Article(id=1241416386879222146, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.03.032, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1733155200000, receivedDateStr=2024-12-03, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773906331032, onlineDateStr=2026-03-19, pubDate=1748707200000, pubDateStr=2025-06-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773906331032, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773906331032, creator=13701087609, updateTime=1773906331032, updator=13701087609, issue=Issue{id=1241416382559081210, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='3', pageStart='1', pageEnd='223', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773906330003, creator=13701087609, updateTime=1773908015401, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241423451685179940, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241423451685179941, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=191, endPage=197, ext={EN=ArticleExt(id=1241416387604836757, articleId=1241416386879222146, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Application and Prospects of Photo-Curing for Ceramic, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

The fundamental principles of stereolithography (SLA), digital light processing (DLP), and two-photon polymerization (TPP) in photo-curing technique for ceramic were reviewed. Based on systematical introduction and analysis of the research status, application fields of SLA, DLP, and TPP technologies, as well as the existing challenges, a comprehensive review was provided of ceramic slurries and their performance optimization, photo-curing mechanisms, and subsequent debinding and sintering processes. Finally, prospects for obtaining ceramic slurries with high performance, finished products with superior mechanical properties and translating research outcomes into practical applications were discussed. Furthermore, several recommendations were proposed, including increasing the types of ceramic slurries, accelerating the development of composite ceramic materials, and making more efforts in research of large-size ceramic components.

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综述了陶瓷光固化技术中立体光刻(SLA)、数字光处理(DLP)和双光子聚合(TPP)技术的基本原理,系统介绍和分析了SLA、DLP、TPP技术的研究现状、应用领域以及存在的问题;在此基础上对陶瓷浆料及其性能优化、光固化机理以及后续脱脂烧结工艺进行了全面概述。最后,对获得优异性能的陶瓷浆料、高力学性能的成品以及研究成果的应用转化等进行了展望,并提出了增加陶瓷浆料种类、加快复合陶瓷材料发展、加大大尺寸陶瓷零件研究力度等建议。

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刘耀(1985—),男,浙江温州人,博士,副教授,主要研究方向为陶瓷增材制造、粉体成形。E-mail:
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张玄(1990—),女,江西萍乡人,讲师,主要研究方向为增材制造、智能仪器仪表。E-mail:

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张玄(1990—),女,江西萍乡人,讲师,主要研究方向为增材制造、智能仪器仪表。E-mail:

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张玄(1990—),女,江西萍乡人,讲师,主要研究方向为增材制造、智能仪器仪表。E-mail:

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(a)SLA;(b)DLP;(c)TPP

, figureFileSmall=ey/9uT8FP1IT/b28atkJrw==, figureFileBig=netsF/8cV7hfkcGlLkD4yA==, tableContent=null), ArticleFig(id=1241422269843567298, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416386879222146, language=EN, label=Fig.2, caption=Light scattering phenomenon in ceramic slurry, figureFileSmall=zMLkvP3D45EliHTqYuxriA==, figureFileBig=VTXmw9t1M0RK+J/8oSZrFA==, tableContent=null), ArticleFig(id=1241422269981979334, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416386879222146, language=CN, label=图2, caption=光在陶瓷浆料中的散射现象, figureFileSmall=zMLkvP3D45EliHTqYuxriA==, figureFileBig=VTXmw9t1M0RK+J/8oSZrFA==, tableContent=null), ArticleFig(id=1241422270166528716, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416386879222146, language=EN, label=Fig.3, caption=Resins after ultraviolet light curing, figureFileSmall=uP85PZxl4MqhH+dentBeWA==, figureFileBig=WVlCXTB9QFqo0/oOSp83Rg==, tableContent=null), ArticleFig(id=1241422270321717969, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416386879222146, language=CN, label=图3, caption=紫外光照射后不同树脂中的固化图像

(a)原始树脂;(b)陶瓷树脂

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陶瓷光固化技术应用及其展望
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张玄 , 钟佳妮 , 俞风英 , 占丽娜 , 刘耀
矿冶工程杂志 | 材料 2025,45(3): 191-197
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矿冶工程杂志 | 材料 2025, 45(3): 191-197
陶瓷光固化技术应用及其展望
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张玄 , 钟佳妮, 俞风英, 占丽娜, 刘耀
作者信息
  • 萍乡学院 机械电子工程学院,江西 萍乡 330034
  • 张玄(1990—),女,江西萍乡人,讲师,主要研究方向为增材制造、智能仪器仪表。E-mail:

通讯作者:

刘耀(1985—),男,浙江温州人,博士,副教授,主要研究方向为陶瓷增材制造、粉体成形。E-mail:
Application and Prospects of Photo-Curing for Ceramic
Xuan ZHANG , Jiani ZHONG, Fengying YU, Lina ZHAN, Yao LIU
Affiliations
  • School of Mechanical and Electronic Engineering, Pingxiang University, Pingxiang 330034, Jiangxi, China
出版时间: 2025-06-01 doi: 10.3969/j.issn.0253-6099.2025.03.032
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综述了陶瓷光固化技术中立体光刻(SLA)、数字光处理(DLP)和双光子聚合(TPP)技术的基本原理,系统介绍和分析了SLA、DLP、TPP技术的研究现状、应用领域以及存在的问题;在此基础上对陶瓷浆料及其性能优化、光固化机理以及后续脱脂烧结工艺进行了全面概述。最后,对获得优异性能的陶瓷浆料、高力学性能的成品以及研究成果的应用转化等进行了展望,并提出了增加陶瓷浆料种类、加快复合陶瓷材料发展、加大大尺寸陶瓷零件研究力度等建议。

陶瓷  /  增材制造  /  光固化  /  立体光刻  /  数字光处理  /  综述  /  3D打印

The fundamental principles of stereolithography (SLA), digital light processing (DLP), and two-photon polymerization (TPP) in photo-curing technique for ceramic were reviewed. Based on systematical introduction and analysis of the research status, application fields of SLA, DLP, and TPP technologies, as well as the existing challenges, a comprehensive review was provided of ceramic slurries and their performance optimization, photo-curing mechanisms, and subsequent debinding and sintering processes. Finally, prospects for obtaining ceramic slurries with high performance, finished products with superior mechanical properties and translating research outcomes into practical applications were discussed. Furthermore, several recommendations were proposed, including increasing the types of ceramic slurries, accelerating the development of composite ceramic materials, and making more efforts in research of large-size ceramic components.

ceramic  /  additive manufacturing  /  photo-curing  /  stereolithography (SLA)  /  digital light processing (DLP)  /  review  /  3D printing
张玄, 钟佳妮, 俞风英, 占丽娜, 刘耀. 陶瓷光固化技术应用及其展望. 矿冶工程杂志, 2025 , 45 (3) : 191 -197 . DOI: 10.3969/j.issn.0253-6099.2025.03.032
Xuan ZHANG, Jiani ZHONG, Fengying YU, Lina ZHAN, Yao LIU. Application and Prospects of Photo-Curing for Ceramic[J]. Mining and Metallurgical Engineering, 2025 , 45 (3) : 191 -197 . DOI: 10.3969/j.issn.0253-6099.2025.03.032
增材制造技术打破了人们对传统制造业的认知,被许多发达国家纳入国家战略规划中。目前,增材制造技术已经被广泛应用于消费电子、汽车、航天航空、医药、军事、造船等诸多领域中。
陶瓷材料因具有高强度、高硬度、耐磨损、耐腐蚀和耐高温等优点而被广泛应用于各行业。然而,陶瓷材料的传统加工方法(如干压、胶带铸造、滑铸、凝胶铸造和注塑成型等)极其依赖模具,很难制备具有复杂结构或高性能的陶瓷材料,极大限制了陶瓷材料的应用与发展。陶瓷增材制造(additive manufacturing,AM)技术采用逐层叠加的制造原理,能制备具有复杂结构的高质量陶瓷零件,从而拓展了陶瓷材料的应用领域。
根据成形方法的不同,陶瓷增材制造技术可分为熔融沉积成形(fused deposition modeling,FDM)、浆料直写成形(direct ink writing,DIW)、分层实体制造(laminated object manufacture,LOM)和光固化(photo-curing)等[1-2]。其中,光固化技术因能制备复杂、致密的陶瓷而备受关注。
光固化技术依据固化机理可分为立体光刻(stereolithography,SLA)、数字光处理(digital light processing,DLP)、双光子聚合(two-photon polymerization,TPP)方法,本文详细阐述了3种光固化技术的原理、研究现状、应用领域和存在的问题,在此基础上对陶瓷浆料及其性能优化、光固化机理以及后续脱脂烧结工艺进行了全面概述。最后对陶瓷浆料种类、复合陶瓷材料发展、大尺寸陶瓷零件制造提出了展望和建议。
光固化过程是典型的光化学反应,其基本原理是在光的照射下,光引发剂吸收紫外线或可见光后产生自由基或阳离子,这些活性物质引发树脂或单体分子的不饱和双键,产生新的自由基,发生双键反应,形成增长链,进一步形成聚合物链,然后形成交联网状结构,从而进一步形成特殊结构[3]
SLA技术最早由美国科学家Chuck Hull于1986年提出[4],随后被3D Systems公司商业化,目前已成为主流的陶瓷增材制造技术之一。该技术利用紫外线激光逐层扫描液态光敏树脂,使其发生固化反应。扫描过程通过移动镜片或镜面控制。SLA技术制备的元件具有较高的精度和表面质量,适用于快速原型制作、模型制作以及小批量产品的制作与生产。
DLP与SLA技术的成型原理基本相似,均利用紫外线光源固化光敏树脂。其差异在于,DLP是通过数字微镜设备(DMD)芯片首先对光信号进行数字化处理,再将处理后的信号以投影的形式转化成图像并投射至浆料打印槽进行逐层固化。相较于SLA技术的逐层扫描线固化,DLP的面曝光形式的打印速度更快、效率更高,且其设备稳定性好,加工成本低。DLP技术主要适用于打印小体积物体,也可用于小批量产品的制作与生产。
TPP技术[5]是一种比DLP更精密的光固化技术,目前该技术的打印精度已达到100 nm以下,可用于生产具有精细结构的小尺寸零件。TPP技术利用两个近红外激光束同时照射光敏聚合物,只有当两个光束同时聚焦到一个非常小的区域时,才会发生光聚合反应。该技术需要控制光束实现特殊的聚焦条件,因此其打印速度较慢,但由于其打印精度高,常被用于制作生物医学器件、精密电子元器件等微纳米结构元件。
3种光固化技术的原理见图1。SLA、DLP和TPP在光照方式、固化效率等方面均存在差异,生产的元件在精度和性能上也存在差异,以适应不同场合和领域的制造需求。
低聚物是一种含有不饱和功能基团的低分子聚合体,是光固化材料中最基本的材料。低聚物是由较少重复单元组成的聚合物,分子量小、化学结构较简单,且在光引发剂的作用下能快速产生聚合反应,由低分子单体合成网状聚合物[6-8]。低聚物一般为环氧丙烯酸酯(EA)、不饱和聚酯(UPE)、聚氨酯丙烯酸酯(PUA)等[9],可通过优化分子设计对不饱和聚酯进行改性来改善低聚物的性能。
低聚物决定了光敏性树脂的基本理化性质,如黏度、硬度和断裂伸长率。文献[10]对脂肪型超支化聚酯添加活性稀释剂进行端基改性后的性能进行了研究,发现其固化性能得到了进一步提高。文献[11]在涂层中加入不同类型的纳米颗粒,结果表明,改性后的聚合物涂层结合强度、硬度、耐磨性等性能均大幅提高;利用所制备的超支化高分子对甲基丙烯酸缩水甘油酯进行修饰,得到了硬度高、固化速率快的膜。文献[12]使用合成超支化聚合物对甲基丙烯酸缩水甘油酯进行改性处理,处理后其固化速率快、固化膜硬度大。文献[13]用EA、MDI(二苯基甲烷二异氰酸酯)、丙烯酸等合成了新的预聚物,该预聚物具有较低的黏度与良好的韧性。文献[14]采用甲苯二异氰酯酸对EA进行接枝改性,增加了涂层的柔韧性。文献[15]用环氧大豆油和丙烯酸在催化作用下合成了预聚物,有效改善了涂层柔韧性,降低了黏度。
稀释剂是一种含有多功能基团的有机小分子,其中的聚合物基团可以在紫外线照射下进行聚合,它是光固化体系中的重要组成部分。
活性稀释剂按固化机理的不同可分为自由基型和阳离子型。自由基型稀释剂包含丙烯酰氧基、甲基丙烯酰基、乙烯基、烯丙基等含有不饱和双键的单体,它的固化反应通过自由基光聚合开展。
活性稀释剂根据单体中的活性基团数量差异还可分为单官能团活性稀释剂、双官能团活性稀释剂和多官能团活性稀释剂等。活性稀释剂的化学结构、官能团数量和分子量等对陶瓷光固化坯体的硬度和韧性有很大影响,其中官能团数量越多,光固化反应速度越快且打印件烧结后收缩越明显。因此,在陶瓷光固化过程中,应尽可能选择单官能团和双官能团单体,使得具有一定光固化反应速度的同时能有效降低坯体收缩率和增加坯体打印过程中的平台附着力。
目前,随着研究的不断深入,稀释剂已经完成了三次更新迭代。第一代光固化稀释剂多为丙烯酸丁酯、苯乙烯等,该稀释剂的优点是活性高、黏度低,缺点是具有一定毒性、对皮肤刺激性大且易燃易爆等,这也限制了其在后续的广泛应用。第二代光固化稀释剂在克服了第一代稀释剂缺点的同时加快了固化速率。第三代光固化稀释剂是以甲氧端基类为代表的丙烯酸酯类,该稀释剂是单官能团单体,双键转换率高,使其不仅拥有多官能团单体反应活性高的优势,还具有低收缩率和高转化率,能有效润湿陶瓷无机粒子,提高光固化坯体与基体的结合强度和其在树脂中的分散性。
引发剂是陶瓷光固化技术的一个重要组成部分,其作用是启动聚合反应,提高光固化反应速率。
引发剂经紫外光辐射后被激发,从而产生自由基或阳离子,激发聚合活性,使得不饱和的双键化合物产生聚合,生成聚合物[16]。根据反应机理可将其分为裂解型、夺氢型和阳离子型。其中,可以苯偶酰衍生物等为原料制备裂解型光引发剂,该类引发剂容易因氧阻聚的作用影响光固化速度。文献[17]研究发现,添加光引发剂Irgacure 184可以很好地抑制氧阻聚现象。文献[18]通过应用涂层技术有效抑制了氧在光聚合反应中的干扰。文献[19]探讨了利用惰性气体环境对光固化反应中氧抑制效应的阻断。在夺氢型自由基光引发系统中,核心催化分子通常为二苯酮或杂环芳酮衍生物,其配合相应的协同助引发剂发挥作用。此类光引发剂由于改变了光引发体系,有效抑制氧阻聚的作用,提高了光固化速度。阳离子型光引发剂是电子给体和受体通过电子或电荷的转移,生成硫鎓盐等。文献[20]在油溶性溶液中加入亲水性的非离子基,合成了一种水基光引发剂。文献[21]合成了四苯基季铵盐引发剂,该引发剂转换率高且不易挥发。
表面改性剂在与陶瓷粉末混合后能降低粉末中的羟基,将亲水性的粉末变为亲油性,从而降低浆料黏度,其作用机理是加入表面改性剂后,它会在材料表面进行吸附、反应、包裹或与材料表面的化学键结合,从而减少粉末中的羟基。通过对陶瓷粉末表面进行涂层改性处理,可以有效降低陶瓷粉体与树脂之间的折射率差,使陶瓷粉体更好地分散在树脂体系中,提高后续打印过程中的打印分辨率,是制备高固相、低黏度浆料的一种有效途径。文献[22]对陶瓷粉末Al2O3进行改性处理,融入二元羧酸系列——丙、丁、戊、己、庚、辛、壬、癸,以拓展研究维度。通过沉降实验发现,由于改性后Al2O3粉末的羟基减少且粉体表面能降低,Al2O3浆料的稳定性得到了显著提升。同时,采用高效液相色谱技术精确测定了双羧酸在其表面的极限吸附量,发现该改性过程遵循单分子层化学吸附原理。文献[23]采用硬脂酸、油酸及多元醇对氧化锆粉体表面进行改性处理,结果表明,在加入质量分数3%油酸及适量BYK分散剂后,所得陶瓷浆料分散性较高。文献[24]在ZrO2中分别加入MAA、γ-MPS和SA进行改性,通过红外光谱图观察发现,此3种改性剂均以化学吸附的方式吸附在氧化锆表面进行改性。经检测,对于ZrO2粉末,MAA、γ-MPS和SA表面改性剂的适宜用量分别为0.5%、1.0%和1.5%。文献[25]用表面活性剂多功能梳妆聚合物电解质对Al2O3和ZrO2进行改性,改性后其分散性得到显著提升,原因为:多功能梳妆聚合物电解质具有较好的亲和力,使陶瓷颗粒被吸附进紫外可固化有机介质中,从而提高陶瓷浆料的分散性。
陶瓷光固化的浆料结构体系主要由陶瓷粉体、预聚物、单体(稀释剂)、分散剂等组成。为了制备结构复杂、致密且性能优异的陶瓷零部件,需尽量达到高固含量和低黏度。研究[26-27]发现,以黏度较低、固含量较高、分散均匀、流动性较好的陶瓷浆料为原料打印的陶瓷生坯具有表面性能优异和内部缺陷较少等优点。相反,以黏度较高、流动性差且分散不均匀的陶瓷浆料为原料制备的陶瓷生坯存在表面粗糙度大和内外部缺陷较多等缺点。不仅如此,在后续脱脂烧结过程中,烧结完成后陶瓷成品件的整体外观以及力学性能也与固相含量密切相关。低固含量的陶瓷浆料在烧结后容易出现微裂纹和高收缩率等问题,导致整体外观不完整。高固含量的陶瓷浆料在高温烧结后能获得整体外观完整、无缺陷且性能优异的零部件。因此,为了获得能满足不同需求的陶瓷零部件,应不断调整工艺以制备固相含量较高、陶瓷浆料黏度较低、流动性能较好的陶瓷浆料,使其均匀分散,减少高温脱脂及烧结后陶瓷材料的收缩、扭曲和变形。
文献[28]对羟基磷灰石(HA)分散于紫外光固化环氧树脂中的现象进行探讨,旨在分析HA浓度变化对陶瓷浆料性能的具体影响。经沉降及流变测试分析发现,通过调控剪切条件能改变浆料的流变性质,从而制得光固化陶瓷浆料,其固含量达47%、黏度达1.68 Pa·s。文献[29]对比了加入羟基磷灰石粉体的浆料与纯树脂单体的反应热,采用动力学评估固化过程,成功配制了光固化陶瓷浆料,其固含量达46%、黏度为2.15 Pa·s。文献[30]采用加热法探究浆料温度对浆料黏度的影响,通过实验发现,浆料的黏度随着浆料温度升高而快速降低,但过高的温度会加速浆料中陶瓷颗粒的团聚沉降,由此认为适宜的加热温度应低于60 ℃。
传统原始树脂的内部结构是均匀的,加入小尺寸陶瓷颗粒后,原始树脂不再均匀,其内部结构变得更加复杂[31]。悬浮在光敏树脂中的亚微米级和微米级陶瓷粒子由于存在光散射现象,极大破坏了光聚合过程。散射是一种光学现象,其由介质中的陶瓷颗粒改变光线路径所致。光在陶瓷浆料中的散射现象如图2所示。
紫外光从外部射入后,与陶瓷颗粒碰撞时会偏转;再次与陶瓷颗粒碰撞时又将发生一次偏转,此过程循环往复[32],降低了固化轮廓中的固化深度Cd,增加了固化宽度Cw。固化深度和固化宽度对颗粒的垂直和横向分辨率有显著影响[33-34]
粒子散射光的效率越高,固化深度越大。粒子散射光的效率取决于中位粒径、颗粒数量、颗粒与介质之间的折射率差(RI)等。中位粒径较小的陶瓷颗粒比中位粒径较大的陶瓷颗粒具有更大的比表面积,而比表面积越大,散射效应越高,因此,由细颗粒组成的陶瓷树脂中存在更多散射现象。粗颗粒能使更多光穿透,使得固化深度Cd更大。颗粒数量对散射效率的影响在于:随着颗粒数量增加,颗粒与颗粒之间以及颗粒与单体之间的间隙减小,导致光的传播距离短,散射随之增加。此外,陶瓷颗粒与树脂之间的折射率差的增加也会导致散射增加,这说明具有较大RI的粒子光散射具有更高的偏转角[35]
光在散射后不会消失,而是改变传播方向并继续在陶瓷浆料中向其他方向传播。针对此现象,文献[36]提出了一个描述陶瓷树脂中光衰减的预测模型:
式中:Dp为透射深度,μm;S为陶瓷颗粒的散射效应,cm-1A为光引发剂和惰性染料对光的吸收特性,mol/L;ϕ为陶瓷粉末在树脂中的体积分数,%。该模型表明:DpSAϕ紧密相关。
式(1)中,A与光引发剂和惰性染料的性质有关,其关系式为:
式中:εp为消光系数,L/(mol·cm);Cp为引发剂浓度,mol/L;以εpCp的乘积来表示引发剂的光吸收;εD为燃料消光系数,L/(mol·cm);CD为染料浓度,mol/L;以εDCD的乘积来量化惰性染料的光吸收。
因此式(1)可以改写成:
原始树脂受到紫外光照射后会发生固化。紫外光照射后不同树脂中的固化图像如图3所示。与原始树脂较窄的Cw不同,陶瓷树脂的轮廓表现出轮廓较宽的特征,这将降低特征分辨率。在陶瓷树脂中,固化轮廓通常较浅且较宽,且具有蘑菇状结构。由此可见,陶瓷树脂中固体颗粒的存在导致光散射增多,从而降低了打印精度。为了获得更高的精度,有必要保持CdCw之间的平衡。
考虑到加入陶瓷粉末后树脂的以上特性,原始树脂中固化深度Cd的解析式为:
式中:Cd为固化深度,mm;d为粉末平均粒径,μm;β为激光波长,nm;Δn2为偏差率(RI)的对比度(即陶瓷粉末RI与树脂RI之差),μm;Ec为临界能量,mJ/cm2Emax为最大能量,mJ/cm2。结合郎伯-比尔定律计算固化深度,可得:
式中Q为物质扩散辐射能力因子,它与颗粒间的距离为h(μm),光的波长为λ(nm),相关表达式为:
此外,固化宽度Cw在水平平台上,可用下式计算:
从式(7)可以看出,CdCw与基本参数均有联系。其中Cd与粉末平均粒径成正比(即粒径越大,固化深度越大),与粉末体积分数、激光波长及RI对比度成反比。文献[37]发现折射率差变小时,浆料的打印分辨率升高,即固化深度Cd增大,固化宽度Cw减小。陶瓷颗粒粒径越大、粒径分布越广时,固化深度Cd变大,固化宽度Cw变小。Cw随着Cd增加而增加,且其与透射深度Dp成反比,即Dp越大,Cw越小。文献[38]针对光固化中的能量剂量、光引发剂含量和固化深度构建了物理模型,通过对不同的曝光能量和不同光引发剂浓度进行浆料的固化,进一步确定了能提高浆料固化深度的曝光能量和光引发剂浓度。
与传统制造方法相比,增材制造(AM)是一种添加剂制造技术,它首先将陶瓷粉末、分散剂和光敏树脂混合并预处理,形成适当的光固化陶瓷悬浮液,然后通过吸收紫外光的激光能量同时诱导光聚合。感光树脂固化后用作黏结剂,将陶瓷颗粒黏结在一起,经过紫外光逐层固化得到陶瓷坯体,最后经过脱脂烧结获得最终成品。由于紫外光是逐层固化树脂,层与层之间在垂直和水平方向上的堆积密度不一致,这表明会出现层状结构[39-40]。在脱脂烧结过程中,树脂从层状结构特别是夹层树脂中脱落,可能会导致坯体内部或表面出现微裂纹,在随后的烧结过程中,高温下产生的热应力很大程度上会影响陶瓷的机械性能,从而导致微裂纹扩展[41-42]。此外,陶瓷生坯零件中层间相邻颗粒间距和层内相邻的颗粒间距不一致,可能会导致陶瓷颗粒间的融合不一致,从而影响陶瓷烧结零件的机械性能。
随着经典烧结理论和计算机技术的不断发展,研究人员开始采用计算机辅助模拟真实烧结过程中的微观结构变化,并对复杂的烧结模型进行了系统性模拟以接近实际烧结情况[43-44]。常用的模拟方法包括蒙特卡罗法(MC)、相场法(PFM)、分子动力学(MD)和元胞自动机(CA)[45-47]。文献[48]首先采用CA模型模拟再结晶、形核和晶粒长大的动态过程,利用CA法模拟晶粒长大的微观结构变化。文献[49]进行了基于热力学的二维晶粒生长CA模拟,研究发现,非真实结构的出现和晶粒粗化与最大取向数密切相关。文献[50]改进了CA方法的状态分配,在此基础上,研究讨论了陶瓷放电离子在烧结过程中烧结的温度梯度以及高温热反应对陶瓷微观结构的影响。文献[51]开发了一个多网格CA模型以模拟镍基高温合金在单程电子束熔炼过程中的枝晶生长过程,并证明了该模型在添加剂制造中的可行性和有效性。
致密度是决定打印产品质量的关键因素,致密度越高,产品性能越高,收缩率越低。文献[52]采用数字光处理(DLP)技术成功制备了氧化铝(Al2O3)陶瓷基坯,经烧结后展现出了510 MPa的抗弯强度及99.6%的高致密度。文献[53]采用Melpers 4350对氧化锆(ZrO2)进行了表面改性,并将改性处理后的粉末均匀分散于丙烯酸酯中形成浆料。该浆料借助DLP技术固化成型,再经烧结制得具有高致密度的氧化锆陶瓷螺钉,抵抗弯曲不断裂强度可达741 MPa。文献[54]利用数字光处理技术研制出带有凹槽的蜂窝状态氧化锆陶瓷及三角形氧化锆陶瓷,致密度为97.14%,并且发生了明显的收缩,最大收缩率为35.26%。
光固化成型技术有诸多优势:它不需要模具、工艺参数更新迭代迅速、可快速且高效地制作精密零部件。光固化技术制备的陶瓷生坯经脱脂烧结后,其致密度可达97%~99%,且光固化技术制备的零部件的部分力学性能接近传统制造法制备的零部件。尽管如此,陶瓷光固化技术仍存在局限性。首先,它在选材上存在一定的局限性。光固化所用陶瓷材料需对紫外光具备较好的光敏性,那些能吸收或反射紫外光的材料不适用于光固化成型技术,限制了光固化技术的进一步发展。此外,陶瓷光固化技术在打印镂空以及存在悬臂部分的零件时,需要打印支撑以防止打印件在打印过程中发生塌陷或扭曲变形,在后续工作中还需要对陶瓷零件进行去支撑处理;由于目前该处理工作还未实现自动化,需要手动辅助进行,导致陶瓷件的表面精度和表面完整性在去支撑的过程中有所降低。
针对光固化技术,国内外在优化和完善工艺流程、新型陶瓷浆料的配制及高性能光固化设备的更新方面获得了阶段性成果与技术革新,为精密铸造、生物医用材料以及航空航天领域带来了实质性应用。尽管成绩显著,光固化技术仍存在进步的空间。综上所述,将陶瓷光固化技术中需解决的问题及其发展展望归纳如下。
1)陶瓷浆料种类的扩展:目前研究较多的陶瓷浆料是Al2O3、ZrO2等氧化物陶瓷浆料,而对非氧化物陶瓷浆料的研究相对较少。随着社会的发展,各行各业对性能优异且精密无缺陷仪器的需求量日益增加,氧化物陶瓷浆料在某些领域无法满足需求,因此,具有优异性能的非氧化物陶瓷浆料(如Si3N4、SiC等)的发展优势日益显著。
2)复合陶瓷材料的发展:在实际应用中,单一陶瓷粉末所制备的陶瓷浆料不足以满足工业领域的需求。针对这一问题,研究人员通过在一种陶瓷粉末中添加另一种或多种陶瓷粉末以提高打印成品的力学性能,从而达到航空航天等极端环境下的应用标准。然而,加入多种陶瓷粉末后,陶瓷浆料原来的低黏度以及高固载的平衡关系将被打破,如何取得二者之间的平衡成为复合陶瓷浆料的研究热点。
3)大尺寸陶瓷零件的制造:受生产成本和技术的限制,以往的陶瓷光固化技术研究主要集中在具有复杂形状的小尺寸零件上。随着技术不断发展,大尺寸零件的研究逐渐受到重视。然而,光固化设备的工作台较小,难以制造大尺寸零件,且大尺寸零件在后续的脱脂烧结工程中容易形成裂纹,严重阻碍了研究成果向实际应用的转化。
未来,除了在日用品和装饰品方面的应用外,光固化技术还将在复合材料、电子元器件等领域发挥更大的作用。随着陶瓷光固化技术不断发展和完善,及人们对节能环保、高效生产等要求的提升,光固化技术将得到更加广泛的应用。同时,辅以互联网及大数据等新兴技术,光固化技术将朝着更信息化、自动化、智能化、产业化和多元化的方向迈进。
1)陶瓷光固化技术的核心在于制备低黏度、高固含量且满足打印条件的浆料,使其均匀分散,从而减少高温脱脂及烧结后陶瓷材料的收缩、扭曲和变形。为了获得低黏度、高固含量的浆料,在原树脂的基础上需添加低聚物、单体、分散剂等来调节浆料的性能。其中分散剂的加入使浆料在较高固含量下能保持较好的流动性和稳定的状态,从而提高浆料的打印性能。
2)散射现象、粉末中位粒径、体积分数、颗粒数和折射率差对陶瓷粉末的散射有一定影响,进而影响打印过程。
3)与传统制造方法不同,增材制造是一种添加剂制造技术,因此在脱脂烧结阶段还需通过不同的温度梯度对内部添加剂进行处理。此外致密度是决定打印产品质量的关键因素,致密度越高,产品性能越高,收缩率越低。
  • 江西省教育厅科学技术研究项目(GJJ2202117)
  • 萍乡市科技计划项目(2023C0106)
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2025年第45卷第3期
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doi: 10.3969/j.issn.0253-6099.2025.03.032
  • 接收时间:2024-12-03
  • 首发时间:2026-03-19
  • 出版时间:2025-06-01
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  • 收稿日期:2024-12-03
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江西省教育厅科学技术研究项目(GJJ2202117)
萍乡市科技计划项目(2023C0106)
作者信息
    萍乡学院 机械电子工程学院,江西 萍乡 330034

通讯作者:

刘耀(1985—),男,浙江温州人,博士,副教授,主要研究方向为陶瓷增材制造、粉体成形。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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