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Emulsion inks for 3D printing porous materials

机译:用于3D打印多孔材料的乳液油墨

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Introduction: 3D printing techniques have been adapted to print novel polymers and biological gels into complex tissue engineering scaffolds. Here, we report a new method of creating high porosity foams with complex shapes by using open source, solid freeform fabrication (SFF) technology and emulsion inks developed in our lab. High internal phase emulsions (HIPE) prepared from hydrophobic photopolymers exhibit shear thinning behavior that permits extrusion, and a high zero-shear viscosity sufficient for shape retention after deposition. Each layer is actively polymerized with a UV Cure-on-Dispense (CoD) technique. In this study, the effects of emulsion viscosity and cure rate on print fidelity were studied. Materials and Methods: HIPEs were fabricated using a FlackTek Speedmixer DAC 150 FVZ-K according to a protocol adapted from Moglia et all1'. Polypropylene glycol) dimethacrylate (PPGDMA, 560 Da), was used as the main HIPE macromer and diurethane dimethacrylate (DUDMA, 471 Da), was used to increase the viscosity of the emulsion. Shapes were designed in Solidworks and exported into the STL file format. Printer G-code was created with Slic3r v1.2.6. Infill (50%, 70%), layer height (0.2 mm), extrusion width (0.6 mm), and a print speed of 10 mm/s were crucial for the formation of accurate, cohesive constructs. Objects were printed on a modified HYREL 3D printer utilizing Arduino Mega+RAMPS v1.4 electronics. An emulsifiable extruder (EMO-25) by HYREL with a 22 gauge dispensing tip were used to deposit the HIPE material. Four, 3 watt UV LEDs mounted to the extruder cure HIPE material as it is dispensed. Cylinders were printed to evaluate the ability to create high fidelity constructs and single lines of extruded material were examined with SEM to evaluate shape retention after extrusion. Results and Discussion: Uncured HIPEs exhibited low viscosity at typical printing shear rates, (10 Pa~*s at 50 1/s), allowing for precise dispensing. Increasing the viscous component, DUDMA, increased the viscosity of the macromer phase, resulting in increased emulsion zero-shear viscosity, (up to 3500 Pa~*s at 0.011/s) while retaining shear-thinning characteristics, Figure 1 (A). Increased viscosity decreased printed line slumping and improved print fidelity (B). Cure-on-dispense printing increased print fidelity relative to post-print curing, but increasing pholoinitiator to 5% showed a smaller decrease in line spreading and increase in shape retention (C). HIPEs with sufficient viscosity produced tall, complex scaffolds with an internal lattice structure and hierarchical porosity, Figure 2. Conclusion: These findings indicate that the viscosity of emulsion inks and cure rate play important roles in print fidelity. Overall, the demonstrated ability to print porous materials using emulsion inks and CoD technology advance current additive manufacturing efforts to generate custom porous materials for tissue engineering and drug delivery applications.
机译:简介:3D打印技术已适应将新颖的聚合物和生物凝胶打印到复杂的组织工程支架中。在这里,我们报告了一种通过使用开放源代码,固体自由形式制造(SFF)技术和在我们的实验室中开发的乳液油墨来制造具有复杂形状的高孔隙率泡沫的新方法。由疏水性光敏聚合物制备的高内相乳液(HIPE)具有剪切稀化行为,可以挤出,并且具有高的零剪切粘度,足以在沉积后保持形状。每层均采用UV点胶固化(CoD)技术进行主动聚合。在这项研究中,研究了乳液粘度和固化速率对印刷保真度的影响。材料和方法:根据Moglia等人的协议,使用FlackTek Speedmixer DAC 150 FVZ-K制造HIPE。聚丙二醇)二甲基丙烯酸酯(PPGDMA,560 Da)用作主要的HIPE大单体,二氨基甲酸酯二甲基丙烯酸酯(DUDMA,471 Da)用于提高乳液的粘度。形状是在Solidworks中设计的,并已导出为STL文件格式。打印机G代码是使用Slic3r v1.2.6创建的。填充物(50%,70%),层高(0.2毫米),挤出宽度(0.6毫米)和10毫米/秒的印刷速度对于形成精确的,具有凝聚力的结构至关重要。使用Arduino Mega + RAMPS v1.4电子设备在经过修改的HYREL 3D打印机上打印对象。使用HYREL的乳化挤出机(EMO-25)和22号点胶针头来沉积HIPE材料。安装在挤出机上的四个3瓦紫外线LED可在分配HIPE材料时对其进行固化。印刷圆柱体以评估产生高保真构造体的能力,并且用SEM检查挤出材料的单线以评估挤出后的形状保持性。结果与讨论:未固化的HIPE在典型的印刷剪切速率下表现出低粘度(在50 1 / s时为10 Pa〜* s),从而可以精确分配。增加粘性组分DUDMA会增加大分子单体相的粘度,从而导致乳液零剪切粘度增加(在0.011 / s时高达3500 Pa·s),同时保持剪切稀化特性,图1(A)。粘度的增加减少了印刷线的塌落并改善了印刷保真度(B)。相对于印后固化,点胶固化印刷提高了印刷保真度,但光引发剂增加到5%则显示线散布减少较小,形状保持力增加(C)。具有足够粘度的HIPE可以生产出具有内部晶格结构和分层孔隙率的高大,复杂的支架,图2。结论:这些发现表明,乳胶油墨的粘度和固化速率在印刷保真度中起着重要的作用。总体而言,使用乳液油墨和CoD技术印刷多孔材料的能力已得到证实,这推动了当前的增材制造工作,从而为组织工程和药物输送应用生成定制的多孔材料。

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