IMR OpenIR
PEEK基生物复合材料的力学性能和体外生物活性研究
其他题名The mechanical properties and bioactivity of PEEK based composite materials for biological applications
冯惺
学位类型硕士
导师杨锐
2007-02-10
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料学
关键词Peek/ha Peek/ha/cf 力学性能 生物活性
摘要摘要 人工骨替代材料是应用于骨修复手术中,用于替代缺损的人体骨的材料,主要有金属材料、陶瓷材料和聚合物基复合材料三类。金属材料的模量相对于人体骨来说太高,易导致应力遮蔽效应,且其生物活性相对较低。生物陶瓷材料则因为强度低、韧性差等弱点不能作为承力骨材料单独使用,通常用作填料来增强其它材料的生物活性。聚合物基复合材料则因为添加了HA等生物陶瓷从而具有较好的生物活性,此外还具有成分、性能可调等优点,然而其强度、模量太低,不能很好的满足人体骨替代材料的力学性能要求。因此,提高聚合物基复合材料的强度、模量等力学性能,制备具有和人体骨强度、模量相匹配的聚合物基复合材料一直是聚合物基骨替代材料的研究目标所在。 PEEK是力学性能最为优异的一种热塑性树脂。研究表明, PEEK/HA复合材料在具有生物活性的同时,能够满足人体骨替代材料力学性能的低端要求,但是,其力学性能还远远没有达到承力骨的力学性能要求。作为最常采用的增强纤维之一,CF具有很好的力学性能和化学稳定性。所以,采用短CF对PEEK/HA复合材料进行增强而得到的PEEK/HA/CF复合材料很可能是一种能够较好满足人体承力骨替代材料要求的复合材料。 本论文采用熔融共混-注射成型法制备了PEEK/HA和PEEK/HA/CF复合材料,对比研究了这两种复合材料的拉伸、弯曲和冲击性能,并通过对复合材料的断口形貌的分析来对复合材料力学性能的变化规律做进一步的探讨。为了研究PEEK/HA和PEEK/HA/CF复合材料的体外生物活性,本文采用了三种不同配制方式的SBF溶液,并对PEEK/HA和PEEK/HA/CF复合材料在体外生物活性实验中出现的表面生长物的生长模式进行了初步的探讨。 本论文采用注塑前对PEEK(和PEEK/CF)和HA熔融共混法来对增强相进行分散处理。BEM图片显示,经过分散处理后制备的试样中的HA和CF都得到了很好的均匀分布。其中CF的分布各处都很均匀,而其取向则因为其在基体中的位置而有所不同。位于试样表面的CF为无序取向,试样中部的CF沿注塑方向具有一定的择优取向。这样的分布情况和注塑过程中的流体力学情况是相吻合的。 力学性能的结果表明,PEEK/HA复合材料的拉伸强度和弯曲强度随着HA含量的增加而降低,其拉伸模量、弯曲模量则随HA含量的增加而升高,对PEEK/HA复合材料的断口SEM照片分析表明,HA的添加抑制了基体的塑性形变,使得复合材料的脆性增大,断裂应变减小。同时,由于PEEK/HA复合材料的冲击性能是由基体的塑形变形和添加物从基体中脱粘、拔出等机制共同决定,所以PEEK/HA复合材料的冲击性能的变化趋势比较复杂。然而,PEEK/HA复合材料的力学性能和人体骨替代材料的力学性能要求还有较大的差距,还不能作为人体骨替代材料来应用。 同PEEK/HA复合材料相比, PEEK/HA/CF复合材料的力学性能有了极大的提高,能够较好的符合人体骨替代材料的力学性能要求。当HA含量相同时,随着CF含量的增加,PEEK/HA/CF复合材料的拉伸强度和模量都随之增加,弯曲强度和模量也同样增加。当CF含量相同时,随着HA含量的增加,PEEK/HA/CF复合材料的拉伸、弯曲强度变化不大,而拉伸、弯曲模量却随之增加。因为HA的拔出、脱粘等变形方式对于PEEK/HA/CF复合材料冲击功的影响不大,其含量的增加反而降低了PEEK/HA/CF复合材料中的基体的塑性变形部分。故PEEK/HA/CF复合材料的冲击性能在HA含量不变时,冲击强度随着CF含量的升高而升高,而当CF含量不变时则随着HA含量的升高而降低。综上所述,CF对于PEEK/HA/CF复合材料力学性能的影响起主导作用 通过对PEEK/HA和PEEK/HA/CF复合材料在三种不同配制方式的SBF溶液(在调校最终pH值为7.42前, 每种SBF溶液的 pH值不同,药品添加过程略有区别。)中的体外生物活性结果的分析表明,PEEK/HA和PEEK/HA/CF复合材料都具有很好的生物活性,且其表面生长物的情况和SBF溶液配置过程中的pH值有着密切的关系。当SBF溶液制备过程中的酸碱度一直保持在中性附近后,浸泡在其中的试样表面表现出较好的HA生长情况。通过SEM照片还观察到,试样表面的HA的生长情况和试样中包含的HA的含量多少有关,HA含量越高,试样表面生长的HA越多。通过浸泡后的试样的横截面的BEM照片的观察和分析表明,复合材料在生物活性实验中生长的表面生成物的形核长大过程和SBF溶液中Ca2+的富集过程有关。 综上所述,PEEK/HA/CF复合材料的拉伸模量、强度,弯曲模量、强度和冲击强度等力学性能指标能够很好的满足人体骨替代材料的力学性能要求,并且具有很好的生物活性,表明PEEK/HA/CF复合材料是一种力学性能优异的可用于替代人体骨的聚合物基生物复合材料。 关键词:PEEK/HA,PEEK/HA/CF,力学性能,生物活性。
其他摘要ABSTRACT Artificial bone materials are those used to substitute broken human bone in bone repair surgery. They include metallic materials, ceramics and polymer based composites.The metallic materials are easy to cause stress shielding effect due to their much higher modulus compared to human bone. As well their biological properties are poor compared to the other two kinds of materials.The bioceramics materials, which can’t be used in load-bearing parts due to the low strength and bad ductility, are always added into other two kinds of materials as fillers to enhance their biological activity. The polymer based composites can be adjusted to achieve good mechanical properties as well be modified to have good biocompatibility by filling with bioceramics (hydroxyapatite(HA), for example). However, its strength and modulus is too low to match the requirements of the mechanical properties of bone substitutes. Therefore, the main research purpose of polymer based bone substitute materials is to increase the strength and modulus to meet the human load-bearing bone’s requirements. Polyetheretherketone (PEEK) is one thermal plastic which has good mechanical properties. It was shown that the biological material of Polyetheretherketone/Hydroxyapatite (PEEK/HA) composites can approach the lower-limit of the mechanical requirements of bone substitutes. However, its mechanical properties were far from catching up with the requirements for load bearing human bone. Carbon fibre (CF) has good mechanical properties and chemical resistance, and is always used as a common reinforcement to reinforce other materials. For these reasons, Polyetheretherketone/Hydroxyapatite/Carbon fibre (PEEK/HA/CF )composites, which is made by adding short CF to reinforce the PEEK/HA composites, might be one material that can well meet the mechanical requirements of load-bearing bone substitutes. In this paper, PEEK/HA and PEEK/HA/CF composites were made by injection molding after blending in rheometer. The tensile, flexural and Izod impact properties of the two kinds of composites were investigated. The reinforcement and fracture mechanisms were discussed by analyzing the scanning electronic microscope (SEM) photomicrograph of the composites fracture surfaces. PEEK/HA and PEEK/HA/CF composites had been soaked in three simulated body fluid (SBF)(each SBF has a different prepared process) for studying the in vitro bioactivity, and the mechanisms of the product growth during soaking were discussed. Rheometer was used to blend HA with PEEK (PEEK/CF) to make homogeneous distribution of the fillers. Back-scattered electronic microscope (BEM) photos showed that HA and CF were well dispersed in PEEK matrix. The CF stayed on surface of the molded samples had a random orientation distribution. In contrast, the CF situated in interior part of the samples had a favorite orientation along the melt flow direction. These orientation features were determined by the fluid mechanics during injection molding process. It was revealed that the tensile and flexural modulus increased with the increase of HA content in PEEK/HA composites. On the other hand, the tensile and flexural strength decreased. Furthermore, the increase of HA content would also cause the PEEK/HA composites more brittle. This was evidenced by SEM photos of fracture surfaces which showed that increase of HA content inhibited the plastic deformation of PEEK matrix and thus induced the decrease of strain at break. This was evidenced by photos of fracture surfaces. The trend of impact strength of PEEK/HA composites with HA content was complicated due to the complex toughening mechanisms from both of the plastic deformation of PEEK resin matrix and the pull-out and debonding of HA particles from the matrix. However, the mechanical properties of PEEK/HA composites is far away from the requirements of human bone substitutes, therefore, it couldn’t be used as one bone substitute material. PEEK/HA/CF composites have much better mechanical properties than PEEK/HA composites. It was shown that with the same HA content the tensile strength and modulus, as well as the flexural strength and modulus, increased with the increase of CF content in PEEK/HA/CF composites. However, when the CF content was fixed, the tensile and flexural modulus increased with the increase of HA content in PEEK/HA/CF composites, while the tensile and flexural strength showed less change. The contribution from the pull-out and debonding of HA particles from PEEK matrix on the impact work absorption is far less than its negative effect of restraining the plastic deformation of PEEK resin matrix. Therefore, for PEEK/HA/CF composites with the same HA content, the impact strength increased with the increase of CF content. On the other hand, for PEEK/HA/CF composites with the same CF content, the impact strength decreased with the increase of HA content. In one word, the CF has dominant influence on the mechanical properties of PEEK/HA/CF composites. There are three SBF, each SBF has its own PH value before the final PH value adjusting process. When soaking these samples of PEEK/HA and PEEK/HA/CF composites into these SBF, we found that there was a close relationship between the PH value during the SBF preparing process and the product growth conditions. It was evidenced that the samples soaked in SBF that had a neutral PH value before and after PH value adjusting process generated more products on their surface than those samples soaked in the other two kinds of SBF. It was also observed that the quantity of the grown product was also determined by the HA content in the original samples. The higher the HA content in the samples, the more product generated on their surfaces. It was further showed that the nucleation stage and growth process of HA product had a close relationship with the enriched process of calcium ions in SBF by observing the BEM photos of cross-section of samples soaked in SBF for a given period. In conclusion, the PEEK/HA/CF composites performed good bioactivity and wonderful mechanical properties, such as high tensile modulus and high tensile strength, which had a good match to the requirements of load-bearing human bone substitutes. Therefore, the PEEK/HA/CF composite is expected to be used as a candidate for human bone substitute materials. Key Words: PEEK/HA,PEEK/HA/CF,mechanical properties,bioactivity。
页数99
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/16855
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
冯惺. PEEK基生物复合材料的力学性能和体外生物活性研究[D]. 金属研究所. 中国科学院金属研究所,2007.
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