CN117602948A - 一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法 - Google Patents
一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，涉及人造骨技术领域。本发明的制备方法是以陶瓷二次颗粒为原料用粘结剂喷射设备获得打印体；再进行脱脂、烧结，得到多孔人造骨；其中，陶瓷二次颗粒的制备如下：S1、按质量份计，取陶瓷粉体50～99.9份、烧结助剂粉体0～20份、玻璃粉体0.1～50份、造孔剂0～40份，混合均匀，获得复合粉体；S2、对复合粉体造粒，得到造粒粉体；S3、对所述造粒粉体进行低温烧结，所述低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，烧结后制得陶瓷二次颗粒。本发明以陶瓷二次颗粒作为粘接剂喷射原料，引入造孔剂，通过控制造孔剂的含量、粒径制备出符合要求的多孔陶瓷人造骨。
Description
技术领域
本发明涉及大尺寸多孔人造骨技术领域，尤其涉及一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法。
背景技术
在现代社会中，养宠物的人群越来越庞大，随着人们对宠物的重视程度越来越高，愿意花钱为生病的宠物进行治疗的需求也随之提高。大型宠物由于意外而发生不可逆的骨损伤时，需要使用人造骨进行替换治疗。当大型野生动物、动物园的珍惜保护动物发生严重骨损伤时，同样也需要进行骨替换治疗。此外，人类身体结构中也有尺寸较大的骨头。因此，具有良好生物相容性的大型人造替代骨的需求不断上升。通常，天然骨的内部具有复杂孔隙结构，这要求人造替代品的内部结构应尽可能仿制天然骨，不仅要达到较高的力学性能，而且需要具有促进骨再生的功能。多孔陶瓷骨支架是骨替代的极佳候选物，但是复杂形状的陶瓷很难通过传统的成型工艺制造。
3D打印为复杂形状的陶瓷材料的制备提供了较好的技术手段。3D打印所需模型可以结合X光影像学技术来获取目标骨的形状尺寸而建立。这也就意味着在未来需要骨替代治疗时，可以使用该模型通过3D打印技术制备多孔陶瓷骨支架。
大尺寸骨支架的长度通常在300mm以上，例如500mm，粘接剂喷射3D打印技术是大尺寸多孔陶瓷骨支架的理想制备方法，其能够构建大而复杂的几何形状的陶瓷零件，并且具有较高精度和较高成型效率。尽管粘结剂喷射制备的陶瓷的孔隙率非常高，但是其密度和强度非常低，并且内部孔隙不可控，限制了其在制备大型多孔人造骨的发展。这主要是由于粘接剂喷射技术在铺粉时需要粉体具有较高流动性，通常选用大于20um的粗粉作为打印粉体，大大降低了陶瓷粉体烧结活性，无法烧结致密，大颗粒陶瓷粗粉之间只能形成部分烧结颈，导致强度低，孔隙缺少可控性。
发明内容
本发明所要解决的技术问题是现有的大尺寸多孔人造骨制备困难且其内部孔形貌难控制。
为了解决上述问题，本发明提出以下技术方案：
第一方面，本发明提供一种基于粘接剂喷射成型的大型多孔人造骨制备方法，包括：
根据目标骨的尺寸形状建模，以陶瓷二次颗粒为原料进行铺粉，使用粘结剂喷射设备制作该多孔人造骨，获得打印体；对所述打印体进行脱脂、烧结，得到多孔人造骨；其中，
所述陶瓷二次颗粒采用以下步骤制得：
S1、按质量份计，取陶瓷粉体50～99.9份、烧结助剂粉体0～20份、玻璃粉体0.1～50份、造孔剂0～40份，混合均匀，干燥过筛，获得复合粉体原料；
S2、将所述复合粉体进行造粒，得到粒径0.1um～150um的造粒粉体；
S3、对所述造粒粉体进行低温烧结，所述低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，烧结后制得陶瓷二次颗粒；
所述陶瓷粉体的粒径范围在10nm～10um，优选范围在50nm～1um；玻璃粉体的粒径范围在100nm～50um，优选范围在500nm～10um；烧结助剂粉体的粒径范围在10nm～10um，优选范围在50nm～1um；造孔剂的粒径范围在0.1～50um。
本发明为了保证粘接剂喷射使用的原料粉体具有高的烧结活性，采用熔融复烧法制备了具有多孔的陶瓷二次颗粒，使打印体可以通过烧结实现多孔、致密化。具体地，通过在陶瓷粉体中加入玻璃粉体及造孔剂，在经过重新造粒和低温烧结后获得高密度、高球形度、高流动性的陶瓷二次颗粒。低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，在低温熔融烧结时，由于毛细管力的作用，熔融玻璃会渗透扩散至陶瓷粉体间隙，使颗粒体积收缩，并粘接陶瓷粉体，从而提高陶瓷二次颗粒的密度。得到的陶瓷二次颗粒十分有利于粘接剂喷射设备的粉床铺粉工作，大大提高了粉床密度，并且保留了陶瓷粉体的高烧结活性。对脱脂完成的打印体进行烧结时，熔融玻璃再次发生渗透扩散，通过液相产生的毛细管力进一步提高了陶瓷烧结体的起始密度，当温度达到陶瓷的烧结温度后，陶瓷粉体开始烧结致密化，液相促进了陶瓷粉体的扩散传质，最终获得高密度的多孔的粘接剂喷射陶瓷。
需要说明的是，在进行打印时，通过控制打印参数(胶水饱和度、铺粉速度、辊子转速等)可以获得形状和精度良好的打印体。
可以理解地，所述步骤S1中，玻璃粉体在原料粉体中的占比不宜过高，以免影响最终陶瓷制品的性能，以玻璃粉体的质量分数＝玻璃粉体/(玻璃粉体+烧结助剂粉体+陶瓷粉体)为1％-35％为宜，以5％-25％为较佳。
其进一步地，所述陶瓷粉体选自氧化铝、氧化锆、氧化锆增韧氧化铝和氮化硅中的至少一种。
其进一步地，所述烧结助剂粉体选自MgO、ZrO2、CaO、SiO2、Cr2O3、Al2O3、SrO、TiO2、Sc2O3、Y2O3、Li2O、MgF2、YF3中的一种或多种。
其进一步地，所述玻璃粉体选自高硅氧玻璃、钠钙玻璃、铅硅酸盐玻璃、铝硅酸盐玻璃、硼硅酸盐玻璃、磷酸盐玻璃中的一种或多种。
一般而言，玻璃粉体的主要成份为SiO2，玻璃粉体中的其他成份可包括：MgO、Al2O3、CaO、Na2O、K2O、Li2O、B2O3、P2O5、PbO、CaF2、Y2O3以及其他的金属卤化物、金属氧化物、金属氮化物、稀土卤化物、稀土氧化物、稀土氮化物等中的一种或多种，但不局限于这几种。
其进一步地，所述造孔剂包括聚苯乙烯、淀粉、PMMA、核桃壳粉、植物纤维中的一种或几种。
其进一步地，所述造粒粉体中含有机物，在步骤S3对所述造粒粉体进行低温烧结之前，还包括，对造粒粉体进行脱脂。
需要说明的是，此步骤的脱脂用于去除有机物造孔剂和在造粒过程中使用的有机物粘结剂。
步骤S2中，造粒所用的方法包括干法成型破碎造粒、湿法成型破碎造粒、湿法造粒、流化床造粒、压力喷雾造粒、旋转喷雾造粒、水雾化喷雾造粒、气雾化喷雾造粒、滴淀成型造粒法中的一种，但局限于这几种。
其进一步地，所述脱脂的温度为300～600℃。
脱脂的方法包括真空热脱脂、空气热脱脂、保护气氛热脱脂中一种或多种，但不局限于这几种，脱脂温度根据所含有机物的受热分解情况，其脱脂温度在300-600℃。
其进一步地，所述步骤S3中低温烧结的温度为900℃～1600℃。
一般而言，受玻璃粉体成份的限制，玻璃粉体的软化点一般在500～1300℃，因此，所述步骤S3中，进行低温烧结的烧结温度为900℃～1600℃，烧结温度应高于玻璃软化点以使玻璃熔融，促进颗粒体积收缩，同时，该低温熔融烧结温度应低于陶瓷粉体的液相烧结温度。需要说明的是，软化点是利用宏观型差示热分析仪(DTA)测定的第四拐点的温度。
本发明对打印体进行烧结的工艺为陶瓷材料的常规制备工艺，根据具体陶瓷材料采用合适设备以及工艺，例如氧化铝、氧化锆采用马弗炉，氮化硅采用气氛炉、气压炉等，但不局限于这几种方式，其烧结温度应在1300-1900℃，由陶瓷的致密化过程决定。
需要说明的是，为了使多孔人造骨的性能接近已知天然骨的密度、强度、孔隙等，本发明在建立模型时，通过在模型内部设计宏观多孔结构，孔隙单元形状可包括：骨骼形、微小曲面形、圆柱形、立方形、六边形、八边形等，不限于以上几种。粘接剂喷射打印技术根据所用粉体，喷头打印分辨率，打印层厚等要求，设计宏观孔的大小控制在100-600um。进一步，通过控制造孔剂的种类、大小和含量来直接决定了陶瓷基体中亚微米级孔隙、微米级孔隙的占比。添加的造孔剂均匀分布在基体内，经过高温烧结后形成孔隙，孔隙的大小形状同造孔剂，通常造孔剂的大小在0.1-150um，造孔剂尺寸越大，含量越高，基体的孔隙率越高。
综上，本发明从材料组成设计到建模宏观孔设计两个方面对人造骨的孔隙结构进行共同调控，以获得理想的多孔人造骨。通过制备试样、性能表征和微观结构观察，以得到模型宏观孔及材料组成配比(造孔剂种类、大小、含量)与制得的人造骨性能以及孔隙结构的关系。
第二方面，本发明提供一种大型多孔人造骨，由所述的制备方法制得。
第三方面，本发明提供一种用于粘接剂喷射成型制备大型多孔人造骨的原料，所述原料为陶瓷二次颗粒，所述陶瓷二次颗粒采用以下步骤制得：
S1、按质量份计，取陶瓷粉体50～99.9份、烧结助剂粉体0～20份、玻璃粉体0.1～50份、造孔剂0～40份，混合均匀，干燥过筛，获得复合粉体原料；
S2、将所述复合粉体进行造粒，得到粒径0.1um～150um的造粒粉体；
S3、对所述造粒粉体进行低温烧结，所述低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，烧结后制得陶瓷二次颗粒；
所述陶瓷粉体的粒径范围在10nm～10um，玻璃粉体的粒径范围在100nm～50um，烧结助剂粉体的粒径范围在10nm～10um，造孔剂的粒径范围在0.1～50um。
需要说明的是，在步骤S1中，为了减少造孔剂被破碎，可以先将陶瓷粉体、添加剂粉体、玻璃粉体混合均匀后，再加入造孔剂混合。
步骤S2得到的造粒粉体应具有高球形度、高流动性。
低温烧结得到的陶瓷二次颗粒，相比于造粒粉体，其密度更高并获得了较高的强度，保持了高球形度和流动性，并且松装密度、振实密度和粉体床密度大大提高。
与现有技术相比，本发明所能达到的技术效果包括：
本发明使用粘接剂喷射成型技术可以制备大尺寸多孔陶瓷人造骨，并且无需支持，不损伤打印表面，成型效率高。通过选用具有生物相容性的陶瓷粉体、烧结助剂、以及玻璃粉体，造孔剂在制备过程中可以完全去除，保证了制得的人造骨对生物体无毒无害。可通过建模构建宏观孔隙结构和具有内部孔隙结构的原料粉体来综合调控大尺寸多孔陶瓷人造骨的孔隙形貌，实现具有亚微米级孔、微米级孔、宏观孔等多级孔的内部结构，为骨再生提供有利的附着再生区域。
本发明提供的基于粘接剂喷射成型的大型多孔人造骨制备方法，通过结构设计、材料组分设计和造孔剂改进，实现了基于粘接剂喷射技术快速成型制备大型多孔人造骨支架的效果，具有性能可控，孔隙结构可控的优点，能够更真实复刻天然骨的结构。
附图说明
图1为本发明基于粘接剂喷射成型的大型多孔人造骨制备方法的工艺流程图；
图2为本发明基于粘接剂喷射成型的大型多孔人造骨制备方法的原理图；
图3为本发明基于粘接剂喷射成型的大型多孔人造骨制备方法的模型设计宏观孔图；
图4为本发明实施例2制得的基于粘接剂喷射成型的大型多孔陶瓷微观高倍SEM图；
图5为本发明实施例2制得的基于粘接剂喷射成型的大型多孔陶瓷微观低倍SEM图。
具体实施方式
下面将结合本发明实施例中的附图，对实施例中的技术方案进行清楚、完整地描述。显然，以下将描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例提供了一种基于粘接剂喷射成型的大型人造骨及其制备方法，具体如下：
粉体原料为氮化硅，中粒径为1um。烧结助剂为氧化铝和氧化钇，中粒径分别为200nm和50nm。玻璃粉体为硼硅酸盐玻璃，其粒径为1um。
S1：按质量份计，取氮化硅85份，氧化铝5份，氧化钇5份，玻璃粉5份，以酒精为介质，加入氮化硅磨球，滚筒球磨混合12小时，使用旋转蒸发仪干燥后过100目筛网，获得均匀混合粉体。
S2：采用冷等-破碎造粒的方式，对S1中和混合粉体进行冷等静压处理，将成型块体破碎后过200目筛网，控制造粒粉体的粒径小于74um。
由于本实施例中的造粒粉体中不含有机物，因此不需要对造粒粉体进行脱脂处理。
S3：将松散的造粒粉体放入气氛烧结炉，在0.1MPa的氩气气氛中进行低温烧结，烧结温度为1300℃，时间为2小时，获得具有高密度高强度的陶瓷二次颗粒。
S4：使用商用粘结剂喷射打印机以及商用胶水打印零件，铺粉厚度设置在150um，并优化打印参数(铺粉速度、喷胶量等)，最后打印出形状和精度良好的陶瓷打印体，在模型设计时内部没有设计宏观孔隙。
S6：使用马弗炉对打印样件进行脱脂，脱脂工艺为真空脱脂和空气脱脂，脱脂温度均为550℃，保温2小时。使用气氛烧结炉对脱脂样件进行烧结，烧结工艺为1800℃烧结2小时，烧结后获得高致密、高性能的氮化硅陶瓷。
实施例2
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，具体如下：
粉体原料、烧结助剂、玻璃粉体的原料同实施例1。另外，本实施例使用造孔剂PMMA，粒径为10um。
S1：按质量份计，取氮化硅85份，氧化铝5份，氧化钇5份，玻璃粉5份，以酒精为介质，加入氮化硅磨球，滚筒球磨混合12小时，加入PMMA粉2份(陶瓷粉体总质量的2％)，用滚筒球磨混合3小时，使用旋转蒸发仪干燥后过100目筛网，获得均匀混合粉体。
S2：采用冷等-破碎造粒的方式，对S1中和混合粉体进行冷等静压处理，将成型块体破碎后过200目筛网，控制造粒粉体的粒径小于74um。
S3粉体脱脂：使用马弗炉对造粒粉体进行脱脂，脱脂工艺为空气脱脂，脱脂温度为550℃，保温2小时。
S4：将脱脂后松散的粉体放入气氛烧结炉，在0.1MPa的氩气气氛中进行低温烧结，烧结温度为1300℃，时间为2小时，获得具有高密度高强度的陶瓷二次颗粒。
S5：使用商用粘结剂喷射打印机以及商用胶水打印零件，铺粉厚度设置在150um，并优化打印参数(铺粉速度、喷胶量等)，最后打印出形状和精度良好的陶瓷打印体，在模型设计时内部没有设计宏观孔。
S6：使用马弗炉对打印样件进行脱脂，脱脂工艺为真空脱脂和空气脱脂，脱脂温度均为550℃，保温2小时。使用气氛烧结炉对脱脂样件进行烧结，烧结工艺为1800℃烧结2小时，烧结后获得高致密、高性能的氮化硅陶瓷。
实施例3
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，原料及制备工艺同实施例2，不同之处在于，造孔剂PMMA的添加量为6份(陶瓷粉体总质量的6％)。
实施例4
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，原料及制备工艺同实施例2，不同之处在于，造孔剂PMMA粉的添加量为20份(陶瓷粉体总质量的20％)。
实施例5
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，原料及制备工艺同实施例3，不同之处在于，造孔剂PMMA粉的粒径为30um。
实施例6
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，原料及制备工艺同实施例3，不同之处在于，步骤S5中构建结构模型时设计宏观孔，孔隙单元结构为圆柱形，孔隙大小为500um，横截面材料去除率为20％。
实施例7
本实施例提供了一种基于粘接剂喷射成型的大型多孔人造骨及其制备方法，原料及制备工艺同实施例3，不同之处在于，步骤S5中构建结构模型时设计宏观孔，孔隙单元结构为圆柱形，孔隙大小为500um，横截面材料去除率为25％。
上述实施例1-6制得的大型多孔人造骨(氮化硅陶瓷)的相关数据见表1。
表1本发明实施例1～3的实验相关数据及其对比数据
从表1中的数据可以看出，本发明实施例1为采用不含造孔剂的陶瓷二次颗粒制备的粘接剂喷射氮化硅陶瓷，其密度较高，孔隙较低，强度也较高。实施例2～4为采用添加造孔剂的陶瓷二次颗粒制备的粘接剂喷射多孔氮化硅陶瓷，实施例2～3中，在添加少量造孔剂后，多孔陶瓷的孔隙率增加，密度和力学性能有所降低；而当造孔剂含量过多时(实施例4)，由于打印体内部孔洞不均，经脱脂和烧结后发生陶瓷体破裂，陶瓷块体的强度极低，无法满足使用需求。实施例5为采用大粒径造孔剂的陶瓷二次颗粒制备的粘接剂喷射多孔氮化硅陶瓷，其孔隙率较实施例3相比，增加较少，强度保持不变。
进一步地，通过对实施例2制得的多孔氮化硅陶瓷的表面进行高倍数微观观察，发现内部形成了由造孔剂脱脂后保留的微米级孔隙结构，如图4、图5所示。
实施例6在实施例3的基础上，设计了宏观孔结构，由于宏观孔的存在，得到的打印件强度被削弱，但是宏观孔具有增加与细胞的接触面积，促进骨再生的作用。实施例7中增加了宏观孔的占比，打印件强度再次降低。
由此，本发明建立在以陶瓷二次颗粒作为粘接剂喷射原料的技术上，引入造孔剂，通过控制造孔剂的含量、粒径，完全可以采用粘接剂喷射技术制备出符合孔隙率、强度等要求的多孔陶瓷人造骨。可以理解地，本发明在建模中对模型内部设计的宏观孔结构可以如图3所示的三种孔结构，但不限于图示几种，以快速制备符合性能需求的大型多孔人造骨。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详细描述的部分，可以参见其他实施例的相关描述。
以上所述，为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到各种等效的修改或替换，这些修改或替换都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以权利要求的保护范围为准。
Claims (10)
1.一种基于粘接剂喷射成型的大型多孔人造骨制备方法，其特征在于，包括：
根据目标骨的尺寸形状建模，以陶瓷二次颗粒为原料进行铺粉，使用粘结剂喷射设备制作该多孔人造骨，获得打印体；对所述打印体进行脱脂、烧结，得到多孔人造骨；其中，
所述陶瓷二次颗粒采用以下步骤制得：
S1、按质量份计，取陶瓷粉体50～99.9份、烧结助剂粉体0～20份、玻璃粉体0.1～50份、造孔剂0～40份，混合均匀，干燥过筛，获得复合粉体原料；
S2、将所述复合粉体进行造粒，得到粒径0.1um～150um的造粒粉体；
S3、对所述造粒粉体进行低温烧结，所述低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，烧结后制得陶瓷二次颗粒；
所述陶瓷粉体的粒径范围在10nm～10um，玻璃粉体的粒径范围在100nm～50um，烧结助剂粉体的粒径范围在10nm～10um，造孔剂的粒径范围在0.1～50um。
2.如权利要求1所述的制备方法，其特征在于，所述陶瓷粉体选自氧化铝、氧化锆、氧化锆增韧氧化铝和氮化硅中的至少一种。
3.如权利要求1所述的制备方法，其特征在于，所述烧结助剂粉体选自MgO、ZrO2、CaO、SiO2、Cr2O3、Al2O3、SrO、TiO2、Sc2O3、Y2O3、Li2O、MgF2、YF3中的一种或多种。
4.如权利要求1所述的制备方法，其特征在于，所述玻璃粉体选自高硅氧玻璃、钠钙玻璃、铅硅酸盐玻璃、铝硅酸盐玻璃、硼硅酸盐玻璃、磷酸盐玻璃中的一种或多种。
5.如权利要求1所述的制备方法，其特征在于，所述造孔剂包括聚苯乙烯、淀粉、PMMA、核桃壳粉、植物纤维中的一种或几种。
6.如权利要求1所述的制备方法，其特征在于，所述造粒粉体中含有机物，在步骤S3对所述造粒粉体进行低温烧结之前，还包括，对造粒粉体进行脱脂。
7.如权利要求1或6所述的制备方法，其特征在于，所述脱脂的温度为300～600℃。
8.如权利要求1所述的制备方法，其特征在于，所述步骤S3中低温烧结的温度为900℃～1600℃。
9.一种大型多孔人造骨，其特征在于，由权利要求1-8任一项所述的制备方法制得。
10.一种用于粘接剂喷射成型制备大型多孔人造骨的原料，其特征在于，所述原料为陶瓷二次颗粒，所述陶瓷二次颗粒采用以下步骤制得：
S1、按质量份计，取陶瓷粉体50～99.9份、烧结助剂粉体0～20份、玻璃粉体0.1～50份、造孔剂0～40份，混合均匀，干燥过筛，获得复合粉体原料；
S2、将所述复合粉体进行造粒，得到粒径0.1um～150um的造粒粉体；
S3、对所述造粒粉体进行低温烧结，所述低温烧结的温度高于玻璃的软化点温度且低于陶瓷粉体的烧结温度，烧结后制得陶瓷二次颗粒；
所述陶瓷粉体的粒径范围在10nm～10um，玻璃粉体的粒径范围在100nm～50um，烧结助剂粉体的粒径范围在10nm～10um，造孔剂的粒径范围在0.1～50um。
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