CN114099769A - 一种采用粘弹膏体3d打印牙科全瓷修复体的材料及方法 - Google Patents
一种采用粘弹膏体3d打印牙科全瓷修复体的材料及方法 Download PDFInfo
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Abstract
本发明公开了一种采用粘弹膏体3D打印牙科全瓷修复体的材料及方法，其由反应性光固化单体及组合、陶瓷粉体、润湿分散剂、触变剂、引发剂等球磨混合或剪切混合或螺杆挤出而制成，牙科全瓷修复体的制作方法是先将待打印牙科全瓷修复体数据进行随形基底设计，然后在牙科全瓷修复体与基底之间设置特定厚度的间隙，再将牙科全瓷修复体、间隙和基底数据合并进行切片，将切片后的数据导入3D打印设备中，刮涂机构循环涂铺所述粘弹膏体，激光扫描所述基底和牙科全瓷修复体，遇见间隙数据时，激光为关闭状态，循环往复，直至完整的数据打印完成，再经过移除基底，清洗步骤，得到牙科全瓷修复体素坯，最后脱脂烧结，得到牙科全瓷修复体。
Description
技术领域
本发明涉及牙科全瓷修复体3D打印制造领域，具体为一种采用粘弹膏体3D打印牙科全瓷修复体的材料及方法。
背景技术
牙科全瓷修复体具有优异的力学性能、生物相容性和美学表现成为牙科固定修复领域理想的修复材料。目前制备牙科全瓷修复体的主流方法是计算机辅助设计和计算机辅助制造(CAD/CAM)，该技术加工精度高、边缘适合性好，但该技术材料浪费严重，而且陶瓷材料的高硬度易磨损刀具，并极易在牙科全瓷修复体表面引入微观裂纹，其应用依旧具有较大的局限性。相比于减材制造，增材制造技术(3D打印)可不受形状复杂程度限制构建任意几何特征零件，目前聚合物和金属3D打印已成功应用于种植导板、金属基底冠、活动义齿支架和隐形矫正等口腔领域，成为增材制造技术迅速拓展应用的重要领域之一。牙科全瓷修复体是一种型面复杂且精度要求极高的不规则曲面拟合体，3D打印技术可满足其精准、个性化和复杂结构构建的基本要求，有望成为牙科全瓷修复体制备的潜在候选技术。
陶瓷材料具有高熔点，选区激光熔融直接制造成型精度低且易出现裂纹。通常采用间接方法把含有陶瓷粉末和粘结剂的混合物构建形成三维素坯，再经有机物脱除和烧结致密化得到陶瓷零件。陶瓷立体光刻3D打印技术因可制备表面光洁度高、显微结构均匀、力学性能优异的复杂形状陶瓷部件，成为最有可能制造牙科全瓷修复体的候选3D打印技术，但该技术仍存在去支撑破坏冠表面完整性的问题，严重阻碍了这项技术在行业的应用。因此，发展一种适合于牙科全瓷修复体制作的3D打印材料和方法具有重要的临床价值。3D打印制备牙科全瓷修复体中获得完整表面、优异力学性能和精准尺寸是陶瓷3D打印技术的重要挑战。立体光刻技术是能够制备最优表面的陶瓷3D打印技术，但是采用该技术在制备悬空/悬臂时需要添加支撑结构，在移除支撑结构时容易破坏表面，甚至导致零件变形和开裂等诸多问题。有学者采用三段式支撑策略实现三单位固定桥的制备，但去支撑时造成的解剖结构破坏使制造精度难以满足使用要求。
发明内容
本发明的目的在于提供一种采用粘弹膏体3D打印牙科全瓷修复体的材料及方法，通过构建具有高屈服应力的粘弹膏体材料，该材料可对上部零件起到自支撑作用，通过3D打印制作具有完整表面的牙科全瓷修复体。
为达到上述目的，本发明提供如下技术方案：
一种采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其由反应性光固化单体及组合、陶瓷粉体、润湿分散剂、触变剂、引发剂等球磨混合或剪切混合或螺杆挤出而制成，其中，所述材料的屈服应力≥10 Mpa，固含量≥25 vol%，静止粘度≥1000 Pa·S，100s-1剪切速率下的粘度值：≤100 Pa·S。
进一步地，所述反应性光固化包括但不限于己二醇二丙烯酸酯(HDDA)、丙烯酸异冰片酯(IBOA)和丙氧基化新戊二醇二丙烯酸酯(PO-NPGDA)在内的反应性光固化单体及组合。
进一步地，所述陶瓷粉体包括但不限于氧化铝、氧化锆、氮化硅粉体及粉体的组合。
进一步地，所述润湿分散剂包括但不限于BYK-AT203，BYK-P104S，BYK-9076，BYK-111，BYK-Anti-Terra-U100。
进一步地，所述触变剂包括但不限于BYK-410，BYK-607。
进一步地，所述引发剂包括但不限于1-羟基环己基苯基甲酮，2,4,6-三甲基苯甲酰基-二苯基氧化膦，苯基双(2,4,6-三甲基苯甲酰基)氧化膦。
进一步地，所述粘弹膏体在100s-1剪切速率下的粘度值≤100 Pa·S。
为了达到上述目的，本发明还提出了采用粘弹膏体3D打印牙科全瓷修复体的方法，其包括如下步骤：
1）将待打印牙科全瓷修复体数据进行随形基底设计，所述基底和所述牙科全瓷修复体之间还设有特定厚度的间隙，且所述基底的上表面与所述牙科全瓷修复体的下表面形貌互补；
2）将牙科全瓷修复体、间隙和基底数据合并并切片；
3）将切片后的数据导入3D打印设备中，刮涂机构循环涂铺所述粘弹膏体，激光扫描所述基底和牙科全瓷修复体，遇见间隙数据时，激光为关闭状态，循环往复，直至完整的数据打印完成；
4）移除基底；
5）清洗，得到牙科全瓷修复体素坯；
6）脱脂烧结，得到牙科全瓷修复体。
进一步地，所述步骤1）中的特定厚度的间隙为切片厚度的1-100倍。
进一步地，所述步骤3）中的打印参数：光源为355nm或405nm点光源，功率为100-3000mw，所述牙科全瓷修复体的扫描速度为100-10000mm/s；或者所述步骤3）中的打印参数：光源为405nm面光源，功率为1-100mw/cm2，所述牙科全瓷修复体的曝光时间为1-10s。
进一步地，所述步骤6）中的脱脂参数：温度范围：室温-800℃，升温速度0-10℃/min，0-10℃/min程序降温至室温。
进一步地，所述步骤6）中的烧结参数：温度范围：室温-2000℃，升温速率0-30℃/min，0-30℃/min程序降温至室温。
本发明与现有技术相比，具有如下优点：
1）上述通过构建具有高屈服应力的粘弹膏体打印材料，可对上部零件起到自支撑作用，因此可以采用非接触支撑策略制作具有完整表面的牙科全瓷修复体；
2）粘弹膏体材料的存在形式使其具有极高的静止粘度，可极大减缓高密度陶瓷粉体的沉降析出；
3）粘弹膏体剪切变稀的流变学特性有利于增材制造成型过程中的工艺适应性，比如刮平。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明所公开的一种采用粘弹膏体3D打印牙科全瓷修复体的流程图。
图2为本发明所公开的牙科全瓷修复体、其基底以及间隙设计图。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其由反应性光固化单体及组合、陶瓷粉体、润湿分散剂、触变剂、引发剂球磨混合或剪切混合或螺杆挤出而制成，所述反应性光固化包括但不限于己二醇二丙烯酸酯(HDDA)、丙烯酸异冰片酯(IBOA)和丙氧基化新戊二醇二丙烯酸酯(PO-NPGDA)在内的反应性光固化单体及组合，所述陶瓷粉体包括但不限于氧化铝、氧化锆、氮化硅粉体及粉体的组合，所述润湿分散剂包括但不限于BYK-AT203，BYK-P104S，BYK-9076，BYK-111，BYK-Anti-Terra-U100，所述触变剂包括但不限于BYK-410，BYK-607，所述引发剂包括但不限于1-羟基环己基苯基甲酮，2,4,6-三甲基苯甲酰基-二苯基氧化膦，苯基双(2,4,6-三甲基苯甲酰基)氧化膦。
所述材料的指标要求：
(1) 屈服应力：≥10Mpa，优选≥100Mpa，更优≥200Mpa；
(2) 固含量：≥25 vol%，优选≥40 vol%，更优≥50 vol%；
(3) 静止粘度：≥1000 Pa·S，优选≥10000 Pa·S，更优≥100000 Pa·S；
(4) 100s-1剪切速率下的粘度值：≤100 Pa·S，优选≤500 Pa·S，更优≤10 Pa·S。
如图1、图2所示，为了达到上述目的，本发明还提出了采用粘弹膏体3D打印牙科全瓷修复体的方法，其包括如下步骤：
s1.将待打印牙科全瓷修复体数据进行随形基底设计，所述基底和所述牙科全瓷修复体之间还设有特定厚度的间隙，且所述基底的上表面与所述牙科全瓷修复体的下表面形貌互补；
S2.将牙科全瓷修复体、间隙和基底数据合并并切片；
S3.将切片后的数据导入3D打印设备中，刮涂机构循环涂铺所述粘弹膏体，激光扫描所述基底和牙科全瓷修复体，遇见间隙数据时，激光为关闭状态，循环往复，直至完整的数据打印完成；
S4.移除基底；
S5.清洗，得到牙科全瓷修复体素坯；
S6.脱脂烧结，得到牙科全瓷修复体。
实施例1
采用氧化铝粘弹膏体3D打印制作氧化铝牙科全瓷修复体的步骤：
先将待打印的牙科全瓷修复体数据、间隙和随形底座进行三维模型设计、切片，将切片后的数据导入陶瓷3D打印机中，激光顺序扫描氧化铝粘弹膏体形成固体的氧化铝牙科全瓷修复体和基底素坯，刮涂机构循环涂铺在间隙，且激光为关闭状态，直至完整的零件打印完成，然后移除基底，再脱脂烧结，最终得到氧化铝牙科全瓷修复体。主要打印参数：光源为355nm，功率为300mw，陶瓷零件和底座支撑的扫描速度均为4000mm/s，间隙为0.21mm，切层厚度为0.07mm。其中脱脂参数：室温至80度，0.5℃/min，80度保温2小时；80-170℃，0.25℃/min，170℃保温2小时；170-350℃，0.25℃/min，350保温4小时；350-600℃，0.125℃/min，600℃保温2小时，烧结参数：室温至1600℃，5℃/min，1600℃保温2小时，10℃/min冷却至室温。
实施例2
采用氧化锆粘弹膏体3D打印制作氧化锆牙科全瓷修复体的步骤：
先将待打印牙科全瓷修复体数据和基底进行三维模型设计、切片，将切片后的数据导入陶瓷3D打印机中，激光顺序扫描氧化锆粘弹膏体形成固体的牙科全瓷修复体和基底素坯，刮涂机构循环涂铺在间隙，且激光为关闭状态，直至完整的零件打印完成，然后移除基底，得到氧化锆牙科全瓷修复体素坯，再脱脂烧结，最终得到氧化锆牙科全瓷修复体。其打印参数：光源为355nm，功率为600mw，氧化锆陶瓷牙齿的扫描速度为2000mm/s，基底支撑的扫描速度为4000mm/s，间隙为0.12mm，切层厚度为0.03mm。其脱脂参数：室温至80度，0.5℃/min，80度保温2小时；80-170℃，0.25℃/min，170℃保温2小时；170-350℃，0.25℃/min，350保温4小时；350-600℃，0.125℃/min，600℃保温2小时，烧结参数：室温至1250℃，1.6℃/min，1250-1450℃，1小时，1450℃保温2小时，0.66℃/min冷却至室温。
本发明提出了一种以粘弹膏体材料为原料的陶瓷立体光刻3D打印技术制作牙科全瓷修复体的新方法，一方面，膏体材料利用陶瓷粉末颗粒间强大的作用力使复杂结构制作时无需额外的支撑结构，为制备悬垂结构提供了可能；另一方面，膏体材料具有极高的静止粘度，相比于低粘度的浆体材料具有更好的稳定性，有利于防止因为陶瓷粉和分散介质密度差产生分相和沉降。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (12)
1.一种采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其特征在于，其由反应性光固化单体及组合、陶瓷粉体、润湿分散剂、触变剂、引发剂等球磨混合或剪切混合或螺杆挤出而制成，其中，所述材料的屈服应力≥10 Mpa，固含量≥25 vol%，静止粘度≥1000 Pa·S，100s-1剪切速率下的粘度值：≤100 Pa·S。
2.根据权利要求1所述的采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其特征在于，所述反应性光固化包括但不限于己二醇二丙烯酸酯(HDDA)、丙烯酸异冰片酯(IBOA)和丙氧基化新戊二醇二丙烯酸酯(PO-NPGDA)在内的反应性光固化单体及组合。
3.根据权利要求1所述的采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其特征在于，所述陶瓷粉体包括但不限于氧化铝、氧化锆、氮化硅粉体及粉体的组合。
4.根据权利要求1所述的采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其特征在于，所述润湿分散剂包括但不限于BYK-AT203，BYK-P104S，BYK-9076，BYK-111，BYK-Anti-Terra-U100。
5.根据权利要求1所述的采用粘弹膏体进行牙科全瓷修复体3D打印的材料，其特征在于，所述触变剂包括但不限于BYK-410，BYK-607。
6.根据权利要求1所述的采用高屈服应力膏体进行牙科全瓷修复体3D打印的材料，其特征在于，所述引发剂包括但不限于1-羟基环己基苯基甲酮，2,4,6-三甲基苯甲酰基-二苯基氧化膦，苯基双(2,4,6-三甲基苯甲酰基)氧化膦。
7.一种采用如权利要求1所述的粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，其包括如下步骤：
1）将待打印牙科全瓷修复体数据进行随形基底设计，所述基底和所述牙科全瓷修复体之间设置特定厚度的间隙，且所述基底的上表面与所述牙科全瓷修复体的下表面形貌互补；
2）将牙科全瓷修复体、间隙和基底数据合并并切片；
3）将切片后的数据导入3D打印设备中，刮涂机构循环涂铺所述粘弹膏体，激光扫描所述基底和牙科全瓷修复体，遇见间隙数据时，激光为关闭状态，循环往复，直至完整的数据打印完成；
4）移除基底；
5）清洗，得到牙科全瓷修复体素坯；
6）脱脂烧结，得到牙科全瓷修复体。
8.根据权利要求7所述的采用粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，所述步骤1）中设置的特定厚度的间隙为分层切片厚度的1-100倍。
9.根据权利要求7所述的采用粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，所述步骤3）中的打印参数：光源为355nm或405nm点光源，功率为100-3000mw，所述牙科全瓷修复体的扫描速度为100-10000mm/s。
10.根据权利要求7所述的采用粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，所述步骤3）中的打印参数：光源为405nm面光源，功率为 1-100mw/cm2，所述牙科全瓷修复体的曝光时间为1-10s。
11.根据权利要求7所述的采用粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，所述步骤6）中的脱脂参数：温度范围：室温-800℃，升温速度0-10℃/min，0-10℃/min程序降温至室温。
12.根据权利要求7所述的采用粘弹膏体进行牙科全瓷修复体3D打印的方法，其特征在于，所述步骤6）中的烧结参数：温度范围：室温-2000℃，升温速率0-30℃/min，0-30℃/min程序降温至室温。
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