CN107235721B - 一种三维打印多孔白硅钙石生物陶瓷支架及其制备方法与应用 - Google Patents
一种三维打印多孔白硅钙石生物陶瓷支架及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种三维打印多孔白硅钙石生物陶瓷支架及其制备方法与应用。本发明首先通过将白硅钙石粉体、烧结助剂和一定比例的粘结剂水溶液进行调和后得到浆料,之后利用三维打印技术制备获得具有可控多孔结构的陶瓷支架坯体,再通过高温烧结得到具有多孔结构与良好力学性能的白硅钙石陶瓷支架材料。本发明所制备的三维打印白硅钙石生物陶瓷支架,其孔径和孔隙率可控,生物相容性好,力学性能显著优于同结构的磷酸钙陶瓷支架,同时具有优异的诱导成骨活性以及成血管活性,预期可用于促进各种类型缺损骨组织的再生修复。
Description
技术领域
本发明属于生物医用材料领域,具体涉及一种三维打印多孔白硅钙石生物陶瓷支架及其制备方法与应用。
背景技术
由创伤、肿瘤、先天性畸形、老龄化及事故等原因导致的骨缺损是威胁人体健康的主要原因。目前被视作临床金标准的自体骨移植经常受供体来源和二次创伤的限制,同种异体或异种骨修复材料存在病毒传播及免疫排斥等风险,因此具有良好的促进骨再生特性的人工合成骨修复材料有着迫切的临床需求和广阔的发展前景。
目前在临床中广泛使用的合成骨修复材料为磷酸盐类生物陶瓷,如羟基磷灰石和β-磷酸三钙陶瓷,其显著优点在于组成与天然骨组织的无机组分类似,因此具有良好的生物相容性和骨传导性,但存在不能主动诱导骨再生及降解过慢等不足。近年来,钙硅基生物活性材料由于在力学、降解性及生物学效应方面表现出了显著优于传统磷酸盐陶瓷的独特优点,因此获得了大量的关注和研究。白硅钙石(bredigite,Ca7MgSi4O16)作为一类具有代表性的硅酸盐生物活性陶瓷,表现出了优异的生物相容性、磷灰石矿化能力和生物活性。白硅钙石生物陶瓷在模拟体液中浸泡后能在其表面形成一层羟基磷灰石矿化层,成骨细胞可在其表面进行良好的贴附和铺展(Wu C,Chang J,Wang J,et al.Preparation andcharacteristics of a calcium magnesium silicate(bredigite)bioactive ceramic.[J].Biomaterials,2005,26(16):2925-2931.),同时在降解过程中白硅钙石陶瓷可释放Ca2+,Mg2+,Si4+等多种离子产物,Ca2+和Si4+能够促进骨髓间充质干细胞增殖和分化,Mg2+也被证实可通过免疫调控过程对血管化和骨再生有显著的促进作用,是制备具有骨诱导功能再生修复材料的理想组成(Wang M,Yu Y,Dai K,et al.Improved osteogenesis andangiogenesis of magnesium-doped calcium phosphate cement via macrophageimmunomodulation[J].Biomaterials Science,2016,4(11):1574-1583.)。
除在组成上含有可促进成骨及成血管的营养元素外,理想的骨修复材料还需要具有良好的多孔结构与优异的力学强度。传统采用造孔剂法、发泡法及冻干法等制备得到的多孔骨修复支架材料存在孔径连通性差、力学性能不足等问题,限制了其在骨缺损修复中的应用。
发明内容
本发明的目的在于提供一种三维打印白硅钙石生物陶瓷支架及其制备方法和用途。该生物陶瓷支架通过三维打印成型可以获得可控的多孔结构,通过高温烧结可以获得致密的微结构与良好的力学性能,并具有良好的生物相容性、成骨以及成血管活性。
本发明的第一方面是提供一种生物陶瓷支架。
本发明所提供的生物陶瓷支架,是利用三维打印技术制备的白硅钙石生物陶瓷支架,即三维打印白硅钙石生物陶瓷支架。
所述三维打印白硅钙石生物陶瓷支架,具有可控的孔结构,孔径为100~500μm,孔隙率为20%~80%。
所述三维打印白硅钙石生物陶瓷支架,由白硅钙石和烧结助剂组成,其中白硅钙石的质量分数为80~99%。
所述烧结助剂具体可为生物玻璃。
本发明的第二方面是提供上述三维打印白硅钙石生物陶瓷支架的制备方法,包括以下步骤:
(1)将白硅钙石粉末、烧结助剂与粘结剂水溶液混合,得到三维打印浆料;
(2)以所述三维打印浆料为原料利用三维打印技术制备白硅钙石生物陶瓷支架坯体;
(3)将所述白硅钙石生物陶瓷支架坯体进行烧结,得到所述生物陶瓷支架。
上述方法步骤(1)中,所述白硅钙石粉末由溶胶凝胶法或沉淀法合成。
上述方法步骤(1)中,所述烧结助剂具体可为生物玻璃。
上述方法步骤(1)中,烧结助剂与白硅钙石粉末的质量比为:0.01~0.2:1。
上述方法步骤(1)中,所述粘结剂可选自:F127、P123、聚乙烯醇、海藻酸钠、羧甲基纤维素钠、羧甲基淀粉、羧甲基壳聚糖、胶原蛋白、透明质酸钠、明胶以及它们的混合物。
上述方法步骤(1)中,所述三维打印浆料中粘结剂水溶液的质量分数为30~50%,所述粘结剂水溶液中粘结剂的质量分数为1~30%。
上述方法步骤(3)中,所述烧结的温度可为1150~1450℃,具体可为1300℃、1350℃,烧结的时间为2~15小时,具体可为3小时、4小时、5小时。
上述三维打印白硅钙石生物陶瓷支架在各种类型骨缺损再生修复材料中的应用也属于本发明的保护范围。
本发明的有益效果为:
(1)支架材料的孔径连通性好,孔隙率高,且可方便地通过三维打印设备的控制参数进行调节。
(2)支架材料经过高温烧结成型,微结构致密,无粘结剂残留。
(3)生物陶瓷支架的主相为白硅钙石,生物相容性好,生物活性高,具有诱导成骨活性以及成血管活性。
(4)力学性能显著优于同结构的磷酸盐陶瓷支架,同时降解性与骨再生同步。
本发明采用三维打印技术制备的生物陶瓷支架由于具有完全贯通的孔结构,同时力学强度也显著优于模板法制备的支架材料,在体内应用时能够促进骨组织长入以及营养物质的传输,有利于促进早期成骨,提升骨再生效果。
附图说明
图1为本发明实施例1制备的三维打印白硅钙石生物陶瓷支架的外观照片(a、b),实施例2制备的结构精细的三维打印白硅钙石生物陶瓷支架的外观照片(c、d)和实施例3制备得到的圆片形三维打印白硅钙石生物陶瓷支架的外观照片(e、f)。
图2为本发明实施例1制备的三维打印白硅钙石生物陶瓷支架的微观照片(a)和SEM照片(b)。
图3为本发明实施例1制备的三维打印白硅钙石生物陶瓷支架的XRD分析结果。
图4为本发明实施例3制备的三维打印白硅钙石生物陶瓷支架与三维打印β-TCP陶瓷支架的抗压强度测试结果。
图5为在兔子桡骨缺损处植入本发明实施例4制备的三维打印白硅钙石生物陶瓷支架与三维打印β-TCP陶瓷支架12周后的Micro-CT照片(a)和组织切片染照片(b)。
具体实施方式
下面通过具体实施例对本发明进行说明,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
实施例1、三维打印白硅钙石生物陶瓷支架的制备
1.原料准备:
(1)白硅钙石粉体合成
以四水硝酸钙、六水硝酸镁及正硅酸乙酯为原料,硝酸作为催化剂,采用溶胶-凝胶法制备白硅钙石(Ca7MgSi4O16)粉体。
取112mL正硅酸乙酯与72mL水及40mL的2mol·L-1硝酸(取69.4mL市售65~68%浓硝酸与适量水搅拌混合后定容至500mL,可得2mol·L-1硝酸)混合,搅拌水解0.5h。依次加入206.6g四水硝酸钙和64.1g硝酸镁,搅拌5h。密封在60℃陈化24h后在120℃干燥48h得到干凝胶。干凝胶球磨后在1150℃温度下煅烧3h,自然冷却后球磨并过200目筛,得到白硅钙石粉体。
(2)粘结剂水溶液的准备
粘结剂选择F127和海藻酸钠。称量20g购买的F127固体粉末和10g海藻酸钠放入玻璃瓶,加入100ml去离子水,盖封,放入-20℃环境30min,取出磁力搅拌30min,得到粘结剂水溶液。
(3)烧结助剂的准备
烧结助剂选择购买的45S5生物活性玻璃粉体。
(4)三维打印设备的准备
三维打印机使用德国GeSiM公司成产的Nano-Plotter TM 2.1,送料气压3.0~5.5个大气压,打印速度6mm/s,打印针头内径0.9mm。
2.三维打印制备白硅钙石生物陶瓷支架:
(1)称取4.5g白硅钙石粉末、0.5g生物玻璃粉体、2.5g粘结剂水溶液充分调和混匀,制备三维打印浆料;
(2)打印浆料放入料筒,安装好针头,装入三维打印机,按照预先设定的程序(层高0.8mm,股间距1.45mm)制备白硅钙石生物陶瓷支架坯体;
(3)将白硅钙石生物陶瓷支架坯体以2℃/min的升温速率升至1300℃,保温3h后自然冷却,即可得到三维打印白硅钙石生物陶瓷支架(图1a,b)。由图2可以看出支架具有大孔结构,孔径约0.4mm,阿基米德法测得孔隙率为44.6%。
实施例2、结构精细的三维打印白硅钙石生物陶瓷支架的制备
1.原料准备:
(1)白硅钙石粉体合成,原料和方法与实施例1相同。
(2)粘结剂水溶液的准备,原料和方法与实施例1相同。
(3)烧结助剂的准备
烧结助剂选择购买的45S5生物活性玻璃粉体。
(4)三维打印设备的准备
三维打印机使用德国GeSiM公司成产的Nano-Plotter TM 2.1,送料气压2.0~3.0个大气压,打印速度6.5mm/s,打印针头内径0.41mm。
2.三维打印制备白硅钙石生物陶瓷支架:
(1)称取4.3g白硅钙石粉末、0.7g生物玻璃粉体、2.8g粘结剂水溶液充分调和混匀,制备三维打印浆料;;
(2)打印浆料装入料筒,开启3D打印机,按照预先设定的程序(层高0.36mm,股间距1.2mm)制备白硅钙石生物陶瓷支架坯体;
(3)将白硅钙石生物陶瓷支架坯体以3℃/min的升温速率升至1350℃,保温5h后自然冷却,即可得到三维打印白硅钙石生物陶瓷支架。
图1(c)和(d)为制备得到结构精细的三维打印白硅钙石生物陶瓷支架的外观照片。
实施例3、圆片形三维打印白硅钙石生物陶瓷支架的制备
1.原料准备:
(1)白硅钙石粉体合成,原料和方法与实施例1相同。
(2)粘结剂水溶液的准备
粘结剂选择聚乙烯醇(聚合度:1750±50)。称量6g购买的聚乙烯醇加入100ml沸水中,搅拌至溶解,得到粘结剂水溶液。
(3)烧结助剂的准备
烧结助剂选择购买的45S5生物活性玻璃粉体。
(4)三维打印设备的准备
三维打印机使用德国GeSiM公司成产的Nano-Plotter TM 2.1,送料气压2.5~3.5个大气压,打印速度6.0mm/s,打印针头内径0.41mm。
2.三维打印制备白硅钙石生物陶瓷支架:
(1)称取6.2g白硅钙石粉末、0.3g生物玻璃粉体、3.5g粘结剂水溶液充分调和混匀,制备三维打印浆料;
(2)打印浆料装入料筒,开启3D打印机,按照预先设定的程序(层高0.36mm,股间距1.1mm)制备白硅钙石生物陶瓷支架坯体;
(3)将白硅钙石生物陶瓷支架坯体以2℃/min的升温速率升至1300℃,保温4h后自然冷却,即可得到三维打印白硅钙石生物陶瓷支架(图1e,f)。
实施例4、三维打印白硅钙石生物陶瓷支架的抗压强度
1.实验组准备:
以实施例1的方法制备出φ8mm×10mm的三维打印白硅钙石生物陶瓷支架,作为实验组。
2.对照组准备:
制备φ8mm×10mm的三维打印β-TCP陶瓷支架作为对照组,粘结剂和打印方法与实施例1相同。
(1)称取5gβ-磷酸三钙粉末、2.75g粘结剂水溶液充分调和混匀,制备浆料;
(2)打印浆料放入料筒,安装好针头,装入三维打印机,制备β-磷酸三钙陶瓷支架坯体;
(3)将β-磷酸三钙陶瓷支架坯体以2℃/min的升温速率升至1100℃,保温3h后自然冷却,即可得到三维打印β-磷酸三钙陶瓷支架。
3.力学强度测试:
将白硅钙石生物陶瓷支架,β-磷酸三钙陶瓷支架各取9个,通过力学测试机(AG-I,Shimadzu,Japan)进行测试,压头速度为0.5mm/min。
记录测试所得抗压强度并进行对比,实验结果见图4。
实施例5、三维打印白硅钙石生物陶瓷支架的体内成骨活性
为验证本发明在体内的成骨活性,对制备的三维打印白硅钙石生物陶瓷支架进行动物实验验证。
本实验选择的动物模型为健康的新西兰大白兔桡骨间断缺损模型。以实施例1的方法制备出的三维打印白硅钙石生物陶瓷支架,作为实验组植入体;以的三维打印β-磷酸三钙陶瓷支架,作为对照组植入体;植入前均进行高温蒸汽灭菌处理。
实验中,选用12只体重在2-2.5kg的雄性新西兰大白兔,随机分配成2组。在无菌状态下,肌肉注射5%的戊巴比妥使之麻醉;然后在左腿桡骨处划开2-2.5cm的矢状切口,在桡骨中间将1cm长的骨连同表面骨膜一起截取;植入三维打印陶瓷支架,经过0.9%无菌生理盐水冲洗后,将肌肉和皮肤分别复位、缝合。手术后正常饲养,注射抗生素3天。
术后12周处死动物取种植体,将标本在福尔马林磷酸盐缓冲液中固定24-48h。
样品通过Micro-CT(μCT-100,Scanco Medical AG,Switzerland)扫描后,采用GEHC MicroView软件(GE Healthcare BioSciences,Chalfont St.Giles,UK)进行三维成像处理并获得3维图像来显示整体形态学。
此外,样本经梯度乙醇(70%、80%、90%、100%)逐级脱水后放入聚甲基丙烯酸甲酯(PMMA)进行包埋,然后使用硬组织切片机(SP1600;Leica,Wetzlar,Germany)纵向切片,切片经打磨、抛光处理后进行Van Gieson(苦味酸品红)染色。切片在显微镜下进行观察和拍照,照片中,成熟骨组织呈鲜红色。
Micro-CT图片显示出两组支架种植在兔子桡骨缺损12周后周围新骨形成的形态,实验组比对照组有更好的骨再生效果:缺损处的重新连接程度更高、再生形态更规则。VanGieson染色结果显示两组支架材料周围都有新骨形成,且实验组比对照组有更多的新骨生成量(图5)。
结论:本发明的三维打印白硅钙石生物陶瓷支架具有良好的组织相容性和体内成骨能力和骨修复效果,可在骨组织工程用于硬骨组织缺损的修复和再生。
显然,上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限制。对于所属领域的技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或改进,凡是在本发明的精神和原则的前提下所作的任何变化和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (4)
1.一种生物陶瓷支架,是利用三维打印技术制备的白硅钙石生物陶瓷支架,即三维打印白硅钙石生物陶瓷支架;
该支架具有可控的孔结构,孔径为100~500 μm,孔隙率为20%~80%;
制备所述生物陶瓷支架的方法,包括以下步骤:
(1) 将白硅钙石粉末、烧结助剂与粘结剂水溶液混合,得到三维打印浆料;
(2) 以所述三维打印浆料为原料利用三维打印技术制备白硅钙石生物陶瓷支架坯体;
(3) 将所述白硅钙石生物陶瓷支架坯体进行烧结,得到所述生物陶瓷支架;
所述方法步骤(1)中,所述烧结助剂为生物玻璃;
烧结助剂与白硅钙石粉末的质量比为:0.01~0.2:1;
所述粘结剂选自:F127、P123、聚乙烯醇、海藻酸钠、羧甲基纤维素钠、羧甲基淀粉、羧甲基壳聚糖、胶原蛋白、透明质酸钠、明胶以及它们的混合物;
所述三维打印浆料中粘结剂水溶液的质量分数为30~50%,所述粘结剂水溶液中粘结剂的质量分数为1~30%;
三维打印机使用德国GeSiM公司成产的Nano-Plotter TM 2.1,送料气压3.0~5.5个大气压,打印速度6 mm/s,打印针头内径0.9 mm。
2.根据权利要求1所述的生物陶瓷支架,其特征在于:所述方法步骤(1)中,所述白硅钙石粉末由溶胶凝胶法或沉淀法合成。
3.根据权利要求1所述的生物陶瓷支架,其特征在于:所述方法步骤(3)中,所述烧结的温度为1150~1450℃,烧结的时间为2~15小时。
4.权利要求1-3中任一项所述的生物陶瓷支架在各种类型骨缺损再生修复材料中的应用。
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