CN110256069B - 一种可光固化的3d打印成型用染色齿科氧化锆陶瓷料浆的制备方法 - Google Patents
一种可光固化的3d打印成型用染色齿科氧化锆陶瓷料浆的制备方法 Download PDFInfo
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Abstract
本发明涉及一种可光固化的3D打印成型用染色齿科氧化锆陶瓷料浆的制备方法,属于陶瓷3D打印成型领域。采用粉体混合(内着色)法,用稀土氧化物和过渡金属氧化物对陶瓷进行着色,以获得自然牙色的氧化锆陶瓷;采用低聚物树脂和活性稀释剂共同作为交联剂,利用球磨法,制得一种可光固化的3D打印成型用染色齿科氧化锆陶瓷的料浆,具有固含量高、粘度低、均匀性好、固化厚度大、打印成型精度高和固化强度高等优点,并且生产工艺简单,便于推广应用。通过本发明的料浆打印成型的齿科陶瓷预制体,经过脱脂、烧结,可获得均匀自然牙色的效果,实现形状、尺寸、牙色的个性化定制,与患者原有牙齿完美契合,节省操作时间,应用前景广阔。
Description
技术领域
本发明涉及一种可光固化的3D打印成型用染色齿科氧化锆陶瓷料浆的制备方法,属于陶瓷3D打印成型领域。该陶瓷料浆材料具有固含量高、粘度低、打印精度高和固化强度高等优点,应用前景广阔。
背景技术
二氧化锆陶瓷具有优良的物理化学性质和生物相容性,广泛用于骨科材料、义齿等领域。但是,由于陶瓷硬度大、脆性大而导致加工难度大,使其应用受到限制,尤其是在形状复杂、尺寸精确、高表面质量和个性化定制的微型陶瓷器件方面。光固化3D打印技术与二氧化锆陶瓷相结合,能较好地解决二氧化锆陶瓷成型的难题,充分发挥出二氧化锆陶瓷的性能优势,实现齿科修复体的个性化定制。
现阶段的3D打印成型氧化锆陶瓷齿科修复体的颜色单一,只有一种白垩色,打印的牙冠色泽单一,打印完成后需要浸泡染色或使用遮色瓷对其进行修饰。而浸泡染色法在修复体支架较厚的部分(如固定桥桥体),由于渗透因素,表面着色较内部着色深,导致着色不均匀,不美观;遮色瓷为了获得层次感和更好的美观效果,其饰面瓷的厚度会增加,这使牙体制备的预留量增加,对牙体组织的保护不利。
本专利采用粉体混合(内着色)法,用稀土氧化物和过渡金属氧化物对氧化锆陶瓷进行着色。过渡金属氧化物进入ZrO2晶格时,能形成呈色结构物,获得自然牙色的氧化锆陶瓷;采用低聚物树脂和活性稀释剂共同作为交联剂,利用球磨法,制得一种3D打印成型用可光固化的染色齿科氧化锆陶瓷的料浆。光固化过程中,光引发剂吸收光子,产生活性自由基,自由基与低聚物单体和活性稀释剂中的C=C结合,并在此基础上进行链式增长,使C=C产生聚合,从而将染色陶瓷的粉体和惰性稀释剂进行原位固定,最后在脱脂、烧结过程中,树脂和惰性稀释剂分解为气体和水挥发掉,制备成颜色均匀的陶瓷齿科植入体,应用前景广阔。
发明内容
本发明的目的在于使用过渡金属氧化物和稀土氧化物染色的氧化锆陶瓷粉体制备一种可光固化的染色齿科氧化锆陶瓷的料浆,结合3D打印成型工艺,实现齿科植入体的个性化定制,提供一种简便的3D打印成型用可光固化的染色齿科氧化锆陶瓷料浆的制备方法。
本发明所制备的染色氧化锆料浆固含量可达77wt%,表现出明显的剪切变稀行为,具有良好的固化性能。使用本料浆制备的氧化锆陶瓷齿科植入体,具有精度高、密度大、力学性能优良等优点,其相对密度达到98%以上,三点弯曲强度可达750MPa。本发明技术方案为:一种简便的3D打印成型用可光固化的染色齿科氧化锆陶瓷料浆的制备方法。
(1)按照设计的配方,分别称取微量Fe2O3、CeO2、Er2O3、Pr6O11和MnO2,将称取的稀土氧化物和ZrO2一起在无水乙醇中球磨混合3h以上,将混合好的粉体在烘箱中干燥至恒重,随后研磨、过筛,备用;
(2)分别取低聚物(20~70wt%)、活性稀释剂(10~40wt%)、惰性稀释剂(1~50wt%)和光引发剂(0.1~5wt%),在水浴锅中加热搅拌30min以上,充分搅拌均匀,获得光固化树脂,备用;
(3)将步骤一制备的染色陶瓷粉按照料浆总体积的50%(陶瓷粉体的体积由已知的粉体真密度换算),分次加入到步骤二制备的光固化树脂(占料浆总体积的50%)中,并加入3wt%(相对于粉的质量)的分散剂span20、2wt%(相对于料浆总质量)的助剂(消泡剂、流平剂),在球磨机中球磨混合12h以上,制得陶瓷料浆。
本发明的有益效果:
(1)采用本方法制备的氧化锆陶瓷料浆,具有固含量高、粘度低、打印精度高和固化强度高等优点,满足光固化3D打印成型机的操作要求;
(2)采用内着色法制备的氧化锆陶瓷料浆,可打印成型出呈色均匀、半透明的氧化锆义齿,能很好地再现自然牙的颜色,满足陶瓷牙的美观要求;制备的义齿能根据患者的具体情况实现形状、尺寸、牙色的个性化定制,与患者原有牙齿完美契合,节省操作时间;
(3)使用此料浆制备的氧化锆陶瓷,其三点弯曲强度可达750MPa,维氏硬度达到15.13GPa,满足齿科陶瓷材料标准的要求。
附图说明
图1为实施例1制备的氧化锆陶瓷料浆的光敏参数曲线图。
图2为实施例2制备的氧化锆陶瓷料浆的光敏参数曲线图。
图3为实施例3制备的氧化锆陶瓷料浆的光敏参数曲线图。
图4中的曲线1为实施例1制备的氧化锆陶瓷料浆的粘度随剪切速率的变化曲线;图4中的曲线2为实施例2制备的氧化锆陶瓷料浆的粘度随剪切速率的变化曲线;图4中的曲线3为实施例3制备的氧化锆陶瓷料浆的粘度随剪切速率的变化曲线。
具体实施方式
下面结合实例对本发明的特点作进一步描述,但是并非仅仅局限于下述实施例。
实施例1
(1)根据牙色实际要求称取适量氧化物:氧化镨0.02wt%、氧化铈0.1wt%、氧化铒0.3wt%、氧化锰0.01wt%(基于陶瓷粉的质量),将称量好的氧化物和氧化锆粉在无水乙醇中球磨分散4h,球磨完成后置于70℃烘箱中进行干燥,待干燥完成后研磨、过筛,制备成陶瓷粉,备用;
(2)按照计算好的光固化树脂配方,分别称取50wt%的甲基丙烯酸羟乙酯(HEMA)、30wt%的三乙二醇二丙烯酸酯(TEGDA)、20wt%的聚乙二醇400、2wt%的784+TPO混合光引发剂(相对于树脂单体的质量),在水浴锅中加热搅拌30min,充分搅拌均匀,制备成光固化树脂,备用;
(3)将步骤一制备的染色陶瓷粉按照料浆总体积的50%(陶瓷粉体的体积由已知的粉体真密度换算),分次加入到步骤二制备的光固化树脂(占料浆总体积的50%)中,3wt%(相对于粉的质量)的span20分散剂、2wt%(相对于料浆总质量)的助剂(消泡剂、流平剂),粉体和分散剂分次加料,通过球磨机球磨12h混合,制得陶瓷料浆。
制备的氧化锆陶瓷料浆进行光固化实验,根据Beer-Lambert方程获得光敏参数曲线,分析其固化性能,其光敏参数曲线见图1;图1表明,Cd与lnE0呈线性关系,直线的斜率为投射深度Sd,直线与横坐标轴的交点为临界曝光量Ed;从图1可以得到,Sd=193.50μm,Ed=158.63mJ/cm2,说明氧化锆陶瓷料浆的投射深度为193.50μm,临界曝光量为158.63mJ/cm2;料浆粘度随剪切速率的变化见图4中的曲线1。
实施例2
(1)根据牙色实际要求称取适量氧化物:氧化镨0.01wt%、氧化铈0.1wt%、氧化铒0.2wt%、氧化锰0.01wt%(基于陶瓷粉的质量),将称量好的微量氧化物和陶瓷粉中在无水乙醇中球磨分散4h,球磨完成后置于80℃烘箱中进行干燥,待干燥完成后研磨、过筛,制备成陶瓷粉,备用;
(2)按照计算好的光固化树脂配方,分别称取50wt%的丙氧化三羟甲基丙烷三丙烯酸酯(PO3-TMPTA)、30wt%的1,6-已二醇双丙烯酸酯(HDDA)、20wt%的聚乙二醇400、2wt%的784+TPO混合光引发剂(相对于树脂单体的质量),在水浴锅中加热搅拌45min,充分搅拌均匀,制备成光固化树脂,备用;
(3)将步骤一制备的染色陶瓷粉按照料浆总体积的50%(陶瓷粉体的体积由已知的粉体真密度换算),分次加入到步骤二制备的光固化树脂(占料浆总体积的50%)中,3wt%(相对于粉的质量)的span20分散剂、2wt%(相对于料浆总质量)的助剂(消泡剂、流平剂),粉体和分散剂分次加料,通过球磨机球磨13h混合,制得陶瓷料浆。
对制得的氧化锆料浆进行固化实验,根据Beer-Lambert方程获得料浆的光敏参数曲线,分析其固化性能,其光敏参数曲线见图2;图2表明,Cd与lnE0呈线性关系,直线的斜率为投射深度Sd,直线与横坐标轴的交点为临界曝光量Ed;从图2可以得到,Sd=150.85μm,Ed=206.02mJ/cm2,说明氧化锆陶瓷料浆的投射深度为150.85μm,临界曝光量为206.05mJ/cm2;料浆粘度随剪切速率的变化见图4中的曲线2。
实施例3
(1)根据牙色实际要求称取适量微量氧化物:氧化镨0.01wt%、氧化铈0.2wt%、氧化铒0.2wt%、氧化锰0.01wt%(基于陶瓷粉的质量),将称量好的微量氧化物和陶瓷粉中在无水乙醇中球磨分散5h,球磨完成后置于90℃烘箱中进行干燥,待干燥完成后研磨均匀、过筛,制备成陶瓷粉,备用;
(2)按照计算好的光固化树脂配方数据分别称取50wt%的三羟甲基丙烷二丙烯酸酯(TMPDA)、30wt%的丙烯酸异辛酯(EHA)、20wt%的聚乙二醇400、2wt%的784+TPO混合光引发剂(相对于树脂单体的质量),在水浴锅中加热搅拌60min,充分搅拌均匀,制备成光固化树脂,备用;
(3)将步骤一制备的染色陶瓷粉按照料浆总体积的50%(陶瓷粉体的体积由已知的粉体真密度换算),分次加入到步骤二制备的光固化树脂(占料浆总体积的50%)中,3wt%(相对于粉的质量)的span20分散剂、2wt%(相对于料浆总质量)的助剂(消泡剂、流平剂),粉体和分散剂分次加料,通过球磨机球磨15h混合,制得陶瓷料浆。
Claims (2)
1.一种可光固化的3D打印成型用牙色齿科氧化锆陶瓷料浆的制备方法,首先采用内着色法制备牙色陶瓷粉体,再用球磨法制得可光固化的3D打印成型用陶瓷料浆,其特征在于:
(1)采用粉体混合内着色法对氧化锆陶瓷进行染色,选用氧化铁、氧化铈、氧化铒、氧化镨、氧化锰、偏钒酸铵着色剂中的一种或几种,引入到氧化锆陶瓷的原料粉中,在无水乙醇中球磨分散3h以上,再置于70℃以上烘箱中干燥,待干燥完成后,研磨均匀待用;
(2)光固化反应树脂的主要组成包括低聚物单体、活性稀释剂、惰性稀释剂、光引发剂;
a.低聚物选用丙烯酸羟乙酯HEA、丙烯酸羟丙酯HPA、甲基丙烯酸羟乙酯HEMA、甲基丙烯酸羟丙酯HPMA、三羟甲基丙烷二丙烯酸酯TMPDA、季戊四醇三丙烯酸酯PETA、丙氧化三羟甲基丙烷三丙烯酸酯PO3-TMPTA中的一种或几种;
b.活性稀释剂选用丙烯酸异辛酯EHA、1,6-已二醇双丙烯酸酯HDDA、三乙二醇二丙烯酸酯TEGDA、季戊四醇三丙烯酸酯PETA中的一种或几种;
c.惰性稀释剂选用正丁醇、异丙醇、聚乙二醇中的一种或几种;
d.光引发剂选用184、784、819、1173、TPO中的一种或几种;
取低聚物20~70wt%、活性稀释剂10~40wt%、惰性稀释剂1~50wt%、光引发剂0.1~5wt%按照比例配料后,在水浴锅中加热搅拌30-60min,充分搅拌,获得混合均匀的光固化树脂;
(3)分别取染色陶瓷粉和光固化树脂各50vol%,加入相对于陶瓷粉体质量的3wt.%的span20作为分散剂、以及相对于料浆总质量2wt.%消泡剂、流平剂,粉体和分散剂分次加料,采用球磨机球磨12h以上混合,制得染色氧化锆陶瓷料浆。
2.根据权利要求1所述的制备方法得到的氧化锆陶瓷料浆,其特征在于该陶瓷料浆的固含量高、粘度低,当剪切速率超过50s-1时,其最佳粘度低于2Pa·s,所制备氧化锆陶瓷的强度可达750MPa。
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