得到混合浆料；
其中，所述木质纤维素浆料中木质纤维素的体积分数为1.5～6％；
步骤2：将所述混合浆料湿磨后快速冷却并冷冻干燥得到木质纤维素和基体陶瓷型纳米复合陶瓷粉体；
步骤3：将所述纳米复合陶瓷粉体置于石墨模具中，并进行真空放电等离子体烧结，控制升温速率为80～100℃·min-1，最终烧结温度为1250～1500℃，接触压力由5～15MPa升至60～100MPa，烧结时间为30～60min，制得三维石墨烯桥连氧化物陶瓷；
其中，所述三维石墨烯桥连氧化物陶瓷包括基体陶瓷纳米粒子和三维石墨烯，所述三维石墨烯均匀包覆所述基体陶瓷纳米粒子外层，且所述三维石墨烯的质量百分比为0.5～4％。
2.如权利要求1所述的三维石墨烯桥连氧化物陶瓷的制备方法，其特征在于，所述步骤1中的pH调节值为8～10。
3.如权利要求1所述的三维石墨烯桥连氧化物陶瓷的制备方法，其特征在于，在所述步骤2中，所述混合浆料湿磨采用：2～5mm的二氧化锆磨球，并以球磨机临界转速的55％旋转，球磨时间为3～6h。
4.如权利要求1所述的三维石墨烯桥连氧化物陶瓷的制备方法，其特征在于，在所述步骤3中，接触压力在2min内由起始的8～10MPa升至最终的70～90MPa。
5.如权利要求1所述的三维石墨烯桥连氧化物陶瓷的制备方法，其特征在于，所述基体陶瓷为氧化铝、氧化锆、氧化铍、尖晶石、莫来石、氧化钇稳定的氧化锆或锆钛酸铅陶瓷中的一种。
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