CN110698196A - 用于增材制造的双固化陶瓷材料及其制备方法和应用 - Google Patents
用于增材制造的双固化陶瓷材料及其制备方法和应用 Download PDFInfo
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- CN110698196A CN110698196A CN201910955375.6A CN201910955375A CN110698196A CN 110698196 A CN110698196 A CN 110698196A CN 201910955375 A CN201910955375 A CN 201910955375A CN 110698196 A CN110698196 A CN 110698196A
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Abstract
本申请公开了一种用于增材制造的双固化陶瓷材料及其制备方法和应用。所述制备方法包括：将低聚物与活性单体搅拌混合，得到溶剂；向所述溶剂中加入分散剂以使液体均匀分散；加入光引发剂、热引发剂和热固化促进剂，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀；加入消泡剂、阻聚剂、流平剂和烧结助剂得到树脂基溶液，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀；将陶瓷粉末分散于树脂基溶液中，待分散完成后对配制的材料进行球磨；待球磨均匀后，将得到的材料进行抽真空搅拌消去气泡。所述双固化陶瓷材料由所述制备方法制得。本申请的双固化陶瓷材料可应用于增材制造。本申请可使材料的固化深度得到提高。
Description
技术领域
本申请涉及增材制造材料技术领域，特别涉及一种用于增材制造的双固化陶瓷材料及其制备方法和应用。
背景技术
增材制造技术(又称3D打印技术或快速成型技术)经过一段时间的发展已经逐渐开始在个性化医疗、航空航天、建筑设计、汽车制造等重要国民经济领域发挥着作用。增材制造技术以数字化模型为基础，运用粉末状金属、热塑性塑料和光固化树脂等可粘合材料，通过逐层打印的方式构造物体。相对于高分子树脂和金属材料等的3D打印材料，陶瓷材料的开发存在着难以攻克的技术难关，如：在立体光刻(SLA，Stereo LithographyAppearance)成型过程中树脂基陶瓷浆料的固化深度受到限制，在有色陶瓷粉末体系中难以成型；这限制了3D打印技术在陶瓷材料成型方面的应用。
以上背景技术内容的公开仅用于辅助理解本申请的发明构思及技术方案，其并不必然属于本申请的现有技术，在没有明确的证据表明上述内容在本申请的申请日已经公开的情况下，上述背景技术不应当用于评价本申请的新颖性和创造性。
发明内容
本申请的发明人经过研究发现：对于在立体光刻成型过程中树脂基陶瓷浆料的固化深度受到限制，其原因在于陶瓷粉末与树脂对于紫外光折射率的差值过大导致紫外光散射；对于在有色陶瓷粉末体系中难以成型，其原因在于紫外光被有色的陶瓷粉末所吸收，从而导致树脂基陶瓷浆料难以建立立体结构。对此，本申请提出一种用于增材制造的双固化陶瓷材料及其制备方法和应用。本申请的双固化陶瓷材料在3D打印过程中的具有足够的固化深度，能够解决部分难固化陶瓷材料难以打印的技术问题。
在第一方面，本申请提供一种用于增材制造的双固化陶瓷材料的制备方法：使用如下重量占比的组分：1％至15％的低聚物；8％至30％的活性单体；1％至5％的光引发剂；1％至5％的热引发剂；0.001％至1％的热固化促进剂；0.1％至4％的分散剂；0.01％至3％的消泡剂；0.01％至1％的流平剂；0.001％至1％的阻聚剂；0.01％至2％的烧结助剂；60％至85％的陶瓷粉末；
将所述低聚物与所述活性单体搅拌混合，得到溶剂；
向所述溶剂中加入所述分散剂以使液体均匀分散；加入所述光引发剂、所述热引发剂和所述热固化促进剂，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀；
加入所述消泡剂、所述阻聚剂、所述流平剂和所述烧结助剂得到树脂基溶液，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀；
将所述陶瓷粉末分散于所述树脂基溶液中，待分散完成后对配制的材料进行球磨；待球磨均匀后，将得到的材料进行抽真空搅拌消去气泡。
在第二方面，本申请提供一种用于增材制造的双固化陶瓷材料，为上述制备方法制得的双固化陶瓷材料。
在第三方面，本申请提供上述双固化陶瓷材料在增材制造中的应用。
与现有技术相比，本申请的有益效果有：
使得材料在立体光刻成型过程中，一方面吸收紫外光引发光固化反应，另一方面利用激光与材料作用时产生的热量引发热聚合反应，从而使材料的固化深度得到提高。
附图说明
图1为本申请实施例的用于增材制造的光-热双固化陶瓷材料的制备方法的流程图。
具体实施方式
为了使本申请实施例所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合图1及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
本实施例提供一种用于增材制造的光-热双固化陶瓷材料的制备方法。该制备方法使用如下重量占比的组分：
1％至15％的低聚物；
8％至30％的活性单体；
1％至5％的光引发剂；
1％至5％的热引发剂；
0.001％至1％的热固化促进剂；
0.1％至4％的分散剂；
0.01％至3％的消泡剂；
0.01％至1％的流平剂；
0.001％至1％的阻聚剂；
0.01％至2％的烧结助剂；
60％至85％的陶瓷粉末。
制备时首先将低聚物与活性单体用电动搅拌器搅拌混合，得到溶剂；然后加入分散剂使液体均匀分散。随后加入光引发剂、热引发剂、热固化促进剂，加入消泡剂、阻聚剂、流平剂和烧结助剂得到树脂基溶液；其中，加入一种试剂(组分)后需要将溶液进行充分搅拌直至混合均匀。
采用超声分散设备将陶瓷粉末于树脂基溶液中分散；分散完毕后将配制的材料分装在球磨罐中，加入球磨珠球磨；待球磨均匀后分离球磨珠，将得到的材料进行抽真空搅拌消去气泡，即可得到光-热双固化树脂基陶瓷材料。
在本实施例中，低聚物可以为以下低聚物中的一种或多种。参与光固化反应的低聚物：具有不饱和双键基团的树脂，如环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚丙甲酸酯和丙烯酸氨基甲酸酯等；具有环氧基团或者乙烯基醚基团的树脂等，如环氧树脂和乙烯基醚树脂。参与热固化反应的树脂：不饱和聚酯树脂、丙烯酸酯树脂、环氧树脂或具有环氧基团的化合物等。
在本实施例中，活性单体为：含有碳碳双键的单体，如丙烯酰氧基化合物、甲基丙烯酰氧基化合物、乙烯基化合物，各类单官能团丙烯酸酯、双官能团丙烯酸酯、三官能团丙烯酸酯、多官能团丙烯酸酯等；含有乙烯基醚或环氧基基团的单体等。
在本实施例中，光引发剂为：裂解型引发剂、夺氢型引发剂和阳离子引发剂等中的一种或多种，如光引发剂819、TPO、651和二芳基碘鎓盐等。
在本实施例中，热引发剂为：环氧树脂固化剂、过氧化合物类热引发剂、偶氮类热引发剂、氧化还原类热引发剂等中的一种或多种，如过氧化苯甲酰(BPO)、偶氮二异丁腈(AIBN)、偶氮二异庚腈(ABVN)等。
在本实施例中，热固化促进剂为：醛胺类促进剂、有机磷化合物类促进剂等中的一种或多种，如：N,N-二甲基苯胺，苄基二甲胺。
在本实施例中，分散剂为：各类表面活性剂以及分散剂等，如柠檬酸钠、三乙醇胺、乙二胺四乙酸钠、聚乙烯醇、聚氨酯改性丙烯酸分散剂、油性聚氨酯润湿分散剂等的化合物中的一种或多种。
在本实施例中，消泡剂为：矿物油类消泡剂、有机硅类消泡剂、聚醚类消泡剂等各种消泡剂中的一种或多种，比如：硬脂酸、2-乙基己醇、磷酸三丁酯、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚和聚氧丙烯甘油醚等。
在本实施例中，流平剂为：丙烯酸类流平剂、有机硅类流平剂和氟碳化合物流平剂等中的一种或多种，如聚丙烯酸类和有机硅树脂等。
在本实施例中，阻聚剂为：酚类阻聚剂，醚类阻聚剂等中的一种或多种，比如特丁基邻苯二酚、对叔丁基邻苯二酚、对苯二酚、2—仲丁基—4.6—二硝基苯酚、羟基苯甲醚等。
在本实施例中，烧结助剂为：MgO-Al2O3-SiO2复合烧结助剂、Li2O-Al2O3-SiO2复合烧结助剂、CaO-Al2O3-SiO2复合烧结助剂等中的一种或多种。
在本实施例中，陶瓷粉末为：深色陶瓷粉末以及其他对紫外光折射率大于1.6的陶瓷粉末。
以下通过实验例和对照例对本实施进行说明。
实验例1
实验例1使用如表一所示重量占比的组分。
表一 实验例1使用的组分
实验例1的具体制备方法如下。
在烧杯中投入聚氨酯丙烯酸酯、环氧树脂、活性单体HEMA(甲基丙烯酸羟乙酯)；使用电动搅拌器分散，转速设置为200r/min，搅拌时间为20min，得到混合均匀的溶剂。
在室温下向溶剂中加入分散剂聚乙二醇、光引发剂TPO、光引发剂二芳基碘鎓盐、热引发剂BPO、热促进剂BDMA、阻聚剂对羟基苯甲醚、Drewplus消泡剂、流平剂BYK-333、MgO-Al2O3-SiO2复合烧结助剂，使用电动搅拌器分散30min，转速设置为200r/min，得到树脂基溶液。本步骤应避光操作。
将树脂基溶液置于超声振荡设备中，使用超声振荡30min；之后一边使用超声一边在溶液中加入3Y-TZP氧化锆粉末；待3Y-TZP氧化锆粉末全部添加完毕后，使用超声振荡10min，得到陶瓷浆料。本步骤应避光操作,使用超声的过程保持溶液和浆料温度为室温。
将陶瓷浆料装入球磨罐中，加入球磨珠；其中，球料比为3：1，转速设置为600r/min；球磨10h，之后用挤压法分离浆料与球磨珠。本步骤应避光操作。
将球磨后的陶瓷浆料放在真空搅拌设备中消除气泡，搅拌转速设置为100r/min，搅拌时间30min，待无明显气泡浮出，即可得到光-热双固化树脂基陶瓷材料。本步骤应避光操作。
实验例2
实验例2使用如表二所示重量占比的组分。
表二 实验例2使用的组分
实验例2的具体制备方法与实验例1的相同。
实验例3
实验例3使用如表三所示重量占比的组分。
表三 实验例3使用的组分
| 成分 | 重量占比 |
| 聚氨酯丙烯酸酯 | 1％ |
| 活性单体TEGDMA | 30％ |
| 光引发剂819 | 1％ |
| 热固化引发剂BPO | 5％ |
| 热促进剂N,N-二甲基苯胺 | 1％ |
| 流平剂BYK-358 | 0.1％ |
| CaO-Al<sub>2</sub>O<sub>3</sub>-SiO<sub>2</sub>复合烧结助剂 | 0.01％ |
| 氧化锆粉末 | 60％ |
| 阻聚剂701 | 1％ |
| 消泡剂BYK-071 | 0.01％ |
| 油性聚氨酯分散剂 | 0.1％ |
实验例3的具体制备方法与实验例1的相同。
对照例
对照例使用如表四所示重量占比的组分。
表四 对照例使用的组分
对照例的树脂基陶瓷浆料的配制方法为：将10份(10％)聚氨酯丙烯酸酯和23份(23％)活性单体HDDA放入烧杯中混合10min，再加入质量分数为3％的光引发剂TPO和质量分数为2％的消泡剂BYK-141和质量分数为2％的油性聚氨酯分散剂(本步骤需要避光)；在恒温磁力搅拌器上继续搅拌20min，待各组分充分混合后一边使用超声一边加入60份(60％)氧化锆粉末；氧化锆粉末加入完毕后再继续使用超声5至10min，从而完成对照例的树脂基陶瓷浆料的制备。
取实验例中的树脂基陶瓷浆料和对照例的树脂基陶瓷浆料，分别测试材料的固化深度，其结果为：对照例的材料的固化深度为0.105mm；实验例的材料的固化深度均大于0.2mm。可以看出，本实施例的双固化树脂基陶瓷浆料的固化深度明显高于单纯光固化成分树脂基陶瓷浆料的固化深度。
在本实施例中，对于氧化锆粉末制备的树脂基陶瓷材料，可提升其固化深度，可提高固化层间的结合力，使得打印成功率高；对于深色陶瓷粉末，可解决其不能打印的技术问题；由于交联度的提升，打印件的力学性能可得到提高。
本实施例的双固化陶瓷材料可应用于增材制造(或者说3D打印)。
以上内容是结合具体/优选的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，其还可以对这些已描述的实施方式做出若干替代或变型，而这些替代或变型方式都应当视为属于本申请的保护范围。
Claims (10)
1.一种用于增材制造的双固化陶瓷材料的制备方法，其特征在于：
使用如下重量占比的组分：
1％至15％的低聚物；
8％至30％的活性单体；
1％至5％的光引发剂；
1％至5％的热引发剂；
0.001％至1％的热固化促进剂；
0.1％至4％的分散剂；
0.01％至3％的消泡剂；
0.01％至1％的流平剂；
0.001％至1％的阻聚剂；
0.01％至2％的烧结助剂；
60％至85％的陶瓷粉末；
将所述低聚物与所述活性单体搅拌混合，得到溶剂；
向所述溶剂中加入所述分散剂以使液体均匀分散；加入所述光引发剂、所述热引发剂和所述热固化促进剂，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀；
加入所述消泡剂、所述阻聚剂、所述流平剂和所述烧结助剂，其中，每加入一种试剂后将溶液充分搅拌直至混合均匀，得到树脂基溶液；
将所述陶瓷粉末分散于所述树脂基溶液中，待分散完成后对配制的材料进行球磨；待球磨均匀后，将得到的材料进行抽真空搅拌消去气泡。
2.根据权利要求1所述的制备方法，其特征在于：
所述低聚物包括参与光固化反应的低聚物中的一种或多种，和/或包括参与热固化反应的树脂中的一种或多种；
所述参与光固化反应的低聚物的种类包括具有不饱和双键基团的树脂和具有环氧基团或者乙烯基醚基团的树脂；
所述参与热固化反应的树脂包括不饱和聚酯树脂、丙烯酸酯树脂、环氧树脂和具有环氧基团的化合物中的一种或多种。
3.根据权利要求1所述的制备方法，其特征在于：所述活性单体的种类包括含有碳碳双键的单体和含有乙烯基醚或环氧基基团的单体。
4.根据权利要求1所述的制备方法，其特征在于：所述光引发剂包括裂解型引发剂、夺氢型引发剂和阳离子引发剂中的一种或多种。
5.根据权利要求1所述的制备方法，其特征在于：所述热引发剂包括环氧树脂固化剂、过氧化合物类热引发剂、偶氮类热引发剂、氧化还原类热引发剂中的一种或多种。
6.根据权利要求1所述的制备方法，其特征在于：
所述热固化促进剂包括醛胺类促进剂、有机磷化合物类促进剂中的一种或多种；
所述分散剂包括柠檬酸钠、三乙醇胺、乙二胺四乙酸钠、聚乙烯醇、聚氨酯改性丙烯酸分散剂、油性聚氨酯润湿分散剂中的一种或多种；
所述消泡剂包括矿物油类消泡剂、有机硅类消泡剂、聚醚类消泡剂中的一种或多种；
所述流平剂包括丙烯酸类流平剂、有机硅类流平剂和氟碳化合物流平剂中的一种或多种；
所述阻聚剂包括酚类阻聚剂、醚类阻聚剂中的一种或多种。
7.根据权利要求1所述的制备方法，其特征在于：所述烧结助剂包括MgO-Al2O3-SiO2复合烧结助剂、Li2O-Al2O3-SiO2复合烧结助剂和CaO-Al2O3-SiO2复合烧结助剂中的一种或多种；所述陶瓷粉末为深色陶瓷粉末或者对紫外光折射率大于1.6的陶瓷粉末。
8.一种用于增材制造的双固化陶瓷材料，其特征在于：为根据权利要求1至7任一项所述的制备方法制得的双固化陶瓷材料。
9.根据权利要求8所述的双固化陶瓷材料，其特征在于：所述双固化陶瓷材料的固化深度大于0.2mm。
10.根据权利要求8或9所述的双固化陶瓷材料在增材制造中的应用。
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