ZnO介晶填料的制备及其齿科复合树脂的性能

doi:10.15541/jim20180598

摘要/Abstract

摘要：

无机填料是齿科修复复合树脂的主要成分, 它对复合树脂的性能和功能至关重要。本文以三乙醇胺为软模板剂, 六水合硝酸锌为主要原料, 水热法制备平均晶粒尺寸37.5 nm ZnO晶粒构筑的微米级多孔介晶微球, 具有良好的有序性。经γ-甲基丙烯酰氧丙基三甲氧基硅烷(γ-MPS)对ZnO介晶微球改性后, 与改性的SiO₂微球混合, 添加到Bis-GMA/TEGDMA树脂体系中, 制成复合树脂。通过形貌和性能测试发现, 20wt% ZnO介晶填充的复合树脂中填料分散均匀、力学和耐磨损性能优异, 其中树脂弯曲强度133 MPa、弯曲模量9.8 GPa; 磨损3000次后, 树脂体积损耗为1.02 mm ³, 磨损量比商业ZnO微球和单纯SiO₂填充的复合树脂分别降低了88.7%和90.8%。而且, 含氧化锌的复合树脂对口腔中变异链球菌的抗菌率达到99.9%。

关键词: 齿科复合树脂, ZnO介晶, 力学性能, 耐磨性能, 抗菌性能

Abstract:

The inorganic filler is the main component of the dental restoration composite resin, which is very important for the properties and functions of composite resin. In this paper, zinc oxide (ZnO) mesocrystal microspheres were prepared from Zn(NO₃)?6H₂O solution in presence of triethanolamine as the soft template by hydrothermal method, these microspheres were self-assembled by 37.5 nm ZnO crystallite and with good order. ZnO mesocrystal microspheres were modified with γ-methacryloxypropyl trimethoxysilane (γ-MPS) and subsequently mixed with modified SiO₂ microspheres as fillers, and then added to the Bis-GMA/TEGDMA system to prepare the composite resin. Through morphology observation and performance test, it is found the filler is uniformly dispersed in composite resin. The one filled with 20wt% ZnO mesocrystals has excellent mechanical properties and wear resistance, among which the flexural strength and modulus reach 133 MPa and 9.8 GPa, respectively with the volume loss at 1.02 mm ³ after 3000 times of wearing, which was 88.7% and 90.8% lower than that of the composite resin filled with commercial ZnO microspheres and bare SiO₂, respectively. Moreover, the antibacterial rate of zinc oxide composite resin against streptococcus mutans in the oral cavity reached 99.9%.

Key words: dental composite resin, ZnO mesocrystal, mechanical property, wear resistance, antibacterial property

中图分类号:

TQ174

刘玉玲, 王瑞莉, 李楠, 刘梅, 张青红. ZnO介晶填料的制备及其齿科复合树脂的性能[J]. 无机材料学报, 2019, 34(10): 1077-1084.

LIU Yu-Ling, WANG Rui-Li, LI Nan, LIU Mei, ZHANG Qing-Hong. Preparation of Zinc Oxide Mesocrystal Filler and Its Properties as Dental Composite Resin[J]. Journal of Inorganic Materials, 2019, 34(10): 1077-1084.

图/表 8

图1 无机填料的SEM照片: 低倍数(a)和高倍数(b)的ZnO介晶; (c)商业氧化锌微球; (d) SiO2微球

Fig. 1 SEM images of inorganic fillers: ZnO mesocrystal at low magnification (a) and high magnification (b), commercial ZnO microsphere (c), and SiO2 microsphere (d)

图2 ZnO微球的XRD图谱(a), ZnO的氮吸附解吸等温线(b), 插入图为ZnO孔径分布图; ZnO微球的TEM(c)及HRTEM(d)照片; ZnO微球的选区电子衍射照片(e)

Fig. 2 XRD spectrum of ZnO microspheres (a); N2 isothermal adsorption and desorption curve of ZnO microspheres with insert showing its pore size distribution (b); TEM (c) and HRTEM (d) images of ZnO microspheres and selected area electron diffraction patterns of ZnO microspheres (e)

图3 (a) ZnO改性前后红外光谱图; (b) SiO2改性前后红外光谱图

Fig. 3 FT-IR spectra of ZnO before and after modification (a) and FT-IR spectra of SiO2 before and after modification (b)

图4 S复合树脂、SZS和SZM复合树脂的弯曲强度(a), 弯曲模量(b)和压缩强度(c)

Fig. 4 Flexural strength (a), flexural modulus (b) and compression strength (c) of S composite resin, SZS and SZM composite resin

图5 复合树脂断面SEM照片: S树脂断面(a); SZS20树脂断面(b); SZM20树脂断面(c~d)

Fig. 5 SEM images of composite resin fracture surfaces: S resin fracture surface (a); SZS20 resin fracture surface (b); SZM20 resin fracture surfaces (c-d)

图6 齿科复合树脂的耐磨损性测试

Fig. 6 Wear resistance test of dental composite resin

图7 S复合树脂、SZS20和SZM20复合树脂磨损试样不同磨损次数下的SEM照片

Fig. 7 SEM images of wear samples of S, SZS20 and SZM20 composite resin under different wear time

图8 S树脂(a)、SZS20(b)和SZM20(c)复合树脂抗菌效果的数码照片

Fig. 8 Digital photos of antibacterial effect of S resin (a) SZS20 (b) and SZM20 (c) composite resins

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