CN106956432A - 一种单喷头实现多材料层级复合3dp技术及其应用 - Google Patents
一种单喷头实现多材料层级复合3dp技术及其应用 Download PDFInfo
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Abstract
本发明涉及一种三维打印技术（3DP），具体涉及使用单一喷头实现多材料层级复合的3DP技术及其应用。本发明是在不改变原有的三维打印技术设备平台基础上，通过设计配置一级、二级物料筒，并经打印喷头的二级联动活塞装置，在不改变打印设备原有运动模式和控制软件的前提下，精确实现不多物料的连续共混挤出打印。本发明提供的多材料复合打印喷头，可充分复合多种打印材料，不同材料间混合充分，复合效果好，打印结构为层级包裹连续复合，具有较好的设备兼容性和可实施性，在生物医学领域具有广阔的应用前景。
Description
技术领域
本发明属于3D打印技术领域，涉及一种生物医用材料成型领域，具体为一种单喷头实现多材料层级复合3DP技术及其应用。
背景技术
增材制造技术（又称3D打印技术）是继传统切削减材成型技术手段后，近20年来飞速发展起来的一项材料成型制造技术，与传统的材料去除加工方法不同，3D打印是基于三维数字模型以点、线、面、体的叠加法通过层层叠加增材柔性制造出具有任意复杂形状的零件。3D打印技术涵盖了产品生命周期前端的“快速原型”（Rapid Prototyping）到全生产周期的“快速制造”（Rapid Manufacturing），以及其他所有相关的打印工艺、技术、设备和应用。目前，应用较多的3D打印技术主要包括光固化立体印刷（SLA）、熔融沉积制造（FDM）、选择性激光烧结/熔化（SLS/SLM）和三维喷印技术（3DP）。3D打印技术具有个性化、精准化、远程化等优点，特别适合于医学领域的应用，必将对整个医疗卫生事业产生深远影响。三维喷印技术（3DP）是打印机在计算机的控制下，把原料装入机身，通过计算机的控制，用打印喷头将原料层层叠加起来，最后实现材料的增材制造。因为3DP技术对设备要求较低，且原料是材料粉末和粘结剂，相对于其他打印方式来说对材料要求较低，故可以加工多种材料，例如石膏、陶瓷、塑料、金属等。3DP可通过增加喷头的数量来实现多材料和多组分的打印。多喷头打印技术目前应用非常广泛，但是其同时存在许多技术缺陷，例如：其一多喷头打印相对于单喷头打印而言对设备的硬件配置和软件参数控制更为复杂，容易导致因为某个环节参数设置不当而导致打印失败；其二根据3DP技术的特点其多喷头实现的多材料复合，不同材料是在不同的喷头中挤出后再进行分别编织复合的，材料之间的复合是分离的、离散的，不同材料层级之间的结合不好，这极大地限制了其在打印复合材料领域的应用。
复合材料是由两种或两种以上不同性质的材料，通过物理或化学的方法，在宏观（微观）上组成具有新性能的材料。各种材料在性能上互相取长补短，产生协同效应，使复合材料的综合性能优于原组成材料而满足各种不同的功能需求。在复合材料中，不同材料的结合方式，对材料的性能影响很大。传统的三维打印技术成型复合材料具有很大的局限性，其通过多喷头实现的复合成型，不同材料之间是通过离散编织的。而在某些特定领域中，需要三维打印的复合材料制品中包含连续的多种材料复合，这种要求传统的多喷头3DP打印技术是无法实现的。例如用于组织工程的微球材料，需要用水凝胶连续相材料包裹活细胞，给细胞提供充足营养。目前3DP在活细胞打印方面，传统的喷头模式无法完成这项任务。
发明内容
本发明目的是针对现有三维打印技术中的不足，提供一种单喷头实现多材料层级复合3DP技术及其应用。本发明基于单喷头打印设备平台，通过对打印喷头构造结构进行改造，可在不增加喷头的前提下实现多材料的连续相成分复合构建。
为了实现上述目的，本发明的具体技术方案为：
一种单喷头实现多材料的层级复合的三维打印技术（3DP），作为优选，本发明应用于三维喷射打印（3DP）成型技术中。在该技术中，两个单喷头组成复合喷头装置，实现多材料的层级复合的三维打印技术（3DP）。
该喷头装置包括一级料筒喷头、二级料筒喷头、二级料筒固定装置、二级料筒、二级料筒活塞、联动活塞推杆、一级料筒活塞和一级料筒，一级料筒上带有一级料筒活塞，二级料筒上带有二级料筒活塞，一级料筒与二级料筒之间通过联动活塞推杆进行同轴活塞式联动的连接，二级料筒固定在二级料筒固定装置上，在二级料筒固定装置上的前端依次设置二级料筒喷头和一级料筒喷头。
作为优选，该喷头装置包含有双层次多物料装载料筒，料筒之间的连接为同轴心嵌套结构。
作为优选，该喷头装置使用的料筒为医用级聚丙烯(PP)材料，其内径为ϕ5mm～ϕ40mm，容量为10～200ml。
作为优选，该喷头装置包含内外部活塞式联动物料筒，根据所选内外部活塞具有相同的线速度运动速率，打印挤出时可将内外料筒中的不同物料（打印材料）同时挤出。
作为优选，该喷头装置包含一个二级料筒固定装置，该装置一方面用于固定内部料筒，确保打印时运动平稳，另外一方面该装置同时起到调节一级料筒（外部料筒）物料进料速度的作用。作为优选，该喷头装置包含内外部物料打印喷头，内部物料打印喷头直径为100-500 um, 外部物料打印喷头直径为200-1000 um,内外部喷头内径比为1:2。
作为优选，该喷头装置内外部物料打印喷头端头长度不一，内部物料打印喷头短，其端口距离外部喷头3-10mm，以保证打印时的多材料充分复合。
本发明的积极效果为：
（一）、本发明在于不增加喷头的数量，不对三维打印设备机进行修改，仅需对喷头料筒进行改造，实施简单，费用低。
（二）、本发明的喷头可以在三维打印技术中实现多材料的层级复合，实现不同打印物料的连续层级复合。
（三）、本发明可通过调节喷头装置内外部物料打印喷头的直径来灵活实现对复合材料的成分调整。
（四）、本发明可通过打印喷头的二级联动活塞装置，在不改变打印设备原有运动模式和控制软件的前提下，精确实现不多物料的共混挤出打印。
（五）、本发明提供的多材料复合打印喷头，可有效充分复合多种打印材料，打印结构为层级包裹连续复合，不同物料间混合充分，复合效果好。
（六）、本发明实现的多材料层级复合，不会改变原有三维打印技术（3DP）的分层模型和打印参数，具有较好的设备兼容性和可实施性。
附图说明
图1为二级料筒固定装置示图。
图2为复合喷头装配的截面结构示意图。
其中，1——外部料筒喷头（也称一级料筒喷头），2——内部料筒喷头（也称二级料筒喷头），3——二级料筒固定装置，4——内部料筒（二级料筒），5——二级料筒活塞，6——联动活塞推杆，7——一级料筒活塞，8——外部料筒（一级料筒）。
图3为实施例1中所打印的双相材料层级复合骨组织支架，其中在二级料筒（内部）内装载调制均匀的生物粘结剂和纳米羟基磷灰石材料，一级料筒（外部）内装载调制均匀的生物粘结剂和纳米磷酸三钙材料，进行双相材料复合打印；
图4为实施例1中所打印的双相材料层级复合骨组织支架横截面图，其中在支架线条内层为纳米羟基磷灰石材料，外层为连续包裹复合的纳米磷酸三钙材料；
图5. 实施例4中所打印的纳米HA、纳米β-TCP为原材料的双相材料层级复合骨组织支架，其具有可控降解的生物学特性，其中外部层β-TCP材料生物降解速率较快，芯部HA生物降解速率较慢，通过控制二者的复合配比，可以实现骨组织修复体的生物降解速度控制。
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，下面结合具体实施方式对本发明作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于下述实施例。本发明所涉及的实现多材料的层级复合的单喷头应用于三维打印技术(3DP)成型设备当中。
本发明实现多材料的层级复合打印喷头所采用的料筒规格型号和所采用的打印原料不限于本发明所述方案。
实施例1：
选用内径为ϕ25mm的一级料筒和内径为ϕ10mm的二级料筒装配喷头装置，内外部物料打印喷头直径各为200μm和400μm，内外部喷头端口距离8mm，按照示意图1进行组装。其中在二级料筒（内部）内装载调制均匀的生物粘结剂和纳米羟基磷灰石材料，一级料筒（外部）内装载调制均匀的生物粘结剂和纳米磷酸三钙材料，进行双相材料层级复合打印。打印完成多孔类骨支架产品，并将打印好的支架进行1100℃高温烧结，得到具有多生物功能效益的骨组织工程支架。复合支架芯部羟基磷灰石材料具有较高的力学强度且生物相容性好；外部复合磷酸三钙材料相比较羟基磷灰石，虽然力学性能差，但却具有较好的生物活性和成骨诱导性，可同时赋予打印产品同时具有良好的力学性能和生物活性功能。
实施例2：
选用内径为ϕ25mm的一级料筒和内径为ϕ10mm的二级料筒装配喷头装置，内外部物料打印喷头直径各为200μm和400μm，内外部喷头端口距离8mm，按照示意图1进行组装。其中在二级料筒（内部）内装载调制均匀的均匀的生物粘结剂和纳米Al3O2粉末材料，一级料筒（外部）内装载调制均匀的生物粘结剂和纳米磷酸三钙材料，进行双相材料层级复合打印。打印完成多孔类骨支架产品，并将打印好的支架进行1100℃高温烧结，得到具有多重生物功能效益的骨组织工程支架。复合支架芯部纳米Al3O2粉末具有优良的力学强度和生物惰性，增韧增强效果明显，其在体内能够稳定存在，生物相容性较好，并且在临床上已经有应用，外部复合磷酸三钙材料具有较好的生物活性和成骨诱导性，可同时赋予打印产品同时具有良好的抗压强度和韧性，同时兼具良好的生物活性功能。
实施例3：
以微粒直径为50～80nm的纳米氧化锆粉末, 纳米双相磷酸钙粉末为原材料，其原料制备及打印喷头装配过程与实施例1相同，不同之处在于内外部料筒内装载的打印材料不同，即在二级料筒（内部）内装载调制均匀的均匀的生物粘结剂和纳米氧化锆粉末，一级料筒（外部）内装载调制均匀的生物粘结剂和纳米双相磷酸钙粉末，其打印制备的骨组织工程支架兼具良好的力学性能和成骨诱导性，可应用于承力部位缺损骨组织修复。
实施例4
以微粒直径为80～100nm的纳米HA粉末, 80～100nm纳米β-TCP粉末为原材料，其原料制备及打印喷头装配过程与实施例1相同，不同之处在于内外部料筒内装载的打印材料不同，同时打印喷头直径也不同，以实现不同物料的不同比例复合。即在二级料筒（内部）内装载调制均匀的均匀的生物粘结剂和纳米HA，一级料筒（外部）内装载调制均匀的生物粘结剂和纳米β-TCP，内外部物料打印喷头直径分别为200μm和300μm。其打印制备的骨组织工程支架在植入人体内具有可控降解的生物学特性，其中外部层β-TCP材料具有较快的生物降解速率，芯部HA材料具有缓慢降解的生物学特性，通过控制二者的复合配比，可以实现骨组织修复体的生物降解速度控制。
应用实例1：
以带有活细胞的培养基及水凝胶材料为打印原料,其原料制备及打印喷头装配过程与实施例1相同，不同之处在于内外部料筒内装载的打印材料不同，以实现活细胞的包裹生物打印。按照示意图1进行组装完成后，在二级料筒（内部）内装载调制带有软骨细胞的培养基，在一级料筒（外部）装载调制好的水凝胶材料。将此打印喷头装载到生物三维打印机中，可打印出包裹好活细胞的软组织工程支架，材料内部的种子细胞有利于促进组织器官的形成，材料外部的基质成分有利于固定细胞和提供营养。
应用实例2：
以带有活细胞的培养基及水凝胶材料为打印原料,其原料制备及打印喷头装配过程与实施例1相同，不同之处在于内外部料筒内装载的打印种子细胞、材料不同，以实现生物活体器件的打印构建。按照示意图1进行组装完成后，在二级料筒（内部）内装载调制带有成骨细胞的培养基，在一级料筒（外部）装载调制好的明胶材料。将此打印喷头装载到生物三维打印机中，可打印出包含成骨种子细胞的硬骨组织修复材料，材料内部的成骨种子细胞有利于促进骨组织的发育，材料外部的基质成分有利于固定细胞和提供营养，同时通过多孔设计打印可以提供外部血管长入空间。
以上所述仅为本发明的优选实施例，对本发明而言仅是说明性的，而非限制性的；本领域普通技术人员理解，在本发明所限定的精神和范围内可对其进行许多改变，修改，甚至等效变更，但都将落入本发明的保护范围。
Claims (4)
1.一种单喷头实现多材料层级复合3DP技术，其特征在于通过单喷头装置实现多材料连续层级复合。
2.根据权利要求1所述单喷头实现多材料层级复合3DP技术，其特征在于：该喷头装置包括一级料筒喷头（1）、二级料筒喷头（2）、二级料筒固定装置（3）、二级料筒（4）、二级料筒活塞（5）、联动活塞推杆（6）、一级料筒活塞（7）和一级料筒（8），一级料筒（8）上带有一级料筒活塞（7），二级料筒（4）上带有二级料筒活塞（5），一级料筒（8）与二级料筒（4）之间通过联动活塞推杆（6）进行同轴活塞式联动的连接，二级料筒（4）固定在二级料筒固定装置（3）上，在二级料筒固定装置（3）上的前端依次设置二级料筒喷头（2）和一级料筒喷头（1）。
3.根据权利要求1所述单喷头实现多材料层级复合3DP技术，其特征在于：该喷头装置中一级料筒喷头（1）和二级料筒喷头（2）的端头长度不一，二级料筒喷头（2）短，其端口距离一级料筒喷头（1）3-10mm。
4.根据权利要求1所述单喷头实现多材料层级复合3DP技术，其特征在于：该喷头装置中，二级料筒喷头（2）的直径为100-500 um, 一级料筒喷头（1）的直径为200-1000 um，内外部喷头内径比为1:2。
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