基于石墨烯的结构功能一体化氧化物陶瓷复合材料: 从制备到性能

doi:10.15541/jim20170363

摘要/Abstract

摘要：

现代社会对于氧化物陶瓷材料的性能不断提出更高的要求, 因此对于氧化物陶瓷复合材料的研究显得尤为重要。石墨烯作为一种具有卓越性能的二维碳材料, 非常适合作为增强相用于提高氧化物陶瓷复合材料的力学和电性能。本文系统总结了过去十年来基于石墨烯的氧化物陶瓷复合材料的相关研究和报道, 从石墨烯/氧化物陶瓷复合材料的制备、烧结、微观结构到性能进行了比较全面的介绍, 从中可以看出: (1)石墨烯的引入使得氧化物陶瓷的力学性能在强度、断裂韧性、应变容忍度等方面获得全面的提升; (2)在电性能方面, 石墨烯/氧化物陶瓷复合材料不仅具有低渗流阈值和良好的电导, 而且其载流子类型还可以通过调节氧化物基体中的氧空位浓度来调控。因此, 基于石墨烯的氧化物陶瓷复合材料有望作为一种高性能结构功能一体化陶瓷获得应用。

关键词: 石墨烯, 陶瓷基复合材料, 材料制备, 力学性能, 电学性能, 综述

Abstract:

It is of great importance to enhance the performance of oxide ceramic composite for fulfilling the increasing requirements from modern society. To this end, graphene is very suitable to be exploited as reinforcement for achieving superior performance in oxide ceramic composites, due to its extraordinary mechanical and electrical properties. In this review, the study of graphene based oxide ceramic composite including the processing, densification, microstructure and properties, based on the reports and researches in the past decade. It can be seen that: (1) the incorporation of graphene can generally improve the strength, fracture toughness and strain tolerance of oxide ceramic composite; (2) for the electrical performance, the graphene/oxide ceramic composites show not only low percolation threshold and high electrical conductivity, but also tunable charge carrier type which can be controlled by the oxygen concentration in oxide matrix. Therefore, it is believed that the graphene based oxide ceramic composites are very promising material for the application requiring both advanced mechanical and functional properties.

Key words: graphene, ceramic matrix composite, materials processing, mechanical property, electrical property, review

中图分类号:

TQ174

范宇驰, 王连军, 江莞. 基于石墨烯的结构功能一体化氧化物陶瓷复合材料: 从制备到性能[J]. 无机材料学报, 2018, 33(2): 138-146.

FAN Yu-Chi, WANG Lian-Jun, JIANG Wan. Graphene Based Oxide Ceramic Composites with High Mechanical and Functional Performance: from Preparation to Property[J]. Journal of Inorganic Materials, 2018, 33(2): 138-146.

图/表 8

图1 从石墨片层中剥离石墨烯的示意图[8]

Fig. 1 Schematic illustration of exfoliating GNSs from graphite pallets [8] The arrows indicate the shear effect in a ball milling process

图2 利用机械剥离法制备的石墨烯/氧化铝复合材料断面的SEM照片[8-9]

Fig. 2 SEM image of fracture surface for graphene nanosheet/ Al2O3 composite prepared via mechanical exfoliation[8-9]

图3 利用异相沉积法制备的石墨烯/氧化铝复合材料的TEM照片[16]

Fig. 3 TEM image of graphene/Al2O3 composite prepared by heteroaggregation[16]

图4 二维材料石墨烯能够更有效的抑制晶粒粗化[21] 除了晶粒大小, 石墨烯对陶瓷基体的影响还体现在晶粒的微观形貌上[21]。以氧化铝为例, 单纯的氧化铝陶瓷烧结之后, 晶粒会呈现不同的楞面, 这是晶界移动达到热力学平衡状态的结果。本课题组发现在石墨烯/氧化铝复合材料中, 很难找到这种含有明显楞面的晶粒, 从复相陶瓷的断面上观察发现大多数晶粒呈现出比较圆滑的表面, 即便进一步提高烧结温度结果仍然如此。研究还发现, 在烧结致密的氧化铝基体中存在一些小于原始粉体粒径的晶粒, 从晶界曲率判断本应该在二次再结晶过程中被周围较大的晶粒吸收, 但由于晶界上存在石墨烯而被完好的保存下来(图5)。这一现象说明由于石墨烯的柔韧性和强大的阻碍晶界移动的能力, 使得在陶瓷复合材料整体达到致密的情况下大量的晶面还未达到热力学平衡的状态。这一独特的结构在其它材料如碳纳米管复合陶瓷材料中并未出现, 这是石墨烯陶瓷复合材料的微观结构特点。

Fig. 4 Schematic illustration showing 2D graphene can retard the coarsening of grain most effectively[21] (a), (b), (c) show the situation for nano-particle, 1D inclusion and 2D inclusion, respectively

图5 石墨烯阻碍晶界移动达到热力学平衡状态[21]

Fig. 5 Graphene prohibits grain boundary reaching dynamic balance[21] The yellow and white arrows indicate grain boundaries with and without graphene, respectively

图6 单相氧化铝(黑)、石墨烯/氧化铝复合材料(红)以及烧蚀后氧化铝复合材料(蓝)在四点抗弯试验中的应力-应变曲线[22]

Fig. 6 Stain-stress plots of monolithic Al2O3 ceramic (black), FLG/Al2O3 composite before (red) and after (blue) burn-off for 20 h during four-point bending test, respectively[22]

表1 一些石墨烯/氧化物陶瓷复合材料的电性能比较

Table 1 Comparison of some reported graphene/oxide ceramic composites

Matrix	Raw material of graphene^*	Mixing method	Percolation threshold	Maximum electrical conductivity	Reference
Al₂O₃	GO	Heteroaggregation	0.38vol%	1038.15 S•m^-1 for 2.35vol%	[16]
Al₂O₃	GO	Heteroaggregation	0.22wt%	11.1 S•m^-1 for 0.45wt%	[31]
Al₂O₃	G	Stirring + Ball milling	7.1vol%	20.1 S•m^-1 for 15vol%	[32]
Al₂O₃	G	Planetary ball milling	<0.5vol%	123.3 S•m^-1 for 2vol%	[33]
Al₂O₃	GN	Attrition ball milling	3vol%	10³S•m^-1 for 15vol%	[34]
Al₂O₃	EG	Planetary ball milling	3vol%	5709 S•m^-1 for 15vol%	[8]
Al₂O₃	EG	Attrition ball milling	4.7-5.7vol%	9.6×10^-2S•m^-1 for 9.4vol%	[35]
YSZ	GO	Sonication	2.5vol%	1.2×10⁴S•m^-1 for 4.1vol%	[36]
SiO₂	GO	Heteroaggregation	<0.58wt%	10^-2S•m^-1 for 0.98wt%	[37]
ZrO₂	GN	Planetary ball milling	<1wt%	98 S•m^-1 for 3wt%	[38]

图7 (a)石墨烯/氧化铝复合材料的电导随石墨烯含量的变化关系; (b)霍尔系数随着石墨烯含量的变化关系[16]

Fig. 7 (a) Electrical conductivity of graphene/Al2O3 composites as a function of filler volume fraction; (b) Hall coefficient plotted against filler volume fraction[16]

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