CN113913805B - 一种冷喷涂改性层及其应用 - Google Patents
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Abstract
本发明涉及一种冷喷涂改性层及其应用,在制备羟基磷灰石纳米粉体的过程中,添加表面活性剂有利于降低纳米粉体的粒径,这一改变可以优化后续冷喷涂改性层的生物相容性、耐腐蚀性及眼刺激性能。但是,在对比了四种不同的表面活性剂(十二烷基苯磺酸钠、甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂)后发现,十二烷基苯磺酸钠不利于人工角膜钛支架改性层的细胞毒性和眼刺激性,其原因可能在于整个制备工艺难以实现表面活性剂的百分百去除,而相对于十二烷基苯磺酸钠,甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂等糖脂类生物表面活性剂会更有利于细胞的增殖生长。
Description
技术领域
本发明涉及冷喷涂领域,具体涉及一种冷喷涂改性层及其应用。
背景技术
冷喷涂又称冷空气动力学喷涂,它是基于空气动力学原理的一种喷涂技术。冷喷涂过程是利用高压气体通过拉瓦尔喷管产生超声速流动,将粉末粒子从轴向送入高速气流中,经加速后,在完全固态下撞击基体,通过较大的塑形变形而沉积于基体表面形成涂层。因具有温度低、对材料的组织影响小、沉积率高、涂层孔隙率低等优点,冷喷涂技术为制备高性能无氧化涂层及纳米结构涂层等提供了一种重要的工艺方法。
羟基磷灰石生物活性陶瓷是由羟基磷灰石构成的一种磷酸钙基生物陶瓷。羟基磷灰石是人体骨骼的基本成分,一直被公认为材料在与硬或软组织连接中起关键作用的物质,在肌肉、韧带或皮下种植时,能与组织密合、无炎症或刺激反应,是一种典型地生物活性陶瓷材料。
人工角膜一般由光学中心和周边支架两部分组成,其中,光学中心是光学部分,术后外界光线可以通过光学中心进入眼内,周边支架则是起到支撑整个人工角膜的作用。传统的研究通常采用高分子材料作为人工角膜的支架材料,而高分子属于生物惰性材料,不能与眼组织形成牢靠的结合,容易引起人工角膜的松动,进而产生一系列的并发症。因此,具有羟基磷灰石生物活性陶瓷在人工角膜领域存在巨大的应用潜力。
发明内容
针对现有技术存在的问题,本发明旨在提供一种冷喷涂改性层,并将其用于人工角膜支架的表面改性。
一种冷喷涂改性层,其特征在于,通过冷喷涂工艺将羟基磷灰石陶瓷纳米材料喷涂于人工角膜支架表面形成改性层;所述冷喷涂过程的工艺参数为衬底温度100-120℃,气体压力4-6MPa,煤油流量9-10kg/h,喷涂距离4-5cm,溶液压力5-6MPa;
所述羟基磷灰石陶瓷纳米材料的制备过程包括以下步骤:
A.称取 Ca(NO3)2·4H2O和表面活性剂溶于蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取(NH4)2HPO4溶于蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.0-11;
D.开启恒温水浴装置,在85-90℃下保温4-4.5h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100-120℃下烘干5-6h,而后在550-600℃下烧结1-2h,放入研钵中研磨即可得到羟基磷灰石粉体。
优选地,所述Ca(NO3)2·4H2O、表面活性剂和(NH4)2HPO4的质量比为23.62∶1.5∶7.92。
优选地,所述表面活性剂为糖脂类生物表面活性剂。
优选地,所述糖脂类生物表面活性剂为甘露糖赤藓糖醇脂、鼠李糖脂或槐糖脂。
优选地,所述改性层的厚度为1-2μm。
优选地,所述支架为钛支架。
另外,本发明还提供了一种冷喷涂改性层的应用,即,将上述冷喷涂改性层应用于人工角膜支架领域。
在制备羟基磷灰石纳米粉体的过程中,添加表面活性剂有利于降低纳米粉体的粒径,这一改变可以优化后续冷喷涂改性层的生物相容性、耐腐蚀性及眼刺激性能。但是,在对比了四种不同的表面活性剂(十二烷基苯磺酸钠、甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂)后发现,十二烷基苯磺酸钠不利于人工角膜钛支架改性层的细胞毒性和眼刺激性,其原因可能在于整个制备工艺难以实现表面活性剂的百分百去除,而相对于十二烷基苯磺酸钠,甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂等糖脂类生物表面活性剂会更有利于细胞的增殖生长。
具体实施方式
下面通过具体实施例来验证本发明的技术效果,但是本发明的实施方式不局限于此。
首先,我们描述羟基磷灰石纳米材料的制备过程,如实施例1-3、试验例及对比例所述。
试验例
A.称取23.62g Ca(NO3)2·4H2O和1.5g十二烷基苯磺酸钠溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取7.92g (NH4)2HPO4溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.6;
D.开启恒温水浴装置,在85℃下保温4h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100℃下烘干5h,而后在600℃下烧结2h,放入研钵中研磨即可得到羟基磷灰石粉体。
实施例1
A.称取23.62g Ca(NO3)2·4H2O和1.5g甘露糖赤藓糖醇脂溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取7.92g (NH4)2HPO4溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.6;
D.开启恒温水浴装置,在85℃下保温4h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100℃下烘干5h,而后在600℃下烧结2h,放入研钵中研磨即可得到羟基磷灰石粉体。
实施例2
A.称取23.62g Ca(NO3)2·4H2O和1.5g鼠李糖脂溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取7.92g (NH4)2HPO4溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.6;
D.开启恒温水浴装置,在85℃下保温4h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100℃下烘干5h,而后在600℃下烧结2h,放入研钵中研磨即可得到羟基磷灰石粉体。
实施例3
A.称取23.62g Ca(NO3)2·4H2O和1.5g槐糖脂溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取7.92g (NH4)2HPO4溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.6;
D.开启恒温水浴装置,在85℃下保温4h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100℃下烘干5h,而后在600℃下烧结2h,放入研钵中研磨即可得到羟基磷灰石粉体。
对比例1
A.称取23.62g Ca(NO3)2·4H2O溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
B.称取7.92g (NH4)2HPO4溶于500mL蒸馏水中,溶解过程中用玻璃棒进行搅拌;
C.先后将 Ca(NO3)2·4H2O溶液和氨水用玻璃棒引流到三口烧瓶中,然后将(NH4)2HPO4溶液用玻璃棒引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.6;
D.开启恒温水浴装置,在85℃下保温4h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100℃下烘干5h,而后在600℃下烧结2h,放入研钵中研磨即可得到羟基磷灰石粉体。
以下,我们对实施例1-4以及对比例1的羟基磷灰石粉体的粒径进行测量,用Scherrer公式计算各样品的平均粒径大小:D=Kλ/B1/2cosθ,其中K为常数0.9,λ为X射线波长,B1/2是单位为弧度的衍射峰半高宽数值,θ为X射线衍射峰的衍射角度,D为晶粒尺寸。实施例1-3、试验例以及对比例1中羟基磷灰石粉体的粒径如表1所述。
表1 各试样样品的粉末粒径
编号 | 粒径/nm |
试验例 | 62.7 |
实施例1 | 53.3 |
实施例2 | 71.8 |
实施例3 | 79.6 |
对比例1 | 110.4 |
进一步地,我们将上述5种羟基磷灰石粉体制备成分散溶液,并通过冷喷涂工艺将羟基磷灰石纳米粉体喷涂于人工角膜钛支架表面,冷喷涂过程的工艺参数如下:衬底温度120℃,气体压力4MPa,煤油流量10kg/h,喷涂距离5cm,溶液压力6MPa,通过调整喷涂时间,在人工角膜钛支架表面形成厚度为1μm的羟基磷灰石改性层。
接下来,对人工角膜钛支架的生物相容性、耐腐蚀性、细胞毒性以及眼刺激性能进行测试,具体方法如下:
生物相容性:通过溶血试验评价各样品的生物相容性,其原理在于:将样品与血液直接接触,测定红细胞膜破裂后释放的血红蛋白量,以检测各样品体外溶血程度。血红蛋白的吸收波长为545nm,可用分光光度计检测其浓度。具体操作步骤如下:
(1)从健康家兔心脏采血100mL,加入2%草酸钾5mL,制成新鲜抗凝血。取抗凝血40mL,加入0.9%氯化钠注射液50mL进行稀释。
(2)取3支硅化试管,一支试管装入试验样品和氯化钠注射液10mL,一支试管空白作为阴性对照组加入氯化钠生理盐水10mL,另外一支试管空白作为阳性对照组分别加入10mL蒸馏水。
(3)所有试管在37℃水浴中恒温30min,分别加入5mL抗凝兔血,并在37℃条件下保温60min。
(4)取试管上层清液,在545nm波长处测定吸光度。每一样品进行三次平行试验并取平均值。
溶血率的计算公式如下:
溶血率(%)=(试样平均吸光度-阴性组吸光度)/(阳性组吸光度-阴性组吸光度)×100
耐腐蚀性能:在模拟体液(SBF)中,37℃下对人工角膜钛支架长期保护能力的测试,即将裸露的人工角膜钛支架进行封装,防止边缘效应,而后将其各自置于盛有模拟液的烧杯中,用保鲜膜封住烧杯口,放入37℃的恒温水浴锅中,每两天更新一次模拟体液,并记录样品开始发生腐蚀的情况。
细胞毒性:将人工角膜钛支架置于浸提液中培养5天,测试细胞的相对生长速率RGR。
眼刺激性能:将人工角膜支架植入兔角膜中,7天后观察其是否存在畏光、流泪、红肿等不良反应。
各样品实验结果如表2所示,其中,溶血率低于5%表示生物相容性合格(√),开始腐蚀的时间超过500h表示耐腐蚀性合格(√),5天后RGR大于90%表示细胞毒性合格(√),7天后不存在畏光、流泪、红肿等不良反应表示眼刺激性能合格(√)。
表2 各样品实验结果
编号 | 生物相容性 | 耐腐蚀性 | 细胞毒性 | 眼刺激性 |
试验例 | √ | √ | × | × |
实施例1 | √ | √ | √ | √ |
实施例2 | √ | √ | √ | √ |
实施例3 | √ | √ | √ | √ |
对比例1 | × | × | √ | × |
在制备羟基磷灰石纳米粉体的过程中,添加表面活性剂有利于降低纳米粉体的粒径,这一改变可以优化后续冷喷涂改性层的生物相容性、耐腐蚀性及眼刺激性能。但是,在对比了四种不同的表面活性剂(十二烷基苯磺酸钠、甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂)后发现,十二烷基苯磺酸钠不利于人工角膜钛支架改性层的细胞毒性和眼刺激性,其原因可能在于整个制备工艺难以实现表面活性剂的百分百去除,而相对于十二烷基苯磺酸钠,甘露糖赤藓糖醇脂、鼠李糖脂和槐糖脂等糖脂类生物表面活性剂会更有利于细胞的增殖生长。为了验证上述猜测,发明人选用了几种常见的表面活性剂(十二烷基硫酸钠、烷基酚聚氧乙烯醚和月桂酸)进行试验,都到了与十二烷基苯磺酸钠相似的结果。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (2)
1.一种冷喷涂改性层,其特征在于,通过冷喷涂工艺将羟基磷灰石陶瓷纳米材料喷涂于人工角膜支架表面形成改性层,所述改性层的厚度为1-2μm,所述冷喷涂过程的工艺参数为衬底温度100-120℃,气体压力4-6MPa,煤油流量9-10kg/h,喷涂距离4-5cm,溶液压力5-6MPa;
所述羟基磷灰石陶瓷纳米材料的制备过程包括以下步骤:
A.称取Ca(NO3)2·4H2O和糖脂类生物表面活性剂溶于蒸馏水中,溶解过程中进行搅拌,所述糖脂类生物表面活性剂为甘露糖赤藓糖醇脂、鼠李糖脂或槐糖脂;
B.称取(NH4)2HPO4溶于蒸馏水中,溶解过程中进行搅拌;
C.先后将Ca(NO3)2·4H2O溶液和氨水引流到三口烧瓶中,然后将(NH4)2HPO4溶液引流到分液漏斗中,并将漏斗颈插入三口烧瓶的一个侧口进行滴定,待(NH4)2HPO4溶液全部滴加到烧瓶后,用塞子堵住三口烧瓶的侧口,其中氨水的作用在于将溶液pH值调整到9.0-11,所述Ca(NO3)2·4H2O、表面活性剂和(NH4)2HPO4的质量比为23.62∶1.5∶7.92;
D.开启恒温水浴装置,在85-90℃下保温4-4.5h,然后自然降温至室温后,对反应产物进行过滤;
E.用蒸馏水洗涤固体过滤产物,并在100-120℃下烘干5-6h,而后在550-600℃下烧结1-2h,放入研钵中研磨即可得到羟基磷灰石粉体。
2.一种如权利要求1所述的冷喷涂改性层的应用,其特征在于:将所述冷喷涂改性层应用于人工角膜支架领域。
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