CN111057420A - 医用钴铬合金的防腐蚀纳米涂层材料及其离子喷涂方法 - Google Patents

医用钴铬合金的防腐蚀纳米涂层材料及其离子喷涂方法 Download PDF

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CN111057420A
CN111057420A CN201911332187.4A CN201911332187A CN111057420A CN 111057420 A CN111057420 A CN 111057420A CN 201911332187 A CN201911332187 A CN 201911332187A CN 111057420 A CN111057420 A CN 111057420A
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chromium alloy
antioxidant
cobalt
anticorrosive
nano
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鄢腊梅
张美玲
林成
李文馨
葛云阳
袁友伟
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Hangzhou Dianzi University
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Abstract

本发明公开医用钴铬合金的防腐蚀纳米涂层材料及其离子喷涂方法。本发明抗氧化涂层材料包括粘合剂、防腐材料、抗氧化剂；其中粘合剂与防腐材料、抗氧化剂总量的质量比为1:1，防腐材料、抗氧化剂总量中防腐材料的质量含量为90～98％，其余为抗氧化剂；本发明通过等离子喷涂法，将涂层的材料加工成些颗粒很小的纳米粒子,能增加材料的密封性,在钴铬合金表面形成一层致密的涂层，以提高钴铬合金的耐腐蚀性能。

Description

医用钴铬合金的防腐蚀纳米涂层材料及其离子喷涂方法
技术领域
本发明属于高分子材料技术领域，涉及一种能增强医用钴铬合金防腐蚀性能的抗氧化涂层的制备方法及离子喷涂方法。
背景技术
钴铬合金是由钴、铬、镍、钼等元素经高真空冶练而成的高强度耐腐蚀的合金，是当前齿科和骨科修复中的主要材料。应用于牙科的钴铬合金，在有无远缘链球菌存在的人工唾液中受腐蚀后，钴铬合金容易析出钴离子。应用于骨科假体的钴铬合金，在人体的体液中，容易被腐蚀,从而导致植入部位pH增加、机械过早失效等不良反应。因此，如何增强医用钴铬合金的耐腐蚀性能是当前的研究热点。
发明内容
本发明的一个目的是针对现有技术的不足，提供一种能增强医用钴铬合金防腐蚀性能的抗氧化涂层材料。
本发明抗氧化涂层材料包括粘合剂、防腐材料、抗氧化剂；其中粘合剂与防腐材料、抗氧化剂总量的质量比为1:1，防腐材料、抗氧化剂总量中防腐材料的质量含量为90～98％，其余为抗氧化剂；
所述的粘合剂包括磷酸铝、硼砂、聚氯丙烯树脂、甲基丙烯酸乙酯、聚丙烯酸酯、呋喃树脂胶粘剂中的一种或者多种；
所述的防腐材料包括铌、贝壳粉、氧化钐、稀土氧化钕、氧化铋、钇铝石榴石、氮化硅中的一种或者多种；
所述的抗氧化剂包括双羟基甲基醚、硫代硫酸钠、3-甲氧基4-羟基苯乙二醇、半胱氨酸、2,3-叔丁基羟基茴香醚中的一种或者多种；
本发明的另一个目的是提供上述抗氧化纳米涂层材料的离子喷涂方法，包括如下步骤：
步骤(1)、基底表面净化：
以钴铬合金为基体，切割成长50mm、宽50mm、厚4mm的长方体,为了获得高的涂层与医用钴铬合金基底的附着力，先用无水酒精清洗钴铬合金基底，再用氧化铝喷丸清理。同时将钴铬合金基底预热至150～225℃。
步骤(2)、防腐材料和抗氧化剂纳米细化：
首先将防腐材料和抗氧化剂混合，然后加入到行星式高能球磨机DECO-PBM-V-0.4L，在球磨过程中加入工艺控制剂，以有效地避免上述粉末粘附在磨球和磨罐上,同时能很好地改善粉末颗粒的均匀性，球磨转速为260～360r/min,球磨时间为6～20h。
所述的工艺控制剂包括乙醇、棕榈酸；每克防腐材料和抗氧化剂总量加入5～15毫升乙醇；棕榈酸为防腐材料和抗氧化剂总量的1～3.5wt％；
步骤(3)、纳米粒径筛选，得到防腐纳米粉末：
将步骤(2)纳米细化后的防腐材料和抗氧化剂混料采用YBS1000摇摆筛，筛选出粒径为40～85nm的防腐纳米粉末。筛层选用1～5层，过滤附件选用1～2层，再配合1～2层的清网装置可获得更加理想的筛分效果。当粒径大于85nm时，重复步骤(2)。
步骤(4)、粘合剂粘度的增强：
将粘合剂置于AIR-1L系列真空反应器中，乳化均质机转速：10000～28000rpm，加热方式：水浴、油浴循环的1种或者2种。搅拌机功率：120～180W，温度加热至65～80℃；保护气为氮气、氩气中的一种或者两种，搅拌3～8小时。
步骤(5)、在步骤(1)经预热的医用钴铬合金基体上，先采用等离子喷涂方法将步骤(4)处理后粘合剂喷涂在基体表面制备得到粘结层，然后继续采用等离子喷涂方法将步骤(3)处理后防腐纳米粉末喷涂在粘结层表面制备得到防腐涂层：粘结层厚度为0.01～0.09mm，防腐涂层厚度为0.08～0.22mm。
等离子喷涂方法参数如下：
采用美国进口AT-3000等离子喷涂设备；电流520～650A；电压45～60V；主气流量：30～60L·s-1；氩气、氮气、氢气中的一种或者多种作为等离子气；送粉压力0.3～0.8MPa；喷涂距离110～140mm；火炮移动速度120～140mm·s-1；移动步距2.2～4.2mm；喷枪与钴铬合金表面的喷涂夹角为50～85°。
步骤(6)、表面的光滑：
防腐涂层表面用不同金刚砂纸(800、1000和1200目)磨，用纯净水清洗后，再用丙酮冲洗，最后在80～150℃下加热20～70分钟以干燥表面，冷却至室温。
步骤(7)、性能测试：
腐蚀试验用的仪器为带回流冷凝器及加热装置的磨口锥形烧瓶，再将上述样品或浸泡在500毫升1M HCl溶液中且保持70天。保持样品完全浸入，且试样与瓶底不能接触，试样之间避免相互接触。
腐蚀性能测试：使用美国普林斯顿应用研究的VersaSTAT4型电化学工作站，数据采集4x16bit(500k)，升压时间(-1.0V to+1.0V)<350ns，扫速3000～5000V/s；测试温度控制在(37士0.5)℃。启动电化学测试软件，输入动电位扫描的参数，测得上述样品的线性极化曲线LPR。
使用Hitachi公司的HITACHIS-4800型扫描电镜观察等离子喷涂制备复合陶瓷涂层的表面形貌。
本发明通过等离子喷涂法，将涂层的材料加工成些颗粒很小的纳米粒子,能增加材料的密封性,在钴铬合金表面形成一层致密的涂层，以提高钴铬合金的耐腐蚀性能。
本发明的有益效果：
1.在本发明中，将防腐材料和抗氧化剂混合纳米细化出粒径为40～85nm的防腐纳米粉末，细小的防腐纳米粉末通过粘结剂增加本发明中防腐涂层与钴铬合金基体的粘附性，构成了一道阻碍氧向钴铬合金基底渗透的屏障，形成了“扎钉效应”，表面形成了致密而连续的氧化膜。
2.本发明选用双羟基甲基醚、硫代硫酸钠、3-甲氧基4-羟基苯乙二醇、半胱氨酸、2,3-叔丁基羟基茴香醚等抗氧化剂，具有吸氧作用，能够抑制氧在钴铬合金内部的扩散，提高了防腐涂层的塑性和抗氧化性能。
附图说明
图1为本发明实施例1所得样品的表面形貌照片；
图2为本发明实施例2所得样品的表面形貌照片；
图3为本发明实施例3所得样品的表面形貌照片；
图4为钴铬合金基底在未涂抗氧化涂层前的表面形貌照片；
图5为本发明实施例1，2,3样品和钴铬合金基底在500毫升1M HCl溶液中的极化曲线；
图6本发明实施例1在500毫升1M HCl溶液中70天的腐蚀动力学曲线模拟图；
图7本发明实施例2在500毫升1M HCl溶液中70天的腐蚀动力学曲线模拟图；
图8本发明实施例3在500毫升1M HCl溶液中70天的腐蚀动力学曲线模拟图；
图9本发明钴铬合金基底在500毫升1M HCl溶液中70天的腐蚀动力学曲线模拟图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细描述：
实施例1：
(1)基底表面净化：为了获得高的涂层与医用钴铬合金基底的附着力，先用无水酒精清洗钴铬合金基底，再用氧化铝喷丸清理。同时将钴铬合金基底预热至150℃。
(2)92wt％防腐涂层材料和8wt％抗氧化剂材料纳米细化：首先将0.3g铌，0.2g贝壳粉，0.15g氧化钐,0.27g稀土氧化钕，0.06g双羟基甲基醚，0.01g的3-甲氧基4-羟基苯乙二醇，0.01g半胱氨酸置于四罐实验室行星式高能球磨机“DECO-PBM-V-0.4L”，快速、高效、精确的样品研制、混合、均化，在球磨过程中加入工艺控制剂(5毫升乙醇和0.01g棕榈酸)，以有效地避免上述粉末粘附在磨球和磨罐上,同时能很好地改善粉末颗粒的均匀性，球磨转速为260r/min,球磨时间为20h。
(3)纳米粒径筛选：再采用YBS1000摇摆筛，筛选出粒径为40nm的粉末。筛层选用1层，过滤附件选用2层.再配合2层的清网装置可获得更加理想的筛分效果。当粒径大于40nm的粉末重复步骤(2)。
(4)粘合剂粘度的增强：先将粘合剂，按重量成分0.5g磷酸铝、0.25g硼砂、0.25g聚氯丙烯树脂：放置在AIR-1L系列真空反应器中，乳化均质机转速：10000rpm，加热方式：水浴、油浴循环。搅拌机功率：120W，温度加热至65℃；保护气为氮气，搅拌3小时。
(5)在步骤(1)经预热的医用钴铬合金基体上，先采用等离子喷涂方法将步骤(4)处理后粘合剂喷涂在基体表面制备得到粘结层，然后继续采用等离子喷涂方法将步骤(3)处理后防腐纳米粉末喷涂在粘结层表面制备得到防腐涂层：粘结层厚度为0.01mm，防腐涂层厚度为0.22mm：
采用美国进口AT-3000等离子喷涂设备，电流：520A；电压45V；主气流量：30L·s-1；其中氩气作为等离子气。送粉压力：0.3MPa；喷涂距离：110mm，火炮移动速度120mm.s-1；移动步距2.2mm；喷枪与钴铬合金表面的喷涂夹角为50°。
(6)表面的光滑：表面用1200目金刚砂纸磨光样品表面，用纯净水清洗后，再用丙酮冲洗，然后在80℃下加热20分钟以干燥表面，冷却至室温即可。
实施例2
(1)基底表面净化：为了获得高的涂层与医用钴铬合金基底的附着力，先用无水酒精清洗钴铬合金基底，再用氧化铝喷丸清理。同时将钴铬合金基底预热至225℃。
(2)98wt％防腐材料和2wt％抗氧化剂纳米细化：
首先将0.08g铌，0.1g贝壳粉，0.3g氧化钐,0.2g稀土氧化钕，0.2g氧化铋，0.1g钇铝石榴石，0.005g硫代硫酸钠，0.01g半胱氨酸，0.005g 2,3-叔丁基羟基茴香醚；置于四罐实验室行星式高能球磨机“DECO-PBM-V-0.4L”，快速、高效、精确的样品研制、混合、均化，在球磨过程中加入工艺控制剂(15毫升乙醇和0.035g棕榈酸)，以有效地避免上述粉末粘附在磨球和磨罐上,同时能很好地改善粉末颗粒的均匀性，球磨转速为360r/min,球磨时间为6h。
(3)纳米粒径筛选：再采用YBS1000摇摆筛，筛选出粒径为85nm的粉末。筛层选用5层，过滤附件选用1层.再配合2层的清网装置可获得更加理想的筛分效果。粒径大于85nm的粉末重复步骤(2)。
(4)粘合剂粘度的增强：将0.25g聚氯丙烯树脂、0.25g甲基丙烯酸乙酯、0.25g聚丙烯酸酯、0.25g呋喃树脂胶粘剂，放置在AIR-1L系列真空反应器中，乳化均质机转速：28000rpm，加热方式：水浴。搅拌机功率：180W，温度加热至80℃；保护气为氩气，搅拌8小时。
(5)在步骤(1)经预热的医用钴铬合金基体上，先采用等离子喷涂方法将步骤(4)处理后粘合剂喷涂在基体表面制备得到粘结层，然后继续采用等离子喷涂方法将步骤(3)处理后防腐纳米粉末喷涂在粘结层表面制备得到防腐涂层：粘结层厚度为0.09mm，防腐涂层厚度为0.12mm：
采用美国进口AT-3000等离子喷涂设备，电流：650A；电压60V；主气流量：60L·s-1；其中氮气作为等离子气，送粉压力：0.8MPa；喷涂距离：140mm，火炮移动速度140mm.s-1；移动步距4.2mm；喷枪与钴铬合金表面的喷涂夹角为85°。
(6)表面的光滑：表面用800目金刚砂纸磨光样品表面，用纯净水清洗后，再用丙酮冲洗，然后在150℃下加热70分钟以干燥表面，冷却至室温。
实施例3
(1)基底表面净化：为了获得高的涂层与医用钴铬合金基底的附着力，先用无水酒精清洗钴铬合金基底，再用氧化铝喷丸清理。同时将钴铬合金基底预热至185℃。
(2)96wt％防腐涂层材料和4wt％抗氧化剂材料纳米细化：首先将0.16g氧化钐,0.2g稀土氧化钕，0.2g氧化铋，0.1g钇铝石榴石,0.3g氮化硅,0.02g的3-甲氧基4-羟基苯乙二醇，0.01g的2,3-叔丁基羟基茴香醚置于四罐实验室行星式高能球磨机“DECO-PBM-V-0.4L”，快速、高效、精确的样品研制、混合、均化，在球磨过程中加入工艺控制剂(10毫升乙醇和0.025g棕榈酸)，以有效地避免上述粉末粘附在磨球和磨罐上,同时能很好地改善粉末颗粒的均匀性，球磨转速为300r/min,球磨时间为12h。
(3)纳米粒径筛选：再采用YBS1000摇摆筛，筛选出粒径为65nm的粉末。筛层选用3层，过滤附件选用2层.再配合2层的清网装置可获得更加理想的筛分效果。粒径大于65nm的粉末重复步骤(2)。
(4)粘合剂粘度的增强：
将0.1g磷酸铝、0.2g聚氯丙烯树脂、0.4g聚丙烯酸酯、0.3g呋喃树脂胶粘剂，放置在AIR-1L系列真空反应器中，乳化均质机转速：18000rpm，加热方式：油浴循环。搅拌机功率：120W，温度加热至80℃；保护气为氮气，搅拌6小时。
(5)在步骤(1)经预热的医用钴铬合金基体上，先采用等离子喷涂方法将步骤(4)处理后粘合剂喷涂在基体表面制备得到粘结层，然后继续采用等离子喷涂方法将步骤(3)处理后防腐纳米粉末喷涂在粘结层表面制备得到防腐涂层：粘结层厚度为0.06mm，防腐涂层厚度为0.18mm：
采用美国进口AT-3000等离子喷涂设备，电流：550A；电压50V；主气流量：45L·s-1；其中氩气、氮气、氢气作为等离子气。送粉压力：0.6MPa；喷涂距离：130mm，火炮移动速度130mm.s-1；移动步距3.2mm；喷枪与钴铬合金表面的喷涂夹角为75°。
(6)表面的光滑：表面用1000目金刚砂纸磨光样品表面，用纯净水清洗后，再用丙酮冲洗，然后在120℃下加热50分钟以干燥表面，冷却至室温。
表面形貌：
使用Hitachi公司的HITACHIS-4800型扫描电镜观察等离子喷涂制备复合陶瓷涂层的表面形貌。图1-4为实施例1，2,3所得样品和钴铬合金基底未未涂抗氧化涂层前的表面形貌照。从图中可以明显看出，本发明实施例1,2,3所得样品，表面形成了致密而连续的氧化膜。而图4为钴铬合金基底未未涂抗氧化涂层前的表面形貌照看出有空洞和严重被氧化的现象。
腐蚀性能测试：
腐蚀试验用的仪器为带回流冷凝器及加热装置的磨口锥形烧瓶，再将上述样品或浸泡在500毫升1M HCl溶液中且保持微沸状态连续16小时。保持样品完全浸入，且试样与瓶底不能接触且试样之间避免相互接触。图5为本发明实施例1，2,3样品和钴铬合金在未涂抗氧化涂层样品前在500毫升1M HCl溶液中的极化曲线，从图中可以明显看出，钴铬合金在未涂抗氧化涂层样品前的腐蚀速率明显高于本发明实施例1,2,3样品。为了进一步研究其各个阶段的腐蚀性能，将本发明的实施例1，2,3样品和钴铬合金在未涂抗氧化涂层样品1MHCl溶液中保持70天，使用美国普林斯顿应用研究的VersaSTAT4型电化学工作站，数据采集4x16bit(500k)，升压时间(-1.0V to+1.0V)<350ns，扫速3000～5000V/s；测试温度控制在(37士0.5)℃。启动电化学测试软件，输入动电位扫描的参数，得到其腐蚀动力学曲线模拟图。图6-9分别为本发明实施例1，2,3样品和钴铬合金基底在500毫升1M HCl溶液中70天的腐蚀动力学曲线模拟图。从4个图明显可以看出，钴铬合金在未涂抗氧化涂层样品前的腐蚀速率明显高于本发明实施例1,2,3样品。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。

Claims (4)

1.医用钴铬合金的防腐蚀纳米涂层材料，其特征在于包括粘合剂、防腐材料、抗氧化剂；其中粘合剂与防腐材料、抗氧化剂总量的质量比为1:1，防腐材料、抗氧化剂总量中防腐材料的质量含量为90～98％，其余为抗氧化剂；
所述的粘合剂包括磷酸铝、硼砂、聚氯丙烯树脂、甲基丙烯酸乙酯、聚丙烯酸酯、呋喃树脂胶粘剂中的一种或者多种；
所述的防腐材料包括铌、贝壳粉、氧化钐、稀土氧化钕、氧化铋、钇铝石榴石、氮化硅中的一种或者多种；
所述的抗氧化剂包括双羟基甲基醚、硫代硫酸钠、3-甲氧基4-羟基苯乙二醇、半胱氨酸、2,3-叔丁基羟基茴香醚中的一种或者多种。
2.权利要求1所述的医用钴铬合金的防腐蚀纳米涂层材料的离子喷涂方法，其特征在于包括如下步骤：
步骤(1)、基底表面净化：
以医用钴铬合金为基底，先用无水酒精清洗钴铬合金基底，再用氧化铝喷丸清理；同时将钴铬合金基底预热至150～225℃；
步骤(2)、防腐材料和抗氧化剂纳米细化：
首先将防腐材料和抗氧化剂混合，然后加入到行星式高能球磨机DECO-PBM-V-0.4L，在球磨过程中加入工艺控制剂，球磨转速为260～360r/min,球磨时间为6～20h；
步骤(3)、纳米粒径筛选，得到粒径为40～85nm的防腐纳米粉末：
步骤(4)、粘合剂粘度的增强：
将粘合剂置于AIR-1L系列真空反应器中，乳化均质机转速：10000～28000rpm，加热方式：水浴、油浴循环的1种或者2种搅拌机功率：120～180W，温度加热至65～80℃；保护气为氮气、氩气中的一种或者两种，搅拌3～8小时；
步骤(5)、在步骤(1)经预热的医用钴铬合金基体上，先采用等离子喷涂方法将步骤(4)处理后粘合剂喷涂在基体表面制备得到粘结层，然后继续采用等离子喷涂方法将步骤(3)处理后防腐纳米粉末喷涂在粘结层表面制备得到防腐涂层：粘结层厚度为0.01～0.09mm，防腐涂层厚度为0.08～0.22mm；
等离子喷涂方法参数如下：
采用美国进口AT-3000等离子喷涂设备；电流520～650A；电压45～60V；主气流量：30～60L·s-1；氩气、氮气、氢气中的一种或者多种作为等离子气；送粉压力0.3～0.8MPa；喷涂距离110～140mm；火炮移动速度120～140mm·s-1；移动步距2.2～4.2mm；喷枪与钴铬合金表面的喷涂夹角为50～85°；
步骤(6)、表面的光滑：
防腐涂层表面用金刚砂纸磨，用纯净水清洗后，再用丙酮冲洗，最后在80～150℃下加热20～70分钟以干燥表面，冷却至室温。
3.如权利要求2所述的离子喷涂方法其特征在于步骤(2)所述的工艺控制剂包括乙醇、棕榈酸；每克防腐材料和抗氧化剂总量加入5～15毫升乙醇；棕榈酸为防腐材料和抗氧化剂总量的1～3.5wt％。
4.如权利要求2或3所述的离子喷涂方法其特征在于步骤(3)具体是将步骤(2)纳米细化后的防腐材料和抗氧化剂混料采用YBS1000摇摆筛，筛选出粒径为40～85nm的防腐纳米粉末筛层选用1～5层，过滤附件选用1～2层，再配合1～2层的清网装置可获得更加理想的筛分效果当粒径大于85nm时，重复步骤(2)。
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