聚醚醚酮/羟基磷灰石复合涂层的制备及性能研究
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摘要
聚醚醚酮(PEEK)优良的力学性能和羟基磷灰石(HA)的生物活性已引起医学专家和材料学专家的广泛关注,目前PEEK/HA复合材料已广泛被学者研究,但是HA在复合材料中的含量过高将降低复合材料的力学性能,故在基体PEEK上附着HA涂层被认为是一种有应用前景的生物材料,它综合利用了HA涂层的生物活性和基体PEEK的力学性能。目前对在基体PEEK上附着HA涂层的研究还较少,本研究为在PEEK上高温烧结制备性能优异的PEEK/HA复合涂层材料。
首先用不同含量(1wt.%、2wt.%、3wt.%和4wt.%)的偶联剂KH560对羟基磷灰石进行表面改性,通过傅氏转换红外线光谱分析仪(FTIR)表征可知:当KH560含量为2wt.%时,它对羟基磷灰石的改性效果达到饱和;通过X射线衍射仪(XRD)分析表明KH560不会影响羟基磷灰石的晶体结构。
然后通过溶液共混法制备PEEK/HA和PEEK/KH560-HA(HA含量为45wt.%)复合材料,然后倾倒在基板PEEK(25mm×6mm×3mm)上,然后放在高温270℃烧结8min制备出具有复合涂层的材料,随后对其通过热处理提高材料的力学性能。对不同热处理条件下制得的复合涂层材料进行XRD表征分析,其结果表明:随着热处理温度的升高和时间的延长,基板PEEK的表面结晶度增加。力学性能分析结果表明:PEEK/HA和PEEK/KH560-HA复合涂层材料样品的拉伸强度均小于无涂层样品的拉伸强度,且PEEK/KH560-HA复合涂层样品的拉伸强度和韧性均优于PEEK/HA复合涂层样品的拉伸强度和韧性。这说明了用KH560对HA进行表面改性的必要性,KH560引入改善了基体PEEK与HA之间的界面结合性能。随着热处理温度的升高和时间的延长,提高了PEEK/HA和PEEK/KH560-HA复合涂层材料的拉伸强度,这与结晶度的变化相对应。
最后,本文通过扫描电子显微镜的配套仪器能谱仪(EDS)分析试样的复合涂层部分可知:经KH560改性的HA较均匀地分散在基体PEEK中且KH560-HA与涂层中的基体PEEK结合紧密;通过扫描电子显微镜研究拉伸断裂和弯曲断裂的断面形貌表明:PEEK/HA和PEEK/KH560-HA复合涂层与基板PEEK结合均紧密,这表明通过高温烧结和后续的热处理能制备出兼具良好的生物活性和力学性能的PEEK/HA复合涂层材料。
HA/PEEK biocomposite materials have been recently investigated due to the favorable biocompatibility of hydroxyapatite (HA) and good mechanical properties of polyetheretherketone (PEEK) polymers. However, a large HA content in PEEK composites could deteriorate the mechanical properties of the composite materials, therefore, HA-coated PEEK is a promising implant material to meet the needs of both good mechanical properties and excellent bioactivity. So far HA-coated PEEK has not been studied in depth. In this thesis bioactive HA/PEEK coatings were fabricated successfully by a high temperature sintering process, and the good properties were expected.
The HA particles were modifed by the different content (1wt.%, 2wt.%, 3wt.%, and 4wt.%) of silane coupling agent (KH560), and the silane modified HA particles were characterized by fourier transform infrared spectroscopy (FTIR). The results show that 2wt.% KH560 can play the best performance. What’s more, the result of X-ray diffraction (XRD) analysis show that KH560 has not influenced the HA crystal structure.
The PEEK/HA and PEEK/KH560-HA (HA content is 45wt.%) composite materials were prepared by a solution blending method. These composite were placed on the PEEK substrate (25mm×6mm×3mm), and samples with PEEK/HA and PEEK/KH560-HA composite coatings were prepared after sintering at 270℃for 8min in furnace. XRD results show that the crystallinity of PEEK substrate increased with the increase of the temperature and time of heat treatment. The mechanical properties of different samples were measured, and the results illustrated that the tensile strength of samples with PEEK/HA and PEEK/KH560-HA composite coatings decreased, compared with the samples without coatings, and the samples with PEEK/KH560-HA composite coatings show higher tensile strength and toughness than the samples with PEEK/HA composite coatings, which explained the necessity of the surface modification of HA with KH560. With the increase of the temperature and time of heat treatment, the tensile strength of samples with PEEK/HA and PEEK/KH560-HA composite coatings was enhanced, which was alterated in accordance with crystallinity.
The microstructure of the tensile and bending fracture section of the composites was observed using scanning electron microscope (SEM), and the composition of the composite coatings of samples with modified HA by KH560 were investigated by energy dispersive spectrometer (EDS). These results show that the good adhesion between PEEK/HA or PEEK/KH560-HA composite coatings and the PEEK substrate was achieved, therefore, the composite coating materials with both high mechanical properties and good bioactivity can be prepared by this coating process.
首先用不同含量(1wt.%、2wt.%、3wt.%和4wt.%)的偶联剂KH560对羟基磷灰石进行表面改性,通过傅氏转换红外线光谱分析仪(FTIR)表征可知:当KH560含量为2wt.%时,它对羟基磷灰石的改性效果达到饱和;通过X射线衍射仪(XRD)分析表明KH560不会影响羟基磷灰石的晶体结构。
然后通过溶液共混法制备PEEK/HA和PEEK/KH560-HA(HA含量为45wt.%)复合材料,然后倾倒在基板PEEK(25mm×6mm×3mm)上,然后放在高温270℃烧结8min制备出具有复合涂层的材料,随后对其通过热处理提高材料的力学性能。对不同热处理条件下制得的复合涂层材料进行XRD表征分析,其结果表明:随着热处理温度的升高和时间的延长,基板PEEK的表面结晶度增加。力学性能分析结果表明:PEEK/HA和PEEK/KH560-HA复合涂层材料样品的拉伸强度均小于无涂层样品的拉伸强度,且PEEK/KH560-HA复合涂层样品的拉伸强度和韧性均优于PEEK/HA复合涂层样品的拉伸强度和韧性。这说明了用KH560对HA进行表面改性的必要性,KH560引入改善了基体PEEK与HA之间的界面结合性能。随着热处理温度的升高和时间的延长,提高了PEEK/HA和PEEK/KH560-HA复合涂层材料的拉伸强度,这与结晶度的变化相对应。
最后,本文通过扫描电子显微镜的配套仪器能谱仪(EDS)分析试样的复合涂层部分可知:经KH560改性的HA较均匀地分散在基体PEEK中且KH560-HA与涂层中的基体PEEK结合紧密;通过扫描电子显微镜研究拉伸断裂和弯曲断裂的断面形貌表明:PEEK/HA和PEEK/KH560-HA复合涂层与基板PEEK结合均紧密,这表明通过高温烧结和后续的热处理能制备出兼具良好的生物活性和力学性能的PEEK/HA复合涂层材料。
HA/PEEK biocomposite materials have been recently investigated due to the favorable biocompatibility of hydroxyapatite (HA) and good mechanical properties of polyetheretherketone (PEEK) polymers. However, a large HA content in PEEK composites could deteriorate the mechanical properties of the composite materials, therefore, HA-coated PEEK is a promising implant material to meet the needs of both good mechanical properties and excellent bioactivity. So far HA-coated PEEK has not been studied in depth. In this thesis bioactive HA/PEEK coatings were fabricated successfully by a high temperature sintering process, and the good properties were expected.
The HA particles were modifed by the different content (1wt.%, 2wt.%, 3wt.%, and 4wt.%) of silane coupling agent (KH560), and the silane modified HA particles were characterized by fourier transform infrared spectroscopy (FTIR). The results show that 2wt.% KH560 can play the best performance. What’s more, the result of X-ray diffraction (XRD) analysis show that KH560 has not influenced the HA crystal structure.
The PEEK/HA and PEEK/KH560-HA (HA content is 45wt.%) composite materials were prepared by a solution blending method. These composite were placed on the PEEK substrate (25mm×6mm×3mm), and samples with PEEK/HA and PEEK/KH560-HA composite coatings were prepared after sintering at 270℃for 8min in furnace. XRD results show that the crystallinity of PEEK substrate increased with the increase of the temperature and time of heat treatment. The mechanical properties of different samples were measured, and the results illustrated that the tensile strength of samples with PEEK/HA and PEEK/KH560-HA composite coatings decreased, compared with the samples without coatings, and the samples with PEEK/KH560-HA composite coatings show higher tensile strength and toughness than the samples with PEEK/HA composite coatings, which explained the necessity of the surface modification of HA with KH560. With the increase of the temperature and time of heat treatment, the tensile strength of samples with PEEK/HA and PEEK/KH560-HA composite coatings was enhanced, which was alterated in accordance with crystallinity.
The microstructure of the tensile and bending fracture section of the composites was observed using scanning electron microscope (SEM), and the composition of the composite coatings of samples with modified HA by KH560 were investigated by energy dispersive spectrometer (EDS). These results show that the good adhesion between PEEK/HA or PEEK/KH560-HA composite coatings and the PEEK substrate was achieved, therefore, the composite coating materials with both high mechanical properties and good bioactivity can be prepared by this coating process.
引文
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[2]杨春莉.羟基磷灰石表面改性、功能化及其应用研究[D].浙江:浙江大学博士论文,2009:16-20.
[3]宋禹奠.溶液共混法制备聚醚醚酮/羟基磷灰石复合材料[D].深圳:哈尔滨工业大学深圳研究生院学位论文,2010:16-19,37-42.
[4]邓迟,李秀芬,邓敏等.生物材料表面改性的研究进展[J].乐山师范学院学报,2009,19(5):78-81.
[5]刘敬肖,杨大智,王伟强等.表面改性在生物医用材料研究中的应用[J].材料研究学报,2000,14(3):225-233.
[6] Huang Yuhong, Zheng Haixing. Audrey Lin et al. Functionalization of Implant Surface[J]. Rare Metal Materials and Engineering,2010,39(2):1-9.
[7]付涛,张玉梅,憨勇等.羟基磷灰石生物涂层的复合制备与生物相容性[J].无机材料学报,2001,16(3):522-528.
[8]申剑锋,常程康,毛大立等.羟基磷灰石涂层材料的制备及其性能表征[J].无机材料学报,2001,16(5):993-998.
[9]徐益,秦传江,赵柏森等.钛基羟基磷灰石涂层的界面结构及梯度设计[J].表面技术,2005,34(1):58-61.
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