CN116063064A - 一种陶瓷的光固化增材制造方法 - Google Patents
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Abstract
本发明公开了一种陶瓷的光固化增材制造方法，按设计比例配取分散剂，光敏树脂，光引发剂、防沉剂进行第一次搅拌获得预混液，预混液中加入纳米陶瓷粉末，第二次搅拌获得陶瓷浆料，再将陶瓷浆料通过施加温度场的光固化设备进行光固化打印，即获得光固化坯体；光固化坯体依次进行脱脂、烧结即可得到陶瓷零件；所述光固化打印时，施加温度场的温度范围为30‑80℃，本发明首创的在陶瓷光固化增材制造中引入温度场，通过温度的提高有利于增加树脂高分子的动能，提高了高分子的流动性，并降低陶瓷浆料的表面张力，从而使得陶瓷浆料的粘度降低和固含量的提高，最终所制得陶瓷零件的具有高的精度以及优异的力学性能、物理性能。
Description
技术领域
本发明属于陶瓷光固化增材制造技术领域，具体涉及一种陶瓷的光固化增材制造方法。
背景技术
陶瓷光固化增材制造技术是一种基于“逐层制造、层层叠加”原理的陶瓷材料成形技术。作为一种由三维数据驱动直接制造陶瓷零件的技术，光固化增材制造技术无需模具就能实现高精度复杂形状零件的快速制造。由于不受传统陶瓷加工技术的的限制，光固化增材制造技术能够实现陶瓷零件在几何结构内的自由设计，能够对结构和功能陶瓷的设计和制备产生革命性的影响。
光固化成形过程是通过紫外光光束曝光并固化单层陶瓷树脂浆料，并层层叠加获得打印生坯。生坯经过脱脂和烧结过程获得最终零件。低粘度高固相含量的光固化陶瓷树脂浆料是获得高质量样品的关键。光固化陶瓷树脂浆料是由陶瓷粉末颗粒、分散剂、活性稀释剂、光引发剂和其它辅助添加剂等组分构成。当浆料的粘度过高时，在打印过程中陶瓷浆料很难流畅均匀地铺散在已固化层导致打印样品的均匀性变差甚至打印失败。同时如果浆料的固含量较低也会造成较大的烧结收缩率和较差的性能。目前一般通过选择增加陶瓷粉末颗粒尺寸来提高浆料的固含量，但颗粒尺寸的增加会减小粉末颗粒的表面能从而降低打印坯体的烧结性能。另一种方法则是选择合适的分散剂来提高浆料的固含量，但选择分散剂的过程不仅耗时长且分散剂提高固含量目前已经达到一个瓶颈。
发明内容
针对现有技术的不足，本发明的目的在于提供一种陶瓷的光固化增材制造方法，采用本发明的方法，可以提高陶瓷光固化增材制造浆料固相含量，从而提高打印样品的成形精度、同时显著改善烧结样品尺寸一致性问题，最终获得高精度高性能的陶瓷零件。
为了实现上述目的，本发明采用如下的技术方案：
本发明一种陶瓷的光固化增材制造方法，按设计比例配取分散剂，光敏树脂，光引发剂、防沉剂进行第一次搅拌获得预混液，预混液中加入纳米陶瓷粉末，第二次搅拌获得陶瓷浆料，再将陶瓷浆料通过施加温度场的光固化设备进行光固化打印，即获得光固化坯体；光固化坯体依次进行脱脂、烧结即可得到陶瓷零件；
所述光固化打印时，施加温度场的温度范围为30-80℃，优选为50-70℃。
本发明的所提供的光固化增材制造方法，首创的在光固化打印过程中，施加了温度场，温度的上升提高了光敏树脂高分子的动能，促进了高分子间的流动，浆料流动性增加粘度减小，同时高分子树脂黏度减小的正效应高于布朗运动所带来阻力所带来的负效应，此外还能够降低液固之间的表面张力，同时发明人发现，光固化过程中温度场温度的增加不仅可以提高陶瓷浆料的固含量，而且可以提高陶瓷浆料的固化速率从而增加固化厚度。在提高固含量的同时可以不改变曝光功率和曝光时间即可打印出高精度高性能的陶瓷样品。
当然，发明人发现，所施加温度场温度需要控制，若温度过高，反而会导致固化失败。
优选的方案，所述陶瓷浆料，按质量份数计，组成如下：纳米陶瓷粉末78-88份，分散剂：3-6份，光引发剂：1-3份，光敏树脂：9-17份，防沉剂1份；其中，所述分散剂为超级分散剂41000；所述光引发剂为TPO，所述防沉剂为BYK410，所述光敏树脂由如下质量份的成分组成：已二醇二丙烯酸(HDDA)75-85份，三羟甲基丙烷三丙烯酸酯(TMPTA)15-25份。
本发明的陶瓷浆料，采用仅超级分散剂41000作为分散剂，超级分散剂41000通过空间位阻效应使纳米粉体解絮凝并保持稳定，同时对纳米粉体提供相同的电荷，由此产生的排斥力和位阻稳定作用可有效避免可能产生的共絮凝，有效降低陶瓷浆料的粘度，从而提高陶瓷浆料的固相含量，再配入少量防沉剂，即可使陶瓷浆料体系均匀，悬浮性能增加，不易沉淀。另外，本发明中的光敏树脂以双官能团的HDDA为主要成份，双官能团的HDDA，树脂粘度低，利于进一步的提升陶瓷的固含量，另外配入少量的多官能团TMPTA，提升固化能力，从而可以在保证固化能力的情况下，提高固含量。最后，在本发明上述陶瓷浆料的配方下，仅加入少量光引发剂TPO，协同光固化打印过程中，施加温度场，即能够通过低能量密度的紫外光照射，制备出高精度和高性能的光固化坯体，本发明中固含量可达到88％及以上。
本发明中，固含量是指陶瓷浆料中纳米陶瓷粉末的质量占比。
优选的方案：所述纳米陶瓷粉末粒径为400-800nm。
发明人发现，采用该粒径范围的纳米陶瓷粉末，粉末表面能较大，打印样品具有较好的烧结性能。
优选的方案，所述第一次搅拌的转速为1500-2000r/min，第一次搅拌的时间为5-10min，第一次搅拌在真空环境下进行。
优选的方案，将纳米陶瓷粉末于80-100℃干燥24-36h，再加入预混液中。
优选的方案，所述第二次搅拌的转速为1500-2000r/min，第二次搅拌的时间为5-10min，第二次搅拌在真空环境下进行。
优选的方案，所述光固化的打印参数为：曝光能量密度：5-50mW/cm2，曝光时间为0.6-1.2s，切片厚度为20-50μm。
优选的方案，所述脱脂过程在氩气气氛下进行，脱脂的温度为300-600℃，脱脂的时间为15-20h。
优选的方案，所述烧结的温度为1300-1550℃，烧结的时间为4-6h。
本发明的优异效果在于：
本发明首创的在陶瓷光固化增材制造中引入温度场，发明人发现，温度的提高有利于增加树脂高分子的动能，提高了高分子的流动性，并降低陶瓷浆料的表面张力，从而使得陶瓷浆料的粘度降低和固含量的提高，相对比不加温度场的陶瓷浆料，本发明中将陶瓷浆料加热到65摄氏度，陶瓷浆料的固含量可提高7-10vol％。同时陶瓷浆料加热到65摄氏度，高固相含量的固化厚度也相应增加，高固相含量的陶瓷浆料可显著降低烧结样品的收缩率并提高烧结样品的性能。
具体实施方式
实施例1：
本实施例1中，陶瓷光固化成形喂料包括以下组分：纳米(D50为500nm)ZrO2/Al2O3陶瓷粉体86份，超级分散剂VOK-Disper41000 3份，紫外光引发剂TPO1份，光敏树脂9份和防沉剂BYK4101份；其中光敏树脂主要组分：HDDA85份，TMPTA15份。将超级分散剂，紫外光引发剂，光敏树脂和防沉剂在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为86％的陶瓷喂料在65℃时100剪切速率陶瓷浆料的粘度为1Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量10mW/cm2，曝光时间为1s，切片厚度为30微米，固化厚度60微米，固化温度为65℃。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为12微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温1h，400℃保温2h，600℃保温1h。脱脂后的样品在1500℃条件下烧结4h即可得到烧结样品。
本实施案例中，烧结样品的收缩率为18％，烧结后样品密度为97.5％，抗压强度为276MPa。
对比例1
其他条件均与实施例1相同，固含量为(质量分数)为86％的陶瓷喂料在室温下于100剪切速率陶瓷浆料的粘度为30a·s，粘度过高无法满足光固化打印条件，未打印成功。
然后调整原料比例，使陶瓷光固化成形喂料包括以下组分：纳米(D50为500nm)ZrO2/Al2O3陶瓷粉体74份，超级分散剂VOK-Disper41000 3份，紫外光引发剂TPO1份，光敏树脂21份，防沉剂BYK4101份；其中光敏树脂主要组分：HDDA85份，TMPTA15份。
将超级分散剂，紫外光引发剂，光敏树脂和防沉剂在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为77％的陶瓷喂料在室温时100剪切速率下陶瓷浆料的粘度为1Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量10mW/cm2，曝光时间为1s，切片厚度为30微米，固化厚度60微米，固化温度为室温(25℃)。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为20微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温1h，400℃保温2h，600℃保温1h。脱脂后的样品在1500摄氏度条件下烧结4h即可得到烧结样品。
本对比案例中，烧结样品的收缩率为24％，烧结后样品密度为94.5％，抗压强度为168MPa。
实施例2：
本实施例2中，陶瓷光固化成形喂料包括以下组分：纳米(D50为800nm)PZT-5H陶瓷粉体83份，超级分散剂VOK-Disper41000 4份，紫外光引发剂TPO3份，光敏树脂9份和防沉剂BYK4101份；其中光敏树脂主要组分：HDDA 85份，TMPTA15份。
将超级分散剂，紫外光引发剂，光敏树脂和防沉剂在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的光固化成形陶瓷喂料。。固含量为(质量分数)为83％的陶瓷喂料在65℃时100剪切速率下陶瓷浆料的粘度为0.6Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量20mW/cm2，单层曝光时间为1.2s，切片厚度为20微米，固化厚度39微米，固化温度为65℃。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为10微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温2h，在300℃、400℃、500℃各保温3h，600℃保温2h。脱脂后的样品在1300摄氏度条件下烧结4h即可得到烧结样品。
本实施案例中，烧结样品的收缩率为25.9％，烧结后样品密度为93.7％，压电常数d33为356pC/N，相对介电常数εr为1580，机电耦合系数kt为0.57。
对比例2：
本对比例2中，陶瓷光固化成形喂料包括以下组分：纳米(D50为800nm)PZT-5H陶瓷粉体72份，超级分散剂VOK-Disper41000 4份，紫外光引发剂TPO3份，光敏树脂20份和防沉剂BYK4101份；其中光敏树脂主要组分：HDDA 85份，TMPTA15份。
将超级分散剂，紫外光引发剂和光敏树脂在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为77％的陶瓷喂料在室温(25℃)时100剪切速率下陶瓷浆料的粘度为0.5Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量20mW/cm2，单层曝光时间为1.2s，切片厚度为20微米，固化厚度38微米，固化温度为室温(25℃)。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为18微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温2h，在300℃、400℃、500℃各保温3h，600℃保温2h。脱脂后的样品在1300摄氏度条件下烧结4h即可得到烧结样品。
本对比案例中，烧结样品的收缩率为34.3％，烧结后样品密度为89.9％，压电常数d33为273pC/N，相对介电常数εr为1085，机电耦合系数kt为0.41。
实施例3：
本实施例3中，陶瓷光固化成形喂料包括以下组分：纳米(D50为950nm)Si3N4陶瓷粉体78份，超级分散剂VOK-Disper41000 4份，紫外光引发剂TPO3份，光敏树脂14份，防沉剂BYK4101份；其中光敏树脂主要组分：HDDA 85份，TMPTA15份。
将超级分散剂，紫外光引发剂和光敏树脂在真空搅拌脱泡机中高速搅拌(2000r/min)15分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)15分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为78％的陶瓷喂料在65℃时100剪切速率下陶瓷浆料的粘度为1.5Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量35mW/cm2，曝光时间为2s，切片厚度为20微米，固化厚度40微米，固化温度为65℃。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为18微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温2h，550℃保温2h。脱脂后的样品在1550摄氏度条件下烧结3h即可得到烧结样品。
本实施案例中，烧结样品的收缩率为26.4％，烧结后样品密度为93.2％，抗弯强度为403MPa。
对比例3：
本对比例3中，陶瓷光固化成形喂料包括以下组分：纳米(D50为950nm)Si3N4陶瓷粉体70份，超级分散剂VOK-Disper41000 4份，紫外光引发剂TPO3份，光敏树脂22份和防沉剂BYK4101份；其中光敏树脂主要组分：HDDA 85份，TMPTA15份。
将超级分散剂，紫外光引发剂，光敏树脂和防沉剂在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r/min)10分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为70％的陶瓷喂料在室温时100剪切速率下陶瓷浆料的粘度为1.5Pa·s，满足光固化打印条件。
将光固化成形喂料加入设备料槽中，设置好光固化工艺参数：曝光能量35mW/cm2，曝光时间为2s，切片厚度为20微米，固化厚度41微米，固化温度为室温(25℃)。按照提前设置好的模型通过层层叠加的方式打印得到样品坯体。加工误差为26微米。
生坯在氩气气氛中进行脱脂处理：在200℃保温2h，550℃保温2h。脱脂后的样品在1550摄氏度条件下烧结4h即可得到烧结样品。
本对比案例中，烧结样品的收缩率为35.8％，烧结后样品密度为89.3％，抗弯强度为328MPa。
对比例4
本对比例4中，陶瓷光固化成形喂料包括以下组分：纳米(D50为950nm)Si3N4陶瓷粉体78份，分散剂油酸4份，紫外光引发剂TPO3份，光敏树脂15份；防沉剂BYK4101份，其中光敏树脂主要组分：HDDA 85份，TMPTA15份。
将分散剂，紫外光引发剂和光敏树脂在真空搅拌脱泡机中高速搅拌(2000r//min)15分钟，得到混合均匀的预混液。然后在预混液中加入在85℃干燥24小时的纳米粉体。随后将混合物在真空搅拌脱泡机中高速搅拌(2000r//min)15分钟，得到混合均匀的光固化成形陶瓷喂料。固含量为(质量分数)为78％的陶瓷喂料在65℃时100剪切速率下陶瓷浆料的粘度为50Pa·s，粘度太高不满足光固化打印条件，无法进行光固化打印。
Claims (10)
1.一种陶瓷的光固化增材制造方法，其特征在于：按设计比例配取分散剂，光敏树脂，光引发剂、防沉剂进行第一次搅拌获得预混液，预混液中加入纳米陶瓷粉末，第二次搅拌获得陶瓷浆料，再将陶瓷浆料通过施加温度场的光固化设备进行光固化打印，即获得光固化坯体；光固化坯体依次进行脱脂、烧结即可得到陶瓷零件；所述光固化打印时，施加温度场的温度范围为30-80℃。
2.根据权利要求1所述的一种陶瓷的光固化增材制造方法，其特征在于：所述光固化打印时，施加温度场的温度范围为50-70℃。
3.根据权利要求1所述的一种陶瓷的光固化增材制造方法，其特征在于：所述陶瓷浆料，按质量份数计，组成如下：纳米陶瓷粉末78-88份，分散剂3-6份，光引发剂1-3份，光敏树脂9-17份，防沉剂1份；其中，所述分散剂为超级分散剂41000；所述光引发剂为TPO，所述防沉剂为BYK410，所述光敏树脂由如下质量份的成分组成：已二醇二丙烯酸75-85份，三羟甲基丙烷三丙烯酸酯15-25份。
4.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述纳米陶瓷粉末粒径为400-800nm。
5.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述第一次搅拌的转速为1500-2000r/min，第一次搅拌的时间为5-10min，第一次搅拌在真空环境下进行。
6.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：将纳米陶瓷粉末于80-100℃干燥24-36h，再加入预混液中。
7.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述第二次搅拌的转速为1500-2000r/min，第二次搅拌的时间为5-10min，第二次搅拌在真空环境下进行。
8.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述光固化的打印参数为：曝光能量密度：5-50mW/cm2，曝光时间为0.6-1.2s，切片厚度为20-50μm。
9.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述脱脂过程在氩气气氛下进行，脱脂温度为300-600℃，脱脂时间为15-20h。
10.根据权利要求1-3任意一项所述的一种陶瓷的光固化增材制造方法，其特征在于：所述烧结的温度为1300-1550℃，烧结的时间为4-6h。
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