超高分子量聚乙烯粉末表面接枝丙烯酸及其块体材料的摩擦学性能研究
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摘要
超高分子量聚乙烯(UHMWPE)以其优异的综合机械性能和生物相容性,在骨替代材料的应用中得到越来越广泛的重视。本实验针对目前UHMWPE失效原因,采用紫外光接枝和溶液接枝的方法,在UHMWPE颗粒表面进行接枝处理,然后再热压成型,并对接枝前后的试样的相关性能进行了测试和评价,得到主要结果如下：
1.对接枝后试样进行接枝率测试,结果表明利用紫外光进行的接枝,当光敏剂含量不多时,接枝率随着光敏剂的浓度增大而增大,在浓度为4phr时达到最大值,为5.5%,之后增大光敏剂浓度,接枝率几乎不发生变化。溶液接枝时改变单体丙烯酸的浓度,当丙烯酸浓度为10phr时接枝率最大,继续增大丙烯酸浓度接枝量会减小。
2.未接枝的UHMWPE的润湿角为83-84°,润湿角的变化随接枝率的增大而减小,接枝后的UHMWPE润湿角最低可达34-35°,说明接枝后的UHMWPE亲水性能得到了很大的提高。
3.接枝后的样品硬度都得到了一定提高,溶液接枝的样品硬度最大。通过光接枝的方法,在接枝率为2.16%时,UHMWPE的抗拉强度和断裂延伸率得到了较大的提高,这是由于接枝的极性支链使分子之间的结合力增大,导致抗拉强度增大。而溶液接枝的试样抗拉强度普遍大幅降低,最低只有纯UHMWPE的1／20。
4.接枝的UHMWPE在润滑液下,其初始摩擦系数较高,随着滑行距离增大,摩擦系数不断减小。由于接枝表面存在亲水性极性分子,在润滑液中形成润滑膜,阻止了摩擦副与基体的直接摩擦,从而大大降低了磨损率,紫外光接枝率为3.5%的UHMWPE磨损率仅为未接枝试样的1／4。溶液接枝的UHMWPE虽然具有最低的摩擦系数,但由于接枝过程破坏了聚乙烯原有性能,磨损率最为严重,是未接枝样品的2倍。
5.表面接枝的UHMWPE具有较低的摩擦系数,但随着滑行距离的增大,表面接枝的聚合物层被磨掉,摩擦系数出现上升。而粉末接枝的试样不同,接枝的聚合物存在试样的任何部位,当表层的聚合物层被磨去后,次表层的丙烯酸可以继续形成聚合物刷,保证润滑性能的稳定性和持久性。最后结果表明,经过24h磨损后,粉末接枝的试样磨损率仅为表面接枝的1／2,很好的解决了以往表面聚合物刷不能持久润滑的问题。
6.对磨损表面进行形貌观察,接枝样品的磨损表面较为光滑平整,未接枝的UHMWPE出现大量犁沟和剥落现象,主要是黏附磨损和磨粒磨损所致：接枝的UHMWPE由于聚合物刷的润滑膜作用,磨损表面主要是疲劳磨损。
Ultra-high molecular weight polyethylene (UHMWPE) get more and more widely appreciated as replacement of the bone because of its excellent comprehensive mechanical properties and biocompatibility. In the present work, aiming at the current failure of UHMWPE, UHMWPE powder is grafted with the method of UV and solution grafting, and then it is molded. A series of experimental approaches were used to investigate performances of the treated and untreated samples, the results are as following:
1. The result of graft rate test shows that, when the reaction was carried on under the UV, the graft rate rised with the ppm of photosensitizer. And the graft rate reached the maximum,5.5%, when the photosensitizer is 4phr.After that, the graft rate keep steady. In the solution graft, when the acrylic acid(AA) concentration is 10phr, the graft rate is the highest, and then if we went on improve the concentration of AA, the graft rate declined.
2. The wetting angle of the untreated UHMWPE is 83-84°, and the wetting angle declined with the improvement of grafting, the lowest was 34-35°, which illustrated that the hydrophilicity of UHMWPE was improved.
3. The hardness of the grafted samples were also improved and the solution grafted samples were the highest. When the graft rate is 2.16% using the UV, the tensile strength and elongation were improved. However, the tensile strength of all samples solution grafted were declined, and the lowest was just the 1/20 of the untreated samples.
4. Under the lubricating fluid, the initial friction coefficient was higher, but it declined with the increasement of the sliding distance. Because the surface of samples was grafted with polar polymer and then format lubricating film, which prevented the direct contact between the basis material surface and the grinding material. The wear rate declined greatly, the wear rate of the sample with 3.5% grafting was just 1/4 of the untreated sample. Although the solution grafted samples had the lower friction coefficient, the wear rate is the highest and twice untreated, because the graft process broke the original properties of UHMWPE.
5. Surface grafting of UHMWPE has a low friction coefficient, but with the increasement of the sliding distance, the grafted polymer layer was grinded off and the friction coefficient rised. The powder grafted samples had the different case. The graft polymer existed everywhere of the samples. When the dermal polymer was grinded off, the polymer from the subsurface could form the polymer brush, which could guarantee the stability and durability of lubricity. The result showed that, the wear rate of powder grafted samples is just half of the surface grafted after 24h worn.
6. The worn surface morphology was observed, the grafted samples looked smoother, the untreated ones had a lot of furrow and peeling, which were the result of adhesion wear and abrasion wear. The major wear mechanism of grafted samples is fatigue wear because of the lubricating film of the polymer brush.
1.对接枝后试样进行接枝率测试,结果表明利用紫外光进行的接枝,当光敏剂含量不多时,接枝率随着光敏剂的浓度增大而增大,在浓度为4phr时达到最大值,为5.5%,之后增大光敏剂浓度,接枝率几乎不发生变化。溶液接枝时改变单体丙烯酸的浓度,当丙烯酸浓度为10phr时接枝率最大,继续增大丙烯酸浓度接枝量会减小。
2.未接枝的UHMWPE的润湿角为83-84°,润湿角的变化随接枝率的增大而减小,接枝后的UHMWPE润湿角最低可达34-35°,说明接枝后的UHMWPE亲水性能得到了很大的提高。
3.接枝后的样品硬度都得到了一定提高,溶液接枝的样品硬度最大。通过光接枝的方法,在接枝率为2.16%时,UHMWPE的抗拉强度和断裂延伸率得到了较大的提高,这是由于接枝的极性支链使分子之间的结合力增大,导致抗拉强度增大。而溶液接枝的试样抗拉强度普遍大幅降低,最低只有纯UHMWPE的1／20。
4.接枝的UHMWPE在润滑液下,其初始摩擦系数较高,随着滑行距离增大,摩擦系数不断减小。由于接枝表面存在亲水性极性分子,在润滑液中形成润滑膜,阻止了摩擦副与基体的直接摩擦,从而大大降低了磨损率,紫外光接枝率为3.5%的UHMWPE磨损率仅为未接枝试样的1／4。溶液接枝的UHMWPE虽然具有最低的摩擦系数,但由于接枝过程破坏了聚乙烯原有性能,磨损率最为严重,是未接枝样品的2倍。
5.表面接枝的UHMWPE具有较低的摩擦系数,但随着滑行距离的增大,表面接枝的聚合物层被磨掉,摩擦系数出现上升。而粉末接枝的试样不同,接枝的聚合物存在试样的任何部位,当表层的聚合物层被磨去后,次表层的丙烯酸可以继续形成聚合物刷,保证润滑性能的稳定性和持久性。最后结果表明,经过24h磨损后,粉末接枝的试样磨损率仅为表面接枝的1／2,很好的解决了以往表面聚合物刷不能持久润滑的问题。
6.对磨损表面进行形貌观察,接枝样品的磨损表面较为光滑平整,未接枝的UHMWPE出现大量犁沟和剥落现象,主要是黏附磨损和磨粒磨损所致：接枝的UHMWPE由于聚合物刷的润滑膜作用,磨损表面主要是疲劳磨损。
Ultra-high molecular weight polyethylene (UHMWPE) get more and more widely appreciated as replacement of the bone because of its excellent comprehensive mechanical properties and biocompatibility. In the present work, aiming at the current failure of UHMWPE, UHMWPE powder is grafted with the method of UV and solution grafting, and then it is molded. A series of experimental approaches were used to investigate performances of the treated and untreated samples, the results are as following:
1. The result of graft rate test shows that, when the reaction was carried on under the UV, the graft rate rised with the ppm of photosensitizer. And the graft rate reached the maximum,5.5%, when the photosensitizer is 4phr.After that, the graft rate keep steady. In the solution graft, when the acrylic acid(AA) concentration is 10phr, the graft rate is the highest, and then if we went on improve the concentration of AA, the graft rate declined.
2. The wetting angle of the untreated UHMWPE is 83-84°, and the wetting angle declined with the improvement of grafting, the lowest was 34-35°, which illustrated that the hydrophilicity of UHMWPE was improved.
3. The hardness of the grafted samples were also improved and the solution grafted samples were the highest. When the graft rate is 2.16% using the UV, the tensile strength and elongation were improved. However, the tensile strength of all samples solution grafted were declined, and the lowest was just the 1/20 of the untreated samples.
4. Under the lubricating fluid, the initial friction coefficient was higher, but it declined with the increasement of the sliding distance. Because the surface of samples was grafted with polar polymer and then format lubricating film, which prevented the direct contact between the basis material surface and the grinding material. The wear rate declined greatly, the wear rate of the sample with 3.5% grafting was just 1/4 of the untreated sample. Although the solution grafted samples had the lower friction coefficient, the wear rate is the highest and twice untreated, because the graft process broke the original properties of UHMWPE.
5. Surface grafting of UHMWPE has a low friction coefficient, but with the increasement of the sliding distance, the grafted polymer layer was grinded off and the friction coefficient rised. The powder grafted samples had the different case. The graft polymer existed everywhere of the samples. When the dermal polymer was grinded off, the polymer from the subsurface could form the polymer brush, which could guarantee the stability and durability of lubricity. The result showed that, the wear rate of powder grafted samples is just half of the surface grafted after 24h worn.
6. The worn surface morphology was observed, the grafted samples looked smoother, the untreated ones had a lot of furrow and peeling, which were the result of adhesion wear and abrasion wear. The major wear mechanism of grafted samples is fatigue wear because of the lubricating film of the polymer brush.
引文
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