等离子活化烧结制备石墨烯/羟基磷灰石复相生物陶瓷

doi:10.15541/jim20180142

无机材料学报 ›› 2018, Vol. 33 ›› Issue (12): 1355-1359.DOI: 10.15541/jim20180142 CSTR: 32189.14.10.15541/jim20180142

等离子活化烧结制备石墨烯/羟基磷灰石复相生物陶瓷

张彪, 杨长安, 施佩

陕西科技大学材料科学与工程学院, 西安 710021

收稿日期:2018-04-02 修回日期:2018-04-26 出版日期:2018-12-20 网络出版日期:2018-11-27
作者简介:张彪(1990-), 男, 博士研究生. E-mail: yunzhuangzhb@163.com
基金资助:
陕西省科技统筹创新工程项目(2017TSCXL-GY-07-05, 2015KTTSGY02-03);陕西科技大学博士科研启动基金(2017BJ-26);陕西科技大学研究生创新基金项目

Synthesis of Graphene/Hydroxyapatite Composite Bioceramics via Plasma Activated Sintering

ZHANG Biao, YANG Chang-An, SHI Pei

School of Materials Science & Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China

Received:2018-04-02 Revised:2018-04-26 Published:2018-12-20 Online:2018-11-27
About author:ZHANG Biao. E-mail: yunzhuangzhb@163.com
Supported by:
Shaanxi Science & Technology Co-ordination & Innovation Project (2017TSCXL-GY-07-05, 2015KTTSGY02-03);Doctoral Scientific Research Fund of Shaanxi University of Science & Technology (2017BJ-26);Graduate Innovation Fund of Shaanxi University of Science and Technology

摘要/Abstract

摘要：

以羟基磷灰石(Hydroxyapatite, HAp)为基体, 石墨烯(Graphene, rGO)作为增强相, 利用等离子活化烧结制备了石墨烯/羟基磷灰石(rGO/HAp)复相生物陶瓷。系统研究了rGO添加量对HAp陶瓷基体物相结构、生物活性及断裂韧性的影响。结果表明, rGO的加入有利于提高HAp陶瓷的生物活性。同时, 复相生物陶瓷的硬度与断裂韧性随rGO添加量的增加均表现出先升高, 后显著降低的变化趋势。当rGO添加量为2wt%时, 样品的硬度与断裂韧性分别达到6.97 GPa和0.84 MPa•m^1/2, 较纯相HAp陶瓷提高了11.5%和37.3%。研究表明rGO的拔出效应是导致复相陶瓷力学性能提高的主要原因。

关键词: 羟基磷灰石, 石墨烯, 等离子活化烧结, 生物活性, 断裂韧性

Abstract:

Graphene/hydroxyapatite (rGO/HAp) composite bioceramics were fabricated by plasma activated sintering using hydroxyapatite (HAp) as matrix and graphene (rGO) as reinforced phase. The effects of rGO addition on phase structure, bioactivity and fracture toughness of HAp ceramics matrix were systematically investigated. The results indicate that the incorporation of rGO is beneficial to promoting the bioactivity of HAp ceramics. Meanwhile, hardness and fracture toughness of composite bioceramics initially increase and then decrease significantly with rGO concentration increasing. The hardness and fracture toughness of the specimen with rGO loading of 2wt% reach 6.97 GPa and 0.84 MPa•m^1/2, which display ~11.5% and ~37.3% improvements as compared to pure HAp ceramics, respectively. It is demonstrated that the pull-out effect of rGO is the major reason for enhancing the mechanical properties of composite ceramics.

Key words: hydroxapatite, graphene, plasma activated sintering, bioactivity, fracture toughness

中图分类号:

TB321

张彪, 杨长安, 施佩. 等离子活化烧结制备石墨烯/羟基磷灰石复相生物陶瓷[J]. 无机材料学报, 2018, 33(12): 1355-1359.

ZHANG Biao, YANG Chang-An, SHI Pei. Synthesis of Graphene/Hydroxyapatite Composite Bioceramics via Plasma Activated Sintering[J]. Journal of Inorganic Materials, 2018, 33(12): 1355-1359.

图/表 7

图1 rGO/HAp复相生物陶瓷的光学照片及断口SEM照片

Fig. 1 Optical photos (insets) and SEM images of fracture surface of rGO/HAp composite bioceramics(a) Pure HAp; (b) 1wt% rGO/HAp; (c) 2wt% rGO/HAp; (d) 5wt% rGO/Hap

图2 rGO/HAp复相生物陶瓷的XRD图谱

Fig. 2 XRD patterns of rGO/HAp composite bioceramics

图3 rGO/HAp复相生物陶瓷的Raman光谱图

Fig. 3 Raman spectra of rGO/HAp composite bioceramics

图4 2wt% rGO/HAp复相生物陶瓷的断口SEM照片及EDS图谱

Fig. 4 SEM images and EDS spectra of fracture surface of 2wt% rGO/HAp composite bioceramics(a) SEM images; (b) EDS spectra; Elemental mappings of (c) Ca, (d) P, and (e) C elements

图5 rGO/HAp复相生物陶瓷表面矿化产物的LSCM照片

Fig. 5 LSCM images of mineralization products on the surface of rGO/HAp composite bioceramics(a) Pure HAp; (b) 1wt% rGO/HAp; (c) 2wt% rGO/HAp; (d) 5wt% rGO/HAp

图6 2wt% rGO/HAp复相生物陶瓷表面沉积物的SEM照片

Fig. 6 SEM images of deposition on the surface of 2wt% rGO/HAp composite bioceramics(a) Morphology of the surface sediment after mineralization; (b) Partial enlarged drawing

图7 rGO/HAp复相生物陶瓷维氏硬度与断裂韧性变化曲线

Fig. 7 Vickers hardness and fracture toughness of rGO/HAp composite bioceramics

参考文献 25

[1]	YU P, BAO R Y, SHI X J,et al. Self-assembled high-strength hydroxyapatite/graphene oxide/chitosan composite hydrogel for bone tissue engineering. Carbohydrate Polymers, 2017, 155: 507-515.
[2]	徐晓宙.生物材料学. 北京: 科学出版社, 2006: 70-75, 159-169.
[3]	DOU J H, ZHANG C Y, CHEN C Z,et al. Effects of sintering temperature on the properties of alumina/hydroxyapatite composites. Journal of Sol-Gel Science and Technology, 2017, 84(1): 23-27.
[4]	HU Z, TONG G, LIN D,et al. Graphene-reinforced metal matrix nanocomposites-a review. Materials Science & Technology, 2016, 32(9): 930-953.
[5]	GAO C D, LIU T T, SHUAI C J, et al. Enhancement mechanisms of graphene in nano-58S bioactive glass scaffold: mechanical Enhancement mechanisms of graphene in nano-58S bioactive glass scaffold: mechanical and biological performance. Scientific Reports, 2014, 4: 4712-1-10.
[6]	GURUNATHAN S, KIM J H.Synthesis, toxicity, biocompatibility, and biomedical applications of graphene and graphene-related materials.International Journal of Nanomedicine, 2016, 11: 1927-1945.
[7]	CRISAN L, CRISAN B, SORITAU O,et al. In vitro study of biocompatibility of a graphene composite with gold nanoparticles and hydroxyapatite on human osteoblasts. Journal of Applied Toxicology, 2015, 35(10): 1200-1210.
[8]	LEE S K, KIM H, SHIM B S.Graphene: an emerging material for biological tissue engineering.Carbon Letters, 2013, 14(2): 63-75.
[9]	ZHU K P, SUN J, YE S,et al. A novel hollow hydroxyapatite microspheres/chitosan composite drug carrier for controlled release. Journal of Inorganic Materials, 2016, 31(4): 434-442.
[10]	LIN J, CHEN X Y, HUANG P.Graphene-based nanomaterials for bioimaging.Advanced Drug Delivery Reviews, 2016, 105: 242-254.
[11]	WANG M H, ZHONG H B, FAN Y C,et al. Spark plasma sintering of bioactive Ca2MgSi2O7 ceramics. Journal of Inorganic Materials, 2017, 32(8): 825-830.
[12]	ERIKSSON M, LIU Y, HU J F,et al. Transparent hydroxyapatite ceramics with nanograin structure prepared by high pressure spark plasma sintering at the minimized sintering temperature. Journal of the European Ceramic Society, 2011, 31(9): 1533-1540.
[13]	HAN Y H, KIM B N, YOSHIDA H,et al. Spark plasma sintered superplastic deformed transparent ultrafine hydroxyapatite nanoceramics. Advances in Applied Ceramics, 2016, 115(3): 174-184.
[14]	CHAMPION E.Sintering of calcium phosphate bioceramics.Acta Biomaterialia, 2013, 9(4): 5855-5875.
[15]	ZHOU X J, ZHANG J L, WU H X,et al. Reducing graphene oxide via hydroxylamine: a simple and efficient route to graphene. Journal of Physical Chemistry C, 2011, 115(24): 11957-11961.
[16]	LIU Y, ZHANG B, ZHANG L F,et al. Effect of hydrothermal etching processes on morphology and bioactivity of hydroxyapatite. Journal of Synthetic Crystals, 2016, 45(2): 441-446.
[17]	宋江凤. 羟基磷灰石陶瓷及其复合材料的烧结行为及力学性能研究. 长沙: 中南大学硕士学位论文, 2012.
[18]	ZHANG L, LIU W W, YUE C G,et al. A tough graphene nanosheet/hydroxyapatite composite with improved in vitro, biocompatibility. Carbon, 2013, 61(11): 105-115.
[19]	BAJPAI I, KIM D Y, HAN Y H, et al. Directional property evaluation of spark plasma sintered GNPs-reinforced hydroyapatite composites. Materials Letters, 2015, 158: 62-65.
[20]	LIU Y, SHEN Z J.Dehydroxylation of hydroxyapatite in dense bulk ceramics sintered by spark plasma sintering.Journal of the European Ceramic Society, 2012, 32(11): 2691-2696.
[21]	BONG S, KIM Y R, KIM I,et al. Graphene supported electrocatalysts for methanol oxidation. Electrochemistry Communications, 2010, 12(1): 129-131.
[22]	BUZNIK V M, KOZLOVA S G, GABUDA S P,et al. Structural changes in carbonated hydroxyapatite at high temperatures as probed by 1H NMR and Raman spectroscopy. Doklady Chemistry, 2007, 413(1): 64-67.
[23]	LOPES J H, MAGALHAE J A, GOUUEIA R F,et al. Hierarchical structures of β-TCP/45S5 bioglass hybrid scaffolds prepared by gelcasting. Journal of the Mechanical Behavior of Biomedical Materials, 2016, 62: 10-23.
[24]	LIU H Y, XI P X, XIE G Q,et al. Simultaneous reduction and surface functionalization of graphene oxide for hydroxyapatite mineralization. Journal of Physical Chemistry C, 2012, 116(5): 3334-3341.
[25]	ZHU J T, WONG H M, YEUNG K W K,et al. Spark plasma sintered hydroxyapatite/graphite nanosheet and hydroxyapatite/ multiwalled carbon nanotube composites: mechanical and in vitro cellular properties. Advanced Engineering Materials, 2011, 13(4): 336-341.

等离子活化烧结制备石墨烯/羟基磷灰石复相生物陶瓷

Synthesis of Graphene/Hydroxyapatite Composite Bioceramics via Plasma Activated Sintering

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 25

相关文章 15

编辑推荐

Metrics

本文评价

[1]	安然, 林锶, 郭世刚, 张冲, 祝顺, 韩颖超. 铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究[J]. 无机材料学报, 2025, 40(5): 457-465.
[2]	杨茗凯, 黄泽皑, 周芸霄, 刘彤, 张魁魁, 谭浩, 刘梦颖, 詹俊杰, 陈国星, 周莹. 基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究[J]. 无机材料学报, 2025, 40(5): 473-480.
[3]	高晨光, 孙晓亮, 陈君, 李达鑫, 陈庆庆, 贾德昌, 周玉. 基于湿法纺丝技术的SiBCN-rGO陶瓷纤维的组织结构、力学和吸波性能[J]. 无机材料学报, 2025, 40(3): 290-296.
[4]	王悦, 王欣, 于显利. 室温铁磁性还原氧化石墨烯基全碳膜[J]. 无机材料学报, 2025, 40(3): 305-313.
[5]	李红兰, 张俊苗, 宋二红, 杨兴林. Mo/S共掺杂的石墨烯用于合成氨: 密度泛函理论研究[J]. 无机材料学报, 2024, 39(5): 561-568.
[6]	孙川, 何鹏飞, 胡振峰, 王荣, 邢悦, 张志彬, 李竞龙, 万春磊, 梁秀兵. 含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能[J]. 无机材料学报, 2024, 39(3): 267-273.
[7]	李承瑜, 丁自友, 韩颖超. 锰掺杂纳米羟基磷灰石的体外抗菌-促成骨性能研究[J]. 无机材料学报, 2024, 39(3): 313-320.
[8]	王艳莉, 钱心怡, 沈春银, 詹亮. 石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO[J]. 无机材料学报, 2024, 39(1): 81-89.
[9]	杨平军, 李铁虎, 李昊, 党阿磊. 石墨烯对环氧树脂泡沫炭石墨化、电导率和力学性能的影响[J]. 无机材料学报, 2024, 39(1): 107-112.
[10]	董怡曼, 谭占鳌. 宽带隙钙钛矿基二端叠层太阳电池复合层的研究进展[J]. 无机材料学报, 2023, 38(9): 1031-1043.
[11]	倪晓诗, 林子扬, 秦沐严, 叶松, 王德平. 硅烷化介孔硼硅酸盐生物玻璃微球对PMMA骨水泥生物活性和力学性能的影响[J]. 无机材料学报, 2023, 38(8): 971-977.
[12]	王雪瑶, 王武港, 李应卫, 彭奇, 梁瑞虹. PZT陶瓷本构行为与断裂性能的相关性研究[J]. 无机材料学报, 2023, 38(7): 839-844.
[13]	吴锐, 张敏慧, 金成韵, 林健, 王德平. 光热核壳TiN@硼硅酸盐生物玻璃纳米颗粒的降解和矿化性能[J]. 无机材料学报, 2023, 38(6): 708-716.
[14]	刘妍, 张宇帆, 王茜蔓, 李婷, 马文婷, 杨富巍, 陈靓, 赵东月, 严小琴. 基于羟基磷灰石材料的风化脆弱骨质文物加固保护研究[J]. 无机材料学报, 2023, 38(11): 1345-1354.
[15]	陈赛赛, 庞雅莉, 王娇娜, 龚䶮, 王锐, 栾筱婉, 李昕. 绿-黄可逆电热致变色织物的制备及其性能[J]. 无机材料学报, 2022, 37(9): 954-960.