CN113425911A - 具有长效抗菌和自润滑功能的3d打印支架的制备方法 - Google Patents
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Abstract
本发明涉及一种具有长效抗菌和自润滑功能的3D打印支架的制备方法,将氧化锌、纳米银、ZIF与PEEK材料进行混合后制备成3D打印线材,利用3D打印机制备成PEEK支架;对PEEK支架进行表面处理使其表面氨基化,并将海藻酸钠或透明质酸接枝到PEEK支架表面,之后将海藻酸钠或透明质酸进行氧化处理,使其表面带有醛基;将带有醛基的PEEK支架浸没负载抗生素的蛋白溶液中,形成凝胶涂层。本发明制备的3D打印支架能够在植入后的初期释放抗生素,中后期通过释放抗菌离子达到长效抗菌效果;此外,支架表面的凝胶层能够起到润滑的效果,从而避免支架植入后对关节或者软骨的摩擦磨损。
Description
技术领域
本发明属于医用3D打印技术领域,具体涉及一种具有长效抗菌和自润滑功能的3D打印支架的制备方法。
背景技术
聚醚醚酮(PEEK)是一种典型的芳香族高分子聚合物,是一种具有高性能的特种工程塑料。PEEK分子式中含有苯环、醚链及羟基,所以该材料除了具有良好的耐热性能之外,还具备耐腐蚀和高强度等优良特性。PEEK以其优良特性与目前飞速发展的3D打印相结合已经在医学中,特别是在骨科中被广泛应用,主要包括:颌面修复、颅骨修复、胸廓修复、关节置换等。当PEEK被用于关节等部位时,由于关节的活动性较大,常常会导致关节面的磨损,致使患者疼痛以及关节置换后愈后较差。此外,由于关节置换的创面较大,3D打印PEEK支架在植入的初期可能会导致感染,且支架和关节面的摩擦同样也可能导致手术部位的感染。手术部位感染后,愈合过程较为缓慢,同时还有可能导致并发症,大大降低了患者的生活质量。
因此,为了解决3D打印PEEK支架在关节置换过程中所存在的感染和磨损的问题,需要制备出具有长效抗菌和自润滑功能的3D打印PEEK支架。本发明首先通过配方设计在材料中负载了具有抗菌效果的物质,其次在PEEK支架的表面形成了稳定的凝胶层,并在凝胶层中负载了抗生素。最终,3D打印PEEK支架能够在植入后的初期释放抗生素,中后期通过释放抗菌离子达到长效抗菌效果;此外,支架表面的凝胶层能够起到润滑的效果,从而避免支架植入后对关节或者软骨的摩擦磨损。
发明内容
为了解决目前PEEK支架材料用于关节置换过程中所遇到的感染问题以及由于支架表面粗糙导致的关节摩擦磨损,本发明提供了一种具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法,该方法能够解决3D打印PEEK支架进行关节置换后的感染和关节磨损而导致的疼痛和愈后较差的问题。
为解决上述技术问题,本发明采用以下技术方案:
本发明的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法包括如下步骤:
1)将PEEK粉末、氧化锌、纳米银和沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机混合均匀后制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架利用混合酸溶液进行处理得到表面具有-NO2基团的PEEK-NO2支架;然后利用SnCl2的酸溶液进行处理得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到透明质酸或海藻酸钠的溶液中反应,使其表面接枝透明质酸或者海藻酸钠分子;然后,将表面接枝透明质酸或者海藻酸钠分子的PEEK支架进行氧化处理,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有抗生素的蛋白溶液中进行反应,得到表面具有凝胶层的PEEK支架。
优选的,步骤1)中所述的3D打印线材中各原料的质量份数分别为:PEEK粉末87-95份、氧化锌2-5份、纳米银1-3份、ZIF 2-5份;所述混合温度为350-370℃;所述的混合时间为10-30min。
优选的,所述步骤2)中所述的混合酸溶液为浓H2SO4和浓HNO3的混合液,二者的体积比为4:1-1:1,反应温度为40-80℃,反应时间为60-120min。
优选的,所述步骤2)中所述的所述的溶解SnCl2的酸溶液为浓HCl、浓H2SO4中的一种或两种;所述的SnCl2的浓度为0.05-0.3g/ml;所述的反应温度为50-90℃,反应时间为4-8h。
优选的,所述步骤3)中透明质酸或海藻酸钠的浓度为0.05-0.2g/ml;所述的氧化透明质酸或海藻酸钠所使用的试剂为高碘酸钠,高碘酸钠的浓度为0.1-0.3g/ml,反应时间为12-24h。
优选的,所述步骤4)中所述的抗生素为万古霉素、氯唑西林、头孢唑林中的一种或两种。
优选的,所述步骤4)中所述的蛋白为明胶、丝素蛋白或胶原蛋白的一种或两种;所述蛋白溶液的浓度为0.01-0.04g/ml,所述反应时间为2-5h,反应温度为0-10℃。
利用本发明的制备方法所制备得到的具有长效抗菌和自润滑功能的3D打印PEEK支架可用于肩关节、膝关节等需要关节置换的部位。
与现有技术相比,本发明制备的具有长效抗菌和自润滑功能的3D打印PEEK支架的优点在于:
(1)本发明所制备的3D打印PEEK支架具有长效抗菌效果,其中凝胶层中的抗生素能够避免手术初期的感染,支架中所负载的抗菌物质能够缓慢释放避免感染的复发,从而具有长效抗菌的效果;
(2)本发明所制备的3D打印PEEK支架的抗菌有效期能够依据患者的实际情况进行调节,从而确保患者在康复期内能够得到较好保障;
(3)本发明所制备的3D打印PEEK支架表面具有凝胶涂层,具有自润滑的功能,从而避免了关节置换后摩擦磨损造成的疼痛及愈后较差的问题;
(4)本发明所制备的凝胶涂层与3D打印PEEK支架表面具有较好的结合能力,从而避免了在使用过程中凝胶层的脱落。
具体实施方式
结合具体实施例对本发明进行进一步的阐述和说明,但本发明的实施方式不限于此。
实施例1
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将95gPEEK粉末、2g氧化锌、1g纳米银和2g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在350℃混合30min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由20ml浓H2SO4和5ml浓HNO3的组成的混合酸溶液中,在40℃条件下搅拌反应120min后得到PEEK-NO2;然后将0.5gSnCl2溶于10ml浓HCl溶液中,于50℃反应8h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.05g/ml的透明质酸的溶液中反应,使其表面接枝透明质酸分子;然后,将表面接枝透明质酸分子的PEEK支架浸没0.1g/ml的高碘酸钠溶液中反应24h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有万古霉素的浓度为0.01g/ml明胶溶液中,在0℃反应5h得到表面具有凝胶层的PEEK支架。
实施例2
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将87gPEEK粉末、5g氧化锌、3g纳米银和5g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在370℃混合10min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由10ml浓H2SO4和10ml浓HNO3的组成的混合酸溶液中,在80℃条件下搅拌反应60min后得到PEEK-NO2;然后将3gSnCl2溶于10ml浓HCl溶液中,于90℃反应4h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.2g/ml的透明质酸的溶液中反应,使其表面接枝透明质酸分子;然后,将表面接枝透明质酸的PEEK支架浸没0.3g/ml的高碘酸钠溶液中反应12h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有万古霉素的浓度为0.04g/ml明胶溶液中,在10℃反应2h得到表面具有凝胶层的PEEK支架。
实施例3
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将92gPEEK粉末、3g氧化锌、2g纳米银和3g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在360℃混合20min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由15ml浓H2SO4和5ml浓HNO3的组成的混合酸溶液中,在60℃条件下搅拌反应90min后得到PEEK-NO2;然后将2gSnCl2溶于10ml浓H2SO4溶液中,于70℃反应6h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.1g/ml的海藻酸钠溶液中反应,使其表面接枝海藻酸钠分子;然后,将表面接枝海藻酸钠的PEEK支架浸没0.2g/ml的高碘酸钠溶液中反应18h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有氯唑西林的浓度为0.02g/ml丝素蛋白溶液中,在5℃反应4h得到表面具有凝胶层的PEEK支架。
实施例4
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将90gPEEK粉末、2g氧化锌、3g纳米银和5g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在350℃混合30min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由20ml浓H2SO4和10ml浓HNO3的组成的混合酸溶液中,在40℃条件下搅拌反应120min后得到PEEK-NO2;然后将1gSnCl2溶于10ml浓H2SO4溶液中,于50℃反应8h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.3g/ml的海藻酸钠溶液中反应,使其表面接枝海藻酸钠分子;然后,将表面接枝海藻酸钠的PEEK支架浸没0.3g/ml的高碘酸钠溶液中反应12h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有头孢唑林的浓度为0.02g/ml胶原溶液中,在5℃反应4h得到表面具有凝胶层的PEEK支架。
实施例5
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将92gPEEK粉末、5g氧化锌、1g纳米银和2g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在370℃混合20min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由10ml浓H2SO4和10ml浓HNO3的组成的混合酸溶液中,在80℃条件下搅拌反应60min后得到PEEK-NO2;然后将3gSnCl2溶于10ml浓HCl溶液中,于50℃反应8h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.05g/ml的透明质酸溶液中反应,使其表面接枝透明质酸分子;然后,将表面接枝透明质酸的PEEK支架浸没0.1g/ml的高碘酸钠溶液中反应24h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有万古霉素和头孢唑林的浓度为0.02g/ml明胶和胶原(重量比1:1)溶液中,在0℃反应5h得到表面具有凝胶层的PEEK支架。
实施例6
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将87gPEEK粉末、5g氧化锌、3g纳米银和5g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在350℃混合30min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由20ml浓H2SO4和10ml浓HNO3的组成的混合酸溶液中,在80℃条件下搅拌反应60min后得到PEEK-NO2;然后将3gSnCl2溶于10ml浓HCl溶液中,于50℃反应8h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.1g/ml的海藻酸钠溶液中反应,使其表面接枝海藻酸钠分子;然后,将表面接枝海藻酸钠的PEEK支架浸没0.1g/ml的高碘酸钠溶液中反应24h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有氯唑西林和头孢唑林的浓度为0.02g/ml明胶和丝素蛋白(重量比1:1)溶液中,在10℃反应2h得到表面具有凝胶层的PEEK支架。
实施例7
本实施例的具有长效抗菌和自润滑功能的3D打印PEEK支架的制备方法如下:
1)将95gPEEK粉末、2g氧化锌、1g纳米银和2g沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机在370℃混合20min后,制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架浸没到由10ml浓H2SO4和10ml浓HNO3的组成的混合酸溶液中,在60℃条件下搅拌反应90min后得到PEEK-NO2;然后将1gSnCl2溶于10ml浓HCl溶液中,于90℃反应4h,得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到0.05g/ml的透明质酸溶液中反应,使其表面接枝透明质酸分子;然后,将表面接枝透明质酸的PEEK支架浸没0.3g/ml的高碘酸钠溶液中反应12h,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有氯唑西林和万古霉素的浓度为0.02g/ml胶原和丝素蛋白(重量比1:1)溶液中,在10℃反应2h得到表面具有凝胶层的PEEK支架。
Claims (9)
1.一种具有长效抗菌和自润滑功能的3D打印支架的制备方法,其特征在于,包括如下步骤:
1)将PEEK粉末、氧化锌、纳米银和沸石咪唑酯骨架结构材料(ZIF)利用双螺杆挤出机混合均匀后制备成3D打印所需要的线材;设计支架的三维结构,利用3D打印机打印出相应的形状;
2)将PEEK支架利用混合酸溶液进行处理得到表面具有-NO2基团的PEEK-NO2支架;然后利用SnCl2的酸溶液进行处理得到表面具有-NH2基团的PEEK-NH2支架;
3)将PEEK-NH2支架浸没到透明质酸溶液或海藻酸钠溶液中反应,使其表面接枝透明质酸或者海藻酸钠分子;然后,将表面接枝透明质酸或者海藻酸钠分子的PEEK支架进行氧化处理,得到表面带有-CHO基团的PEEK-CHO支架;
4)将PEEK-CHO支架浸没到溶解有抗生素的蛋白溶液中进行反应,得到表面为凝胶层的具有长效抗菌和自润滑功能的3D打印PEEK支架。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤1)中3D打印线材中各原料的质量份数分别为:PEEK粉末87-95份、氧化锌2-5份、纳米银1-3份、沸石咪唑酯骨架结构材料(ZIF)2-5份;所述双螺杆挤出机的混合温度为350-370℃,混合时间为10-30min。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤2)中的混合酸溶液为浓H2SO4和浓HNO3的混合液,二者的体积比为4:1-1:1,利用混合酸溶液进行处理的反应温度为40-80℃,反应时间为60-120min。
4.根据权利要求1所述的制备方法,其特征在于,所述步骤2)中SnCl2的酸溶液中采用的酸为浓HCl、浓H2SO4中的一种或两种;所述SnCl2的酸溶液中SnCl2的浓度为0.05-0.3g/mL;所述利用SnCl2的酸溶液进行处理的反应温度为50-90℃,反应时间为4-8h。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤3)中透明质酸溶液的浓度为0.05-0.2g/mL,海藻酸钠溶液的浓度为0.05-0.2g/mL。
6.根据权利要求1所述的制备方法,其特征在于,所述步骤3)中将表面接枝透明质酸或者海藻酸钠分子的PEEK支架进行氧化处理所使用的试剂为高碘酸钠,高碘酸钠的浓度为0.1-0.3g/mL,反应时间为12-24h。
7.根据权利要求1所述的制备方法,其特征在于,所述步骤4)中的抗生素为万古霉素、氯唑西林、头孢唑林中的一种或两种;所述蛋白为明胶、丝素蛋白或胶原蛋白的一种或两种,蛋白溶液的浓度为0.01-0.04g/mL。
8.根据权利要求1所述的制备方法,其特征在于,所述步骤4)中的反应时间为2-5h,反应温度为0-10℃。
9.根据权利要求1-8任一任意所述的制备方法制得的具有长效抗菌和自润滑功能的3D打印PEEK支架用于需要关节置换的肩关节、膝关节。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116285096A (zh) * | 2022-12-16 | 2023-06-23 | 沪金(苏州)实业有限公司 | 一种长效抗菌聚丙烯盛装容器及制造方法 |
Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080188938A1 (en) * | 2004-10-06 | 2008-08-07 | Bayco Tech Limited | Bone Implant Device |
EP2213315A1 (en) * | 2009-01-30 | 2010-08-04 | Mero S.r.L. | Antibacterial hydrogel and use thereof in orthopedics |
US20120101593A1 (en) * | 2010-10-20 | 2012-04-26 | BIOS2 Medical, Inc. | Implantable polymer for bone and vascular lesions |
US20130197660A1 (en) * | 2010-04-22 | 2013-08-01 | Nobil Bio Ricerche S.R.L. | Implantable devices having antibacterial properties and multifunctional surfaces |
CN103977451A (zh) * | 2014-05-19 | 2014-08-13 | 吉林大学 | 钽涂层多级孔聚醚醚酮人工骨支架的3d打印制造方法 |
CN104667345A (zh) * | 2015-01-30 | 2015-06-03 | 深圳迈普再生医学科技有限公司 | 一种具有生物活性的颅骨修复假体及其制备方法 |
US20150250923A1 (en) * | 2012-09-18 | 2015-09-10 | Corticalis As | Hydrogel coated scaffold |
CN105105875A (zh) * | 2015-08-04 | 2015-12-02 | 西安交通大学 | 一种具有内生长功能的仿生人工髋关节 |
US20180028724A1 (en) * | 2015-02-16 | 2018-02-01 | Tecres S.P.A. | Material for the molding of devices to be implanted into the human body or of articular spacers |
CN107778497A (zh) * | 2017-11-09 | 2018-03-09 | 华东师范大学 | 一种按需释放的复合共价水凝胶及其制备方法和应用 |
WO2018095578A1 (de) * | 2016-11-25 | 2018-05-31 | Stimos Gmbh | Material für ein knochenimplantat und verfahren zum herstellen eines solchen |
US20180236132A1 (en) * | 2015-02-24 | 2018-08-23 | Universitaet Konstanz | Material for bone implants and method of producing same |
US20190201584A1 (en) * | 2018-01-02 | 2019-07-04 | Shandong Branden Medical Device Co.,Ltd | Porous bionic skull repairing material, preparation method and implement method thereof |
CN110511419A (zh) * | 2019-09-02 | 2019-11-29 | 吉林大学 | 一种改善碳纤维增强聚醚醚酮复合材料表面生物活性的方法 |
CN110665064A (zh) * | 2019-09-19 | 2020-01-10 | 安徽理工大学 | 一种仿生人工关节材料及其制备方法 |
CN111440342A (zh) * | 2020-05-18 | 2020-07-24 | 东华大学 | 具有化学键强界面的cf/peek复合材料及其制备方法 |
US20200308440A1 (en) * | 2016-06-24 | 2020-10-01 | University Of Iowa Research Foundation | Durable photopolymerizable cross-linked anti-fouling coatings |
US20200330510A1 (en) * | 2019-03-29 | 2020-10-22 | Board Of Trustees Of Michigan State University | Resurrection Of Antibiotics That MRSA Resists By Silver-Doped Bioactive Glass-Ceramic Particles |
US20200376168A1 (en) * | 2017-05-01 | 2020-12-03 | New York Society For The Ruptured And Crippled Maintaining The Hospital For Special Surgery | A method of and a mold for the manufacture, making and/or production of a multi-component implant, device, construct or material |
CN112206349A (zh) * | 2020-10-19 | 2021-01-12 | 吉林大学 | 在金属医用植入材料表面制备的zif-8@抗菌离子涂层及其制备方法 |
WO2021013303A1 (de) * | 2019-07-19 | 2021-01-28 | Stimos Gmbh | Material für ein knochenimplantat |
US20210046221A1 (en) * | 2019-08-15 | 2021-02-18 | Axogen Corporation | Tissue repair membrane adapted for adhesion and lubrication, and methods for preparing the same |
WO2021067145A1 (en) * | 2019-10-01 | 2021-04-08 | Duke University | Artificial cartilage |
-
2021
- 2021-07-21 CN CN202110823078.3A patent/CN113425911B/zh active Active
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080188938A1 (en) * | 2004-10-06 | 2008-08-07 | Bayco Tech Limited | Bone Implant Device |
EP2213315A1 (en) * | 2009-01-30 | 2010-08-04 | Mero S.r.L. | Antibacterial hydrogel and use thereof in orthopedics |
US20130197660A1 (en) * | 2010-04-22 | 2013-08-01 | Nobil Bio Ricerche S.R.L. | Implantable devices having antibacterial properties and multifunctional surfaces |
US20120101593A1 (en) * | 2010-10-20 | 2012-04-26 | BIOS2 Medical, Inc. | Implantable polymer for bone and vascular lesions |
US20150250923A1 (en) * | 2012-09-18 | 2015-09-10 | Corticalis As | Hydrogel coated scaffold |
CN103977451A (zh) * | 2014-05-19 | 2014-08-13 | 吉林大学 | 钽涂层多级孔聚醚醚酮人工骨支架的3d打印制造方法 |
CN104667345A (zh) * | 2015-01-30 | 2015-06-03 | 深圳迈普再生医学科技有限公司 | 一种具有生物活性的颅骨修复假体及其制备方法 |
US20180028724A1 (en) * | 2015-02-16 | 2018-02-01 | Tecres S.P.A. | Material for the molding of devices to be implanted into the human body or of articular spacers |
US20180236132A1 (en) * | 2015-02-24 | 2018-08-23 | Universitaet Konstanz | Material for bone implants and method of producing same |
CN105105875A (zh) * | 2015-08-04 | 2015-12-02 | 西安交通大学 | 一种具有内生长功能的仿生人工髋关节 |
US20200308440A1 (en) * | 2016-06-24 | 2020-10-01 | University Of Iowa Research Foundation | Durable photopolymerizable cross-linked anti-fouling coatings |
WO2018095578A1 (de) * | 2016-11-25 | 2018-05-31 | Stimos Gmbh | Material für ein knochenimplantat und verfahren zum herstellen eines solchen |
US20200376168A1 (en) * | 2017-05-01 | 2020-12-03 | New York Society For The Ruptured And Crippled Maintaining The Hospital For Special Surgery | A method of and a mold for the manufacture, making and/or production of a multi-component implant, device, construct or material |
CN107778497A (zh) * | 2017-11-09 | 2018-03-09 | 华东师范大学 | 一种按需释放的复合共价水凝胶及其制备方法和应用 |
US20190201584A1 (en) * | 2018-01-02 | 2019-07-04 | Shandong Branden Medical Device Co.,Ltd | Porous bionic skull repairing material, preparation method and implement method thereof |
US20200330510A1 (en) * | 2019-03-29 | 2020-10-22 | Board Of Trustees Of Michigan State University | Resurrection Of Antibiotics That MRSA Resists By Silver-Doped Bioactive Glass-Ceramic Particles |
WO2021013303A1 (de) * | 2019-07-19 | 2021-01-28 | Stimos Gmbh | Material für ein knochenimplantat |
US20210046221A1 (en) * | 2019-08-15 | 2021-02-18 | Axogen Corporation | Tissue repair membrane adapted for adhesion and lubrication, and methods for preparing the same |
CN110511419A (zh) * | 2019-09-02 | 2019-11-29 | 吉林大学 | 一种改善碳纤维增强聚醚醚酮复合材料表面生物活性的方法 |
CN110665064A (zh) * | 2019-09-19 | 2020-01-10 | 安徽理工大学 | 一种仿生人工关节材料及其制备方法 |
WO2021067145A1 (en) * | 2019-10-01 | 2021-04-08 | Duke University | Artificial cartilage |
CN111440342A (zh) * | 2020-05-18 | 2020-07-24 | 东华大学 | 具有化学键强界面的cf/peek复合材料及其制备方法 |
CN112206349A (zh) * | 2020-10-19 | 2021-01-12 | 吉林大学 | 在金属医用植入材料表面制备的zif-8@抗菌离子涂层及其制备方法 |
Non-Patent Citations (5)
Title |
---|
DENG,LJ: "simvastin delivery on peek for bioactivity and osteogenesis enhancements", 《JOURNAL OF BIOMATERIALS SCIENCE POLYMER EDITION》 * |
HE, XH等: "Drug-loaded/grafted peptide-modified porousPEEKto promote bone tissue repair and eliminate bacteria", 《COLLOIDS AND SURFACES B-BIOINTERFACES》 * |
ZHAO,XD等: "bio-inspired surface modification of peek through the dual cross-linked hydrogel layers", 《JOURNAL OF THE MECHANICAL BEHAVIOR OF BIOMEDICAL MATERIALS》 * |
潘亮: "含烯丙基聚芳醚酮合成及表面水凝胶涂层制备", 《中国优秀硕士学位论文全文数据库》 * |
赵晓铎: "聚醚醚酮表面仿生承载润滑层的构建及其摩擦性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑;》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116285096A (zh) * | 2022-12-16 | 2023-06-23 | 沪金(苏州)实业有限公司 | 一种长效抗菌聚丙烯盛装容器及制造方法 |
CN116285096B (zh) * | 2022-12-16 | 2024-03-26 | 沪金(苏州)实业有限公司 | 一种长效抗菌聚丙烯盛装容器及制造方法 |
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