CN110092653A - 一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及其制备方法和用途 - Google Patents

一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及其制备方法和用途 Download PDF

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CN110092653A
CN110092653A CN201910381175.4A CN201910381175A CN110092653A CN 110092653 A CN110092653 A CN 110092653A CN 201910381175 A CN201910381175 A CN 201910381175A CN 110092653 A CN110092653 A CN 110092653A
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tricalcium phosphate
printing
bata
powder
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戴红莲
马遇乐
黄孝龙
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Wuhan University of Technology WUT
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Abstract

本发明涉及一种3D打印可降解β‑磷酸三钙多孔生物陶瓷支架及制备方法和用途，包括以下步骤：(1)将c粉末、生物玻璃超微粉末、纳米二氧化硅粉末和打印助剂混合均匀制备3D打印墨水；(2)将3D打印墨水放入打印设备，设计三维支架模型和打印参数，通过三维打印技术打印出多孔陶瓷支架；(3)将打印出的多孔陶瓷支架经常温干燥后，设置烧结制度烧结，即得。与现有技术相比，本发明具有以下有益效果：有效降低了β‑磷酸三钙多孔陶瓷支架的烧结温度，显著提高了β‑磷酸三钙多孔陶瓷支架的降解速率和生物活性；材料利用率大大优于传统减材制造工艺，具有较好经济效益；可根据患者骨缺损需求进行个性化定制，满足个性化医疗需求。

Description

一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及其制备方 法和用途
技术领域
本发明涉及一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及制备方法和用途，属于生物材料领域。
背景技术
长期以来，由于交通事故、骨肿瘤和创伤等原因造成的骨缺损病例逐年增加，成为了一个世界性的健康医疗问题。其中金标准自体骨移植来源有限以及可能引起供体炎症反应，异体骨移植存在着伦理问题和免疫排斥缺点，因此，组织工程被视为解决这一问题的较佳方式。β-磷酸三钙[β-Ca3(PO4)2]为磷酸三钙的低温稳定相，组成成分与人体骨组织无机成分类似，具有可降解、生物相容性良好、骨传导、骨诱导等优点。然而传统方法制备β-磷酸三钙多孔生物陶瓷存在孔隙贯通性差，难以控制孔的形状和尺寸以及β-磷酸三钙降解速率慢与新生骨组织长入速率不匹配的问题。3D(三维)打印技术可以自由设计和制造多孔支架的形状以及孔结构等诸多优势，成为近年来生物材料研究的热点。
中国专利CN107802884A提供了一种作为骨修复生物材料3D打印支架及其制备方法，以β-磷酸三钙、煅自然铜、聚丙烯酸钠、羟丙基甲基纤维素为原料，搅拌均匀制备打印浆料并经3D打印成型。其在3D打印β磷酸三钙的原料中，添加煅自然铜，来提高β-磷酸三钙支架的成骨活性。
中国专利CN107721408A提供了一种3D打印制备β-磷酸三钙多孔生物陶瓷的方法，将β-磷酸三钙粉体、光敏树脂、分散剂通过球磨混合均匀制得陶瓷浆料，再经3D打印光固化成型，烧结后得到致密的β-磷酸三钙多孔陶瓷。
中国专利CN105311673B提供了一种3D打印介孔生物活性玻璃改性的生物陶瓷支架及制备方法，其将β-磷酸三钙粉末与粘接剂进行充分混合，利用三维打印技术制备β-磷酸三钙支架，烧结后在支架表面旋涂介孔生物活性玻璃，通过介孔生物玻璃来增强β-磷酸三钙生物活性支架的力学性能、生物活性。
发明内容
本发明的目的在于提供一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及其制备方法，其在骨修复材料中的应用，以解决现有技术中骨修复材料降解速率慢、生物活性低的问题。
本发明采用的技术方案如下：一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，包括以下步骤：
(1)将c粉末、生物玻璃超微粉末、纳米二氧化硅粉末和打印助剂混合均匀制备3D打印墨水；
(2)将3D打印墨水放入打印设备，设计三维支架模型和打印参数，通过三维打印技术打印出多孔陶瓷支架；
(3)将打印出的多孔陶瓷支架经常温干燥后，设置烧结制度烧结，即得。
按上述方案，β-磷酸三钙粉末为形貌规则接近球形的颗粒，粒径分布范围为0.2μm～2μm，生物玻璃超微粉末粒径分布范围为0.9μm～3μm，纳米二氧化硅粉末粒径分布范围为10nm～50nm。
按上述方案，所述的生物玻璃超微粉末通过以下方法制备：按照质量份Na2O:CaO:MgO:P2O5＝18份:10份:7份:65份的比例，以碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵为原料，通过熔融法制备，并进行球磨得到。
按上述方案，步骤(1)中的打印助剂为质量浓度为5％～20％的海藻酸钠溶液、质量浓度为10％～30wt％的普朗尼克F-127溶液和超纯水的混合。
按上述方案，步骤(1)中的打印助剂还包括有起泡剂。
按上述方案，所述的起泡剂为十二烷基硫酸钠、碳酸铵、碳酸氢铵其中的一种或组合。
按上述方案，其中生物玻璃超微粉末的添加量为β-磷酸三钙粉末/生物玻璃超微粉/纳米二氧化硅总质量的1％～50％，纳米二氧化硅的添加量为β-磷酸三钙粉末、生物玻璃超微粉末和纳米二氧化硅粉末总质量的0.1％～5％，步骤(1)中的β-磷酸三钙粉末+生物玻璃超微粉末+纳米二氧化硅粉末、海藻酸钠、普朗尼克F-127、超纯水的质量比例为30～44：18～25：3～9：0～7。
按上述方案，步骤(3)中多孔陶瓷支架的烧结制度为：5℃/min从室温升至500℃～550℃，保温1～4小时，然后10～20℃/min升至700～900℃，保温0.5～2小时，随炉冷却。
上述任意制备方法所得的3D打印可降解β-磷酸三钙多孔生物陶瓷支架，所述的多孔生物陶瓷支架宏观上有100μm～800μm相互连通的大孔，其内部存在1μm～5μm的相互连通的微孔。
所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架在骨修复材料中的应用。
本发明在3D打印β-磷酸三钙多孔生物陶瓷支架的打印墨水当中添加具有较低熔点的生物玻璃组分，高能球磨后的生物玻璃超微粉具有较高的比表面积和反应活性，能与β-磷酸三钙粉末充分接触并反应，有效降低了β-磷酸三钙多孔生物陶瓷支架的烧结温度；同时，纳米二氧化硅的加入，提升了3D陶瓷墨水的流动性，使得可以制备更高固含量的β-磷酸三钙陶瓷墨水；并提高了β-磷酸三钙多孔生物陶瓷支架的降解活性和生物活性。
与现有技术相比，本发明具有以下有益效果：
本发明通过三维打印技术制备宏观多孔支架，添加低熔点的生物玻璃超微粉以及纳米二氧化硅，有效降低了β-磷酸三钙多孔陶瓷支架的烧结温度，显著提高了β-磷酸三钙多孔陶瓷支架的降解速率和生物活性；
本发明使用三维打印快速成型技术，无多余切削废料产生，材料利用率大大优于传统减材制造工艺，具有较好经济效益；
本发明的多级孔隙生物陶瓷支架可根据患者骨缺损需求进行个性化定制，满足个性化医疗需求。
附图说明
图1为实施例1制备的β-磷酸三钙粉末、生物玻璃超微粉末的粒径分布图；
图2为实施例1制备的β-磷酸三钙多孔陶瓷支架图片；
图3为实施例1制备的β-磷酸三钙多孔陶瓷支架陶瓷扫描电镜微观图；
图4为实施例1～3制备的多孔陶瓷支架和对照组纯β-磷酸三钙陶瓷支架的体外降解速率曲线；
图5为将实施例3制备的β-磷酸三钙多孔陶瓷支架和纯β-磷酸三钙多孔陶瓷支架植入大鼠股骨髁缺损处，4周和8周后经MicroCT测试后得到的新骨生成量BV/TV统计值。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合实施例，对本发明进行进一步说明。应当理解，此处的具体实施例仅用于解释本发明，并不用于限定本发明。本发明多级孔隙生物陶瓷支架用于修复人体硬骨组织的缺损，本发明所采用的孔结构设计及材料组份配比不限于本发明所述方案。
本发明β-磷酸三钙粉末为形貌规则接近球形的颗粒，粒径分布范围为0.2μm～2μm，生物玻璃超微粉末粒径分布范围为0.9μm～3μm，纳米二氧化硅粉末粒径分布范围为10nm～50nm。
实施例1：
(1)将354.23g四水硝酸钙溶解于1.5L超纯水中；将132.06g磷酸氢二铵溶解于1L超纯水中；在40℃下将溶解的硝酸钙溶液逐滴加入磷酸氢二铵溶液中，利用氨水调节溶液pH值并稳定在pH＝7.0；静置陈化1天后，过滤并用超纯水清洗前驱体沉淀；干燥去除水分后，将前驱体放入坩埚，在马弗炉中煅烧，10℃/min快速升温至800℃并保温2h，随炉冷却，即得到β-磷酸三钙粉末；
(2)按照Na2O:CaO:MgO:P2O5＝18wt％:10wt％:7wt％:65wt％的比例称取碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵，通过熔融法制备生物玻璃；将生物玻璃投入球磨罐中并加入无水乙醇和氧化锆球磨子，高速球磨6h，随后放入干燥箱干燥，即得到生物玻璃超微粉末；
(3)将β-磷酸三钙粉末、生物玻璃超微粉末、平均粒径D50为15nm的纳米二氧化硅按照质量比β-磷酸三钙粉末：生物玻璃超微粉末：纳米二氧化硅粉末＝98.9：1：0.1的比例，加入无水乙醇通过球磨混合均匀；随后放入干燥箱干燥，即得到β-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末；
(4)将5g海藻酸钠与95g超纯水混合，溶解搅拌2h使之充分溶解，得到海藻酸钠溶液；将10g普朗尼克F-127与90g超纯水混合，溶解搅拌10h使之充分溶解，得到普朗尼克F-127溶液；将44gβ-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末、18g海藻酸钠溶液、9g普朗尼克F-127溶液、7g超纯水投入球磨罐，加入适量球磨子，在250rpm转速下高能球磨4h，得到3D打印陶瓷墨水；
(5)将3D打印墨水置入三维打印设备，采用软件设计直径为6mm，高度为10mm的圆柱形模型STL文件，采用喷头直径0.26mm，气压0.5MPa，打印速度3mm/s，层厚0.28mm，相邻间距800μm的打印参数，3D打印多孔陶瓷支架材料，室温下干燥24小时；
(6)将打印好的支架放入马弗炉中，烧结制度为：5℃/min从室温升至500℃，在500℃保温1h，然后10℃/min从500℃升至700℃，在700℃保温4h，随炉冷却，得到多孔生物陶瓷支架。
如图1所示，从中可以看出，制备的β-磷酸三钙粉末、生物玻璃超微粉末粒径分布分别为0.2μm～2μm、0.9μm～3μm。
如图2所示，从中可以看出，3D打印技术可以自由制造不同形状、不同尺寸和不同孔隙率的陶瓷支架，在材料的可定制化制备上具有较大的优势。
如图3所示，从图中可以看出，陶瓷支架为宏观多孔结构，Z轴方向垂直孔隙孔径为～400μm，横截面孔隙孔径为～100μm在陶瓷支架内部，β-磷酸三钙颗粒通过生物玻璃粘接作用，存在1μm～5μm相互连通的微小孔隙。
如图4所示，从图中可以看出，添加1wt％生物玻璃和0.1wt％纳米二氧化硅的β-磷酸三钙多孔陶瓷支架的降解速率较纯β-磷酸三钙多孔陶瓷支架要快。
实施例2：
(1)将354.23g四水硝酸钙溶解于1.5L超纯水中；将132.06g磷酸氢二铵溶解于1L超纯水中；在40℃下将溶解的硝酸钙溶液逐滴加入磷酸氢二铵溶液中，利用氨水调节溶液pH值并稳定在pH＝7.0；静置陈化1天后，过滤并用超纯水清洗前驱体沉淀；干燥去除水分后，将前驱体放入坩埚，在马弗炉中煅烧，10℃/min快速升温至800℃并保温2h，随炉冷却，即得到β-磷酸三钙粉末；
(2)按照Na2O:CaO:MgO:P2O5＝18wt％:10wt％:7wt％:65wt％的比例称取碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵，通过熔融法制备生物玻璃；将生物玻璃投入球磨罐中并加入无水乙醇和氧化锆球磨子，高速球磨6h，随后放入干燥箱干燥，即得到生物玻璃超微粉末；
(3)将β-磷酸三钙粉末、生物玻璃超微粉末、粒径D50为30nm的纳米二氧化硅按照质量比β-磷酸三钙：生物玻璃超微粉末：纳米二氧化硅＝89：10：1的比例，加入无水乙醇通过球磨混合均匀；随后放入干燥箱干燥，即得到β-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末；
(4)将10g海藻酸钠与90g超纯水混合，溶解搅拌2h使之充分溶解，得到海藻酸钠溶液；将20g普朗尼克F-127与80g超纯水混合，溶解搅拌10h使之充分溶解，并消除气泡，得到普朗尼克F-127溶液；将30gβ-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末、20g海藻酸钠溶液、5g普朗尼克F-127溶液、6g超纯水和和5g十二烷基硫酸钠投入球磨罐，加入适量球磨子，在250rpm转速下高能球磨4h，得到3D打印陶瓷墨水；
(5)将3D打印墨水置入三维打印设备，采用软件设计10mm×10mm×10mm，的立方体模型STL文件，采用喷头直径0.26mm，气压0.5MPa，打印速度3mm/s，层厚0.28mm，孔径100μm的打印参数，3D打印多孔陶瓷支架材料，室温下干燥24小时；
(6)将打印好的支架放入马弗炉中，烧结制度为：5℃/min从室温升至500℃，在550℃保温1h，然后20℃/min从550℃升至800℃，在800℃保温1h，随炉冷却，得到多孔生物陶瓷支架。
如图4所示，从图中可以看出，添加10wt％生物玻璃和1wt％纳米二氧化硅的β-磷酸三钙多孔陶瓷支架的降解速率较纯β-磷酸三钙多孔陶瓷支架、实施例1制备的陶瓷支架要快。
实施例3：
(1)将354.23g四水硝酸钙溶解于1.5L超纯水中；将132.06g磷酸氢二铵溶解于1L超纯水中；在40℃下将溶解的硝酸钙溶液逐滴加入磷酸氢二铵溶液中，利用氨水调节溶液pH值并稳定在pH＝7.0；静置陈化1天后，过滤并用超纯水清洗前驱体沉淀；干燥去除水分后，将前驱体放入坩埚，在马弗炉中煅烧，10℃/min快速升温至800℃并保温2h，随炉冷却，即得到β-磷酸三钙粉末。
(2)按照Na2O:CaO:MgO:P2O5＝18wt％:10wt％:7wt％:65wt％的比例称取碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵，通过熔融法制备生物玻璃；将生物玻璃投入球磨罐中并加入无水乙醇和氧化锆球磨子，高速球磨6h，随后放入干燥箱干燥，即得到生物玻璃超微粉末。
(3)将β-磷酸三钙粉末、生物玻璃超微粉末和平均粒径D50为50nm的纳米纳米二氧化硅按照质量比β-磷酸三钙粉末：生物玻璃超微粉末：纳米二氧化硅粉末＝78：20：2的比例，加入无水乙醇通过球磨混合均匀；随后放入干燥箱干燥，即得到β-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末。
(4)将20g海藻酸钠与80g超纯水混合，溶解搅拌2h使之充分溶解，得到海藻酸钠溶液；将30g普朗尼克F-127与70g超纯水混合，溶解搅拌10h使之充分溶解，并消除气泡，得到普朗尼克F-127溶液；将30gβ-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末、25g海藻酸钠溶液、3g普朗尼克F-127溶液、7g超纯水和5g碳酸铵投入球磨罐，加入适量球磨子，在250rpm转速下高能球磨4h，得到3D打印陶瓷墨水。
(5)将3D打印墨水置入三维打印设备，采用软件设计直径为6mm，高度为8mm的圆柱形模型STL文件，采用喷头直径0.26mm，气压0.5MPa，打印速度3mm/s，层厚0.28mm，相邻间距700μm的打印参数，3D打印多孔陶瓷支架材料，室温下干燥24小时
(6)将打印好的支架放入马弗炉中，烧结制度为：5℃/min从室温升至500℃，在500℃保温4h，然后20℃/min从500℃升至900℃，在900℃保温0.5h，随炉冷却，得到多孔生物陶瓷支架。
(7)将烧结后的支架经灭菌后，植入大鼠股骨髁缺损模型中，观察4周以及8周后观察骨缺损修复结果。
如图4所示，从图中可以看出，添加20wt％生物玻璃和2wt％纳米二氧化硅的β-磷酸三钙多孔陶瓷支架的降解速率较纯β-磷酸三钙多孔陶瓷支架、实施例1和实施例2制备的陶瓷支架要快。
如图5所示，从图中可以看出，实施例3制备的β-磷酸三钙多孔陶瓷支架在第4周、第8周的新骨生成量均要高于纯β-磷酸三钙多孔陶瓷支架。
实施例4：
(1)将354.23g四水硝酸钙溶解于1.5L超纯水中；将132.06g磷酸氢二铵溶解于1L超纯水中；在40℃下将溶解的硝酸钙溶液逐滴加入磷酸氢二铵溶液中，利用氨水调节溶液pH值并稳定在pH＝7.0；静置陈化1天后，过滤并用超纯水清洗前驱体沉淀；干燥去除水分后，将前驱体放入坩埚，在马弗炉中煅烧，10℃/min快速升温至800℃并保温2h，随炉冷却，即得到β-磷酸三钙粉末。
(2)按照Na2O:CaO:MgO:P2O5＝18wt％:10wt％:7wt％:65wt％的比例称取碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵，通过熔融法制备生物玻璃；将生物玻璃投入球磨罐中并加入无水乙醇和氧化锆球磨子，高速球磨6h，随后放入干燥箱干燥，即得到生物玻璃超微粉末。
(3)将β-磷酸三钙粉末、生物玻璃超微粉末和平均粒径D50为15nm的纳米二氧化硅按照β-磷酸三钙粉末：生物玻璃超微粉末：纳米二氧化硅粉末＝45：50：5的比例，加入无水乙醇通过球磨混合均匀；随后放入干燥箱干燥，即得到β-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末。
(4)将10g海藻酸钠与90g超纯水混合，溶解搅拌2h使之充分溶解，得到海藻酸钠溶液；将20g普朗尼克F-127与80g超纯水混合，溶解搅拌10h使之充分溶解，并消除气泡，得到普朗尼克F-127溶液；将30gβ-磷酸三钙粉末/生物玻璃超微粉末/纳米二氧化硅混合粉末、20g海藻酸钠溶液、5g普朗尼克F-127溶液和5g碳酸氢铵投入球磨罐，加入适量球磨子，在250rpm转速下高能球磨4h，得到3D打印陶瓷墨水。
(5)将3D打印墨水置入三维打印设备，采用软件设计直径为6mm，高度为10mm的圆柱形模型STL文件，采用喷头直径0.26mm，气压0.5MPa，打印速度3mm/s，层厚0.28mm，相邻间距1000μm的打印参数，3D打印多孔陶瓷支架材料，室温下干燥24小时(6)将打印好的支架放入马弗炉中，烧结制度为：5℃/min从室温升至500℃，在500℃保温2h，然后10℃/min从500℃升至710℃，在710℃保温2h，随炉冷却，得到多孔生物陶瓷支架。
3D打印参数的设计，与3D打印设备的精度与密切的关系，因此，3D打印过程中，3D打印模型的改变，孔径大小的改变，打印速度的改变，打印喷头的改变，其所解决的技术问题仍然与本发明一致的，均应当包含在本发明的保护范围之内。
上述实施例仅为本发明的优选实施方式之一，不应当用于限制本发明的保护范围，但凡在本发明的主体设计思想和精神上做出的毫无实质意义上的改动和润色，其所解决的技术问题仍然与本发明一致的，均应当包含在本发明的保护范围之内。

Claims (10)

1.一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，包括以下步骤：
(1)将c粉末、生物玻璃超微粉末、纳米二氧化硅粉末和打印助剂混合均匀制备3D打印墨水；
(2)将3D打印墨水放入打印设备，设计三维支架模型和打印参数，通过三维打印技术打印出多孔陶瓷支架；
(3)将打印出的多孔陶瓷支架经常温干燥后，设置烧结制度烧结，即得。
2.根据权利要求1所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，β-磷酸三钙粉末为形貌规则接近球形的颗粒，粒径分布范围为0.2μm～2μm，生物玻璃超微粉末粒径分布范围为0.9μm～3μm，纳米二氧化硅粉末粒径分布范围为10nm～50nm。
3.根据权利要求1所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，所述的生物玻璃超微粉末通过以下方法制备：按照质量份Na2O:CaO:MgO:P2O5＝18份:10份:7份:65份的比例，以碳酸钠、碳酸钙、碱式碳酸镁、磷酸二氢铵为原料，通过熔融法制备，并进行球磨得到。
4.根据权利要求1所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，步骤(1)中的打印助剂为质量浓度为5％～20％的海藻酸钠溶液、质量浓度为10％～30wt％的普朗尼克F-127溶液和超纯水的混合。
5.根据权利要求4所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，步骤(1)中的打印助剂还包括有起泡剂。
6.根据权利要求5所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，所述的起泡剂为十二烷基硫酸钠、碳酸铵、碳酸氢铵其中的一种或组合。
7.根据权利要求4所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，其中生物玻璃超微粉末的添加量为β-磷酸三钙粉末/生物玻璃超微粉/纳米二氧化硅总质量的1％～50％，纳米二氧化硅的添加量为β-磷酸三钙粉末、生物玻璃超微粉末和纳米二氧化硅粉末总质量的0.1％～5％，步骤(1)中的β-磷酸三钙粉末+生物玻璃超微粉末+纳米二氧化硅粉末、海藻酸钠、普朗尼克F-127、超纯水的质量比例为30～44：18～25：3～9：0～7。
8.根据权利要求1所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架的制备方法，其特征在于，步骤(3)中多孔陶瓷支架的烧结制度为：5℃/min从室温升至500℃～550℃，保温1～4小时，然后10～20℃/min升至700～900℃，保温0.5～2小时，随炉冷却。
9.权利要求1-8任意制备方法所得的3D打印可降解β-磷酸三钙多孔生物陶瓷支架，所述的多孔生物陶瓷支架宏观上有100μm～800μm相互连通的大孔，其内部存在1μm～5μm的相互连通的微孔。
10.权利要求9所述的3D打印可降解β-磷酸三钙多孔生物陶瓷支架在骨修复材料中的应用。
CN201910381175.4A 2019-05-08 2019-05-08 一种3D打印可降解β-磷酸三钙多孔生物陶瓷支架及其制备方法和用途 Pending CN110092653A (zh)

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