CN112430086A - 一种生物陶瓷表面涂覆医学植入体的制备方法 - Google Patents
一种生物陶瓷表面涂覆医学植入体的制备方法 Download PDFInfo
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Abstract
本发明公开了一种生物陶瓷表面涂覆医学植入体的制备方法,属于医工结合领域,可以制备形状复杂、尺寸精准的植入体,采用所述方法制备的医学植入体对人体组织无损害,同时其强度等力学性能满足植入体的使用要求。本发明方法首先用陶瓷增材制造的方式,制备氧化锆胚体,通过脱脂烧结方法将氧化锆基体最终成形,再将基体放入配置的羟基磷灰石—聚乙烯醇浆料中,通过离心作用在基体表面覆盖一层浆料后风干固化;重复上述浸入—离心—风干步骤制备均匀的涂层,最后通过脱脂烧结得到致密的生物陶瓷涂层。制件保留了氧化锆多孔陶瓷的优良力学性能,并且通过羟基磷灰石涂层获得了出色的生物性能。
Description
技术领域
本发明属于医工结合领域,具体涉及一种生物陶瓷表面涂覆医学植入体的方法。
背景技术
近年来,增材制造技术发展势头迅猛,在各行各业都能看到它的身影。将增材制造技术应用于骨修复,可以规避传统骨移植存在的一些弊端,并带来一系列可以用作骨缺损修复的材料。例如金属材料、生物陶瓷材料、高分子材料、复合材料等等,这些材料利用增材制造技术能实现个性化定制,较高程度地还原患者骨骼原来的形貌。另外利用这项技术,还能够实现一些特定结构的打印,例如多孔结构,有利于养分的运输和细胞组织的生长,对骨修复具有重要意义。
虽然这些材料能够达到作为骨缺损修复某些方面的要求,在其他方面却存在缺陷。金属材料有着卓越的力学性能,能够承担较大的力,但作为植入物其生物相容性较差,长期处于人体体液环境会出现腐蚀,金属离子析出等问题,对人体造成损害。另外金属弹性模量无法与人骨相匹配,容易导致应力屏蔽,造成植入物松动。在高分子材料中应用较为广泛的PLA(聚乳酸),最终降解产物只有水和CO2,具有优秀的生物降解性能,但是过快的降解速率、较低的强度限制了其在骨骼修复领域的使用。
氧化锆陶瓷具有良好的耐磨性能和化学稳定性,在体内不会发生降解。目前氧化锆陶瓷主要应用的方面是作为牙科修复的材料。磷酸钙类陶瓷具有与人体骨骼相似的化学组分,并且具有良好的生物活性。从现有针对骨植入的研究表明,使用磷酸钙类陶瓷具有良好的骨传导性,有效促进成骨细胞附着在支架表面上。此外,磷酸钙类陶瓷在体内会发生降解,降解的产物可以作为形成新骨组织的原料,并且促进骨组织细胞生长和分化。尽管磷酸钙类陶瓷具有良好的生物活性,但是机械强度无法满足作为骨植入物的需求。
现有研究表明,作为骨植入物需要有多孔结构,多孔结构直接影响细胞的生长和细胞代谢,多孔结构在细胞生长的过程中起到营养供给,气体交换以及运输代谢产物。在实际应用中,现有的植入物支架可以满足多孔结构和孔隙率,但是无法保证支架具有优异的力学性能。基于以上考虑,多孔陶瓷支架具有良好的生物相容性并且具有较好的生物学力学性能更加符合作为植入体的需求。
传统方法生产多孔支架有很多方案,较为常见的方案有添加造孔剂法、有机泡沫浸渍法、溶液-凝胶法和冷冻干燥法,这些方法制造的多孔支架很难满足作为植入物需要的复杂结构。
发明内容
本发明提出了一种生物陶瓷表面涂覆医学植入体的制备方法,所述方法可以制备形状复杂、尺寸精准的植入体,采用所述方法制备的医学植入体对人体组织无损害,同时其强度等力学性能满足植入体的使用要求。
为实现以上目的,本发明采用以下技术方案:
一种生物陶瓷表面涂覆医学植入体的制备方法,包括以下步骤:
步骤1:将光敏树脂、分散剂以及氧化锆陶瓷粉末混合,所述光敏树脂的质量百分比为20%-50%,分散剂的质量百分比为1%-3%,其余组分为氧化锆陶瓷粉末;真空分散20min后,高速搅拌20min得到混合均匀的浆料;
步骤2:将上述得到的浆料采用DLP(数字光打印)的方式成型多孔氧化锆陶瓷胚体,清洗后对胚体进行脱脂和高温烧结处理;
步骤3:在上述处理后的胚体上涂覆磷酸钙类陶瓷—聚乙烯醇混合浆料涂层,将涂层经过风干后进行脱醇、高温烧结、除菌处理得到多孔生物陶瓷医学植入体。
以上所述步骤中,步骤1中所述氧化锆陶瓷粉末颗粒的中位粒径约为3μm,光敏树脂成分为丙烯酸酯,所述光敏树脂的反应波长为405nm,所述氧化锆陶瓷粉末与树脂质量配比为(4:1)-(1:1);
步骤2中成型厚度为20-50μm;所述脱脂的过程为:(1)25~120℃升温速度2℃/min,保温1h;(2)120~250℃升温速度1℃/min,保温2h;(3)250~370℃升温速度1℃/min,保温2h;(4)370~500℃升温速度1℃/min,保温2h;(5)炉冷至室温;
高温烧结处理的过程为:(1)25~1100℃,升温速度5℃/min,保温1h;(2)1100~1450℃,升温速度1.5℃/min,保温2h;(3)1450~900℃,降温速度3℃/min;(4)炉冷至室温;
步骤3中磷酸钙类陶瓷—聚乙烯醇混合浆料的制备过程为:将去离子水加热至90℃,加入聚乙烯醇粉末的质量百分比为10%-15%,完全溶解后超声振动去除气泡得到聚乙烯醇溶液;将质量比为1:1的聚乙烯醇溶液和羟基磷灰石陶瓷粉末混合,真空分散20min后加入浆料质量50%的氧化锆磨球,以80rpm的搅拌速度搅拌2h,得到羟基磷灰石—聚乙烯醇混合浆料;其中羟基磷灰石陶瓷颗粒的中位粒径为60nm;所述的磷酸钙类陶瓷包括羟基磷灰石、磷酸三钙、磷酸八钙、磷酸钙中的至少一种;
步骤3中采用浸渍与高速离心作用的方式分层控制基体表面所涂覆的浆料厚度,每层浆料厚度为20-50μm,涂覆每层后再经过风干固化,涂层总厚度约为100μm;
步骤3中所述脱醇处理的过程为:(1)25~120℃中升温速度2℃/min,保温1h;(2)120~250℃中升温速度1℃/min,保温2h;(3)250~370℃中升温速度1℃/min,保温2h;(4)370~550℃,升温速度1℃/min,保温2h;(5)炉冷至室温;
步骤3中所述烧结处理的过程为:(1)25~900℃中升温速度5℃/min,保温1h;(2)900~1100℃中升温速度1.5℃/min,保温2h;(3)1100~900℃中降温速度3℃/min;(4)炉冷至室温;
步骤3中所述除菌处理处理温度为120℃,压力为0.15Mpa,处理时间为20min,除菌后使用紫外线辐照30分钟。
有益效果:本发明提供了一种生物陶瓷表面涂覆医学植入体的制备方法,使用DLP光固化3D打印技术生产具有复杂形状的多孔支架,使用具有良好机械性能的材料作为基体材料,在支架表面进行涂覆磷酸钙类材料,从而改善支架的生物学性能;本发明使用的氧化锆、羟基磷灰石等材料与人体相容性较好,制备后的医学植入体对人体组织无损害,同时其强度等力学性能满足植入体的使用要求;本发明制备的涂层骨诱导性很好,可以促进骨缺损部位迅速长出新骨,与植入体能够很好的结合。本发明的制备方法使用的增材制造方式,可以制备形状复杂、尺寸精准的植入体,并且形状可控的多孔结构有利于人体骨组织的长入。本发明的方法可与3D扫描技术相结合,为不同患者定制与受损部位最匹配的医学植入体,缩短患者术后恢复周期。
附图说明
图1为本发明的制备方法的制备流程图;
图2为本发明实施例中体外细胞培养时光学显微镜下细胞的粘附图;
图3为本产品实施例中体外细胞培养7天后细胞在支架上的黏附图。
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的说明:
实施例1
如图1所示,一种生物陶瓷表面涂覆医学植入体的制备方法,包括以下步骤:
步骤1:氧化锆陶瓷浆料的制备步骤如下:
(1)在真空搅拌杯中加入100g光敏树脂材料,其主要成分为丙烯酸酯,密度约1.1g/cm3,反应波长为405nm(近紫外波段);
(2)在光敏树脂中添加350g的氧化锆粉末,其纯度为99%,中位粒径为3μm,随后添加2g分散剂,将手动预搅拌的浆料置于搅拌机内,在真空条件下进行分散搅拌并去除浆料中的空气;
(3)打开搅拌机开始搅拌,搅拌速度为1000rpm,搅拌时间为20min,让氧化锆颗粒在浆料中分散均匀,从而提高氧化锆陶瓷胚体的打印质量,脱脂烧结后的氧化锆陶瓷基体的力学性能也能够得到保证。
步骤2:氧化锆陶瓷胚体的制备步骤如下:
(1)将制备的浆料倒入DLP打印成型缸,设置每层成型厚度为20μm,成型时间设置为30s/层;
(2)打印完成后将打印产品置于酒精烧杯内,放入超声波清洗机进行清洗,将胚体内部多余的浆料溶去,最后用气枪吹去残余酒精;
步骤3:氧化铝陶瓷胚体的脱脂具体步骤如下:
(1)将氧化锆陶瓷胚体放置在匣钵内,并放入真空脱脂炉内,紧闭炉门后用真空泵将气压降低至0.01Mpa;
(2)在25~120℃阶段,升温速度2℃/min,保温1h;
(3)在120~250℃阶段,升温速度1℃/min,保温2h;
(4)在250~370℃阶段,升温速度1℃/min,保温2h;
(5)在370~500℃阶段,升温速度1℃/min,保温2h;
(6)炉冷至室温。
步骤4:氧化锆陶瓷胚体的具体烧结步骤如下:
(1)将脱脂后的植入体放入匣钵中,并置于箱式烧结炉内,用真空泵将气压降低至0.01Mpa;
(2)在25~1100℃阶段,升温速度5℃/min,保温1h;
(3)在1100~1450℃阶段,升温速度1.5℃/min,保温2h;
(4)在1450~900℃阶段,降温速度3℃/min;
(5)炉冷至室温。
步骤5:羟基磷灰石—聚乙烯醇陶瓷浆料的具体制备步骤如下:
(1)将去离子水倒入烧杯中,放入磁力搅拌机的转子,烧杯放入磁力搅拌机的水浴锅中,将水浴锅加热至90℃;
(2)往烧杯中加入10g聚乙烯醇粉末,缓缓搅拌直至溶解完成;
(3)重复步骤(2)十次,共加入100g聚乙烯醇;
(4)将完全溶解的聚乙烯醇溶液置于超声波清洗机中,超声波振动15min,去除溶液中残余气泡;
(5)在聚乙烯醇溶液中添加100g羟基磷灰石粉末,将浆料倒入不锈钢球磨罐中,并加入100g、5mm直径的氧化锆磨球,用真空泵抽去磨罐中的空气后,将其置于行星球磨机内进行球磨,转速为80rpm,球磨时间为6h,每球磨30min后,球磨机暂停5min,并改变旋转方向。
步骤6:羟基磷灰石涂层的制备步骤如下:
(1)将制备的浆料在水浴炉内加热至50℃,使其获得更好的流动性能,随后将氧化锆陶瓷基体浸入浆料中,同时使用超声振动进一步促进液体的流动,整个浸泡时间为15min;
(2)将氧化锆陶瓷基体固定在高速分散机上,转速为100rpm,温度保持在25℃,离心时间为2min,涂层厚度约为50μm;
(3)将覆盖浆料层的基体置于80℃热风循环炉内,风干20min;
(4)重复步骤(2)、(3),直至涂层厚度为100μm。
步骤7:涂层的脱醇具体步骤如下:
将具有涂层的基体放置在匣钵上,并放入热风循环炉内;
(1)在25~120℃阶段,升温速度2℃/min,保温1h;
(2)在120~250℃阶段,升温速度1℃/min,保温2h;
(3)在250~370℃阶段,升温速度1℃/min,保温2h;
(4)在370~550℃阶段,升温速度1℃/min,保温2h;
(5)炉冷至室温。
步骤8:涂层的具体烧结步骤如下:
(1)将脱脂后的植入体放入匣钵中,并置于箱式烧结炉内,用真空泵将气压降低至0.01Mpa。
(2)25~900℃,升温速度5℃/min,保温1h;
(3)900~1100℃,升温速度1.5℃/min,保温2h;
(4)1100~900℃,降温速度3℃/min;
(5)炉冷至室温。
对烧结后的植入体进行除菌处理,以120℃、1.5Mpa的温度和压力进行高温高压灭菌20min,此后在紫外环境下将植入体静置30min,完成生物陶瓷涂层复合医学植入体的制备。
植入体细胞生物相容性实验:
步骤1:将上述制备得到的植入体放入到高温高压灭菌锅内进行灭菌,灭菌的温度为124℃,保温时间为1小时,然后将支架放入到烘干箱内烘干,烘干温度为60℃,烘干时间为2小时,最后将植入体在紫外线灯下辐照30分钟,完后以备细胞相容性实验;
步骤2:将步骤1得到的植入体放入到24孔细胞培养板内,将MC3T3-E1细胞进行种植,然后在24孔板内部加入1ml培养基,最后将24孔板放入到培养箱进行培养,培养环境温度为37℃,CO2含量为5%,湿度为100%,培养时间为7天,隔天更换培养基,如图2所示,是在细胞培养7天时,在光学显微镜下,支架表现出很好的粘附效果;
步骤3:将步骤3中的植入体从培养板取出,使用PBS冲洗3次,然后将其放入到-20℃冰箱内保存3小时,完成后使用冷冻干燥机进行干燥,干燥时间为4小时;
步骤4:将步骤4得到的样品使用SEM观察表面形貌,效果图如图3所示,箭头指引的是支架上粘附的细胞,进一步验证了细胞可以很好的在支架上生长。
以上仅为本发明的优选实施例,但本发明的技术特征并不局限于此。应当指出,任何以本发明为基础,为实现基本相同的技术效果,所做出的简单变化、等同替换等,皆涵盖于本发明的保护范围之内。
Claims (10)
1.一种生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,包括以下步骤:
步骤1:将光敏树脂、分散剂以及氧化锆陶瓷粉末混合,所述光敏树脂的质量百分比为20%-50%,分散剂的质量百分比为1%-3%,其余组分为氧化锆陶瓷粉末,真空分散20min后,高速搅拌20min得到混合均匀的浆料;
步骤2:将上述得到的浆料采用DLP(数字光打印)的方式成型多孔氧化锆陶瓷胚体,清洗后对胚体进行脱脂和高温烧结处理;
步骤3:在上述处理后的胚体上涂覆磷酸钙类陶瓷—聚乙烯醇混合浆料涂层,将涂层经过风干后进行脱醇、高温烧结、除菌处理得到多孔生物陶瓷医学植入体。
2.根据权利要求1所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤1中所述氧化锆陶瓷粉末颗粒的中位粒径约为3μm,所述光敏树脂的反应波长为405nm。
3.根据权利要求1或2所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,所述氧化锆陶瓷粉末与光敏树脂质量配比为(4:1)-(1:1)。
4.根据权利要求1所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤2中成型厚度为20-50μm。
5.根据权利要求1或4所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤2中所述脱脂的过程为:(1)25~120℃升温速度2℃/min,保温1h;(2)120~250℃升温速度1℃/min,保温2h;(3)250~370℃升温速度1℃/min,保温2h;(4)370~500℃升温速度1℃/min,保温2h;(5)炉冷至室温;所述高温烧结处理的过程为:(1)25~1100℃,升温速度5℃/min,保温1h;(2)1100~1450℃,升温速度1.5℃/min,保温2h;(3)1450~900℃,降温速度3℃/min;(4)炉冷至室温。
6.根据权利要求1所述的生物陶瓷表面涂覆医学植入体制备放啊,其特征在于,步骤3中所述的磷酸钙类陶瓷包括羟基磷灰石、磷酸三钙、磷酸八钙、磷酸钙中的至少一种。
7.根据权利要求1所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤3中磷酸钙类陶瓷—聚乙烯醇混合浆料的制备过程为:将去离子水加热至90℃,加入聚乙烯醇粉末的质量百分比为10%-15%,完全溶解后超声振动去除气泡得到聚乙烯醇溶液;将质量比为1:1的聚乙烯醇溶液和羟基磷灰石陶瓷粉末混合,真空分散20min后加入浆料质量50%的氧化锆磨球,以80rpm的搅拌速度搅拌2h,得到羟基磷灰石—聚乙烯醇混合浆料。
8.根据权利要求6或7所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,所述磷酸钙类陶瓷粉末颗粒的中位粒径为60nm。
9.根据权利要求1所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤3中采用浸渍与高速离心作用的方式分层控制基体表面所涂覆的浆料厚度,每层浆料厚度为20-50μm,涂覆每层后经过风干固化,涂层总厚度约为100μm。
10.根据权利要求1所述的生物陶瓷表面涂覆医学植入体的制备方法,其特征在于,步骤3中所述脱醇处理的过程为:(1)25~120℃中升温速度2℃/min,保温1h;(2)120~250℃中升温速度1℃/min,保温2h;(3)250~370℃中升温速度1℃/min,保温2h;(4)370~550℃,升温速度1℃/min,保温2h;(5)炉冷至室温;所述烧结处理的过程为:(1)25~900℃中升温速度5℃/min,保温1h;(2)900~1100℃中升温速度1.5℃/min,保温2h;(3)1100~900℃中降温速度3℃/min;(4)炉冷至室温。
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