CN107216155B - 一种用于激光3d打印/冷等静压复合成型的pf/pva双覆膜陶瓷粉末及其制备方法 - Google Patents
一种用于激光3d打印/冷等静压复合成型的pf/pva双覆膜陶瓷粉末及其制备方法 Download PDFInfo
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Abstract
本发明提供一种用于激光3D打印/冷等静压复合成型的酚醛树脂/聚乙烯醇双覆膜陶瓷粉末及其制备方法，该方法第一步将陶瓷粉末、柔软剂PEG、分散剂与水按一定比例混合得陶瓷浆料，接着向其中加入1wt％的PVA，烘干研磨过筛得PVA覆膜陶瓷粉末；第二步将PVA覆膜陶瓷粉末、酚醛树脂2123与甲醇混合均匀后，烘干粉碎研磨过筛，得酚醛树脂2123/PVA双覆膜陶瓷粉末。本发明制备的酚醛树脂2123/PVA双覆膜陶瓷粉末，有利于SLS技术成型陶瓷材料，促进CIP过程的致密化处理，从而提高初始形坯的强度和形状，并且具有工艺简单、设备要求低、不会对环境造成污染等诸多优点。
Description
技术领域
本发明涉及3D打印快速成型技术领域，具体涉及一种用于激光3D打印/冷等静压复合成型的酚醛树脂/聚乙烯醇双覆膜陶瓷粉末及其制备方法。
背景技术
随着电子计算机技术的发展，利用计算机直接制造各种复杂形状零件的技术取得了长足进步，90年代初H.Marcus等人提出了固体无模成型制造思路。选择性激光烧结技术(Selective Laser Sintering，简称SLS)是无模成型中使用比较广泛的方法，其工作原理是：在可升降的台面上铺上一层固体材料粉末，用激光对粉末进行扫描照射，激光扫过的部位粉末被烧结未扫描的部位粉末不烧结仍留在原处，成为新的一层粉末的支撑部分；烧结好一层后台面下降，进行第二层铺粉、烧结；如此反复进行直到零件坯体被制造出来。SLS成型工艺简单，能成型结构复杂的零件，对零件结构的复杂性没有任何限制，并且能够根据需要随时轻松更改零件结构。如今，SLS成型方法普遍用于金属材料、高分子材料的成型，在陶瓷材料成型方面有很大的缺陷，主要存在陶瓷材料成型复杂零件比较困难、成型零件密度低、机械性能差等问题。
为了提高陶瓷材料SLS技术成型零件的机械强度，华中科技大学史玉升教授等人提出采用冷等静压技术(Cold Isostatic P ressing，简称CIP)对SLS陶瓷材料成型坯体进行补强处理[史玉升，刘凯，贺文婷等.选择性激光烧结/冷等静压复合制造高密度Al2O3异形陶瓷件的研究[J].应用激光,2013,33(1):1-6]。CIP技术是指在常温下采用液体均匀传压的特性，对橡胶包套中的粉末施加各向均匀压力使粉末成型的一种成型技术。该技术使得坯体中粒子位移变形，坯体致密化程度更高，从而增强陶瓷零件的机械强度。
陶瓷材料分子结构稳定熔点高，在激光烧结时不易成型为固定结构。陶瓷材料SLS成形时需添加成型粘接剂，在进行激光烧结时，粘接剂融化将陶瓷粉末粘接成型。陶瓷粉末中添加粘接剂的方法一般有两种：一种是机械混合法，即将陶瓷粉末和粘接剂粉末进行简单的机械混合，使得粘接剂大致均匀的分布在陶瓷粉末中；另一种是覆膜法，即陶瓷粉末作为晶核被紧紧的包覆在有机粘接剂内部，参见CN100432019C以及CN103601502A。采用覆膜法时，粘接剂会相对均匀的分布在陶瓷粉末中，成型的形坯强度比较高；且覆膜法粘接剂加入量少，在脱脂处理后，坯体中的孔隙少，最终烧结体的密度和强度也较高。然而，目前用于SLS/CIP成型的覆膜陶瓷粉末仍存在粘接剂种类少、粘接性能差、制备成本高、SLS成型坯体在CIP阶段易变形等缺陷。
发明内容
本发明的目的在于克服现有用于SLS/CIP成型的陶瓷粉末存在的上述种种缺陷，提供一种用于激光3D打印/冷等静压复合成型的酚醛树脂/聚乙烯醇双覆膜陶瓷粉末及其制备方法。该方法利用酚醛树脂2123软化点低、粘接性强、成型收缩率小等优点，将其作为SLS陶瓷粉末成型时的粘接剂，利用聚乙烯醇(PVA)的润滑作用促进坯体在CIP阶段的致密化，最终制备出了性能优异的酚醛树脂2123-聚乙烯醇双覆膜陶瓷粉末。
本发明的目的之一在于提供一种用于激光3D打印/冷等静压复合成型的PF/PVA双覆膜陶瓷粉末，该双覆膜陶瓷粉末包括陶瓷粉末基体和包覆在基体上的内层、外层，其中陶瓷粉末基体为氧化铝、碳化硅、氧化锆、高白土、氮化硅中的一种，内层为聚乙烯醇(PVA)层，外层为酚醛树脂(PF)层。陶瓷粉末表面覆上PVA层，用于CIP致密化处理过程；最外面再覆上酚醛树脂2123层，用于SLS成型过程，在SLS成型过程中PVA层不被烧结。
本发明的另一目的在于提供一种用于激光3D打印/冷等静压复合成型的PF/PVA双覆膜陶瓷粉末的制备方法，包括以下步骤：(a)首先将陶瓷粉末、柔软剂、分散剂与去离子水混合搅拌均匀，得到陶瓷浆料；(b)向步骤(a)所得陶瓷浆料中加入聚乙烯醇(PVA)并搅拌均匀，加热保温反应，反应完成后经干燥、粉碎得到PVA覆膜陶瓷粉末；(c)将步骤(b)所得PVA覆膜陶瓷粉末与酚醛树脂、有机溶剂混合均匀，搅拌加热反应，反应完成后经干燥、粉碎得到PF/PVA双覆膜陶瓷粉末。
按照上述方案，所述陶瓷粉末为纳米级或亚微米级的氧化铝、碳化硅、氧化锆、高白土、氮化硅中的一种。采用纳米或亚微米级陶瓷粉末是因为其表面自由能高，烧结活性好。
按照上述方案，所述柔软剂为聚乙二醇(PEG)，所述分散剂为四甲基氢氧化铵(TMAH)或柠檬酸铵(TAC)。
按照上述方案，所述有机溶剂为甲醇，所述酚醛树脂型号为2123。
按照上述方案，步骤(a)柔软剂的加入量为陶瓷粉末的0.3-0.6wt％，分散剂的加入量为陶瓷粉末的0.1-0.5wt％。
按照上述方案，步骤(b)中聚乙烯醇的加入量占陶瓷浆料的1wt％。
按照上述方案，步骤(c)中按照4-15:1的质量比将PVA覆膜陶瓷粉末、酚醛树脂混合，再加入足量有机溶剂。
按照上述方案，向陶瓷浆料中加入聚乙烯醇时，搅拌并升温至75℃保温反应1-2h。
按照上述方案，将PVA覆膜陶瓷粉末、酚醛树脂以及有机溶剂混合均匀后，在0.5-1h升温至45℃，保温反应2-3h。
本发明采用PVA、酚醛树脂2123对陶瓷粉末进行双覆膜处理，利用酚醛树脂2123软化点低、粘接性强、成型精度高、机械强度高等优点，将其作为SLS陶瓷粉末成型时的粘接剂；由于SLS坯体强度较低，在CIP阶段易发生变形、破碎等缺陷，所以本发明采用PVA对陶瓷粉末进行第一层覆膜，利用PVA材料的润滑作用促进粉末在CIP阶段的致密化处理。在SLS陶瓷粉末成型阶段，激光扫描粉末，仅烧熔外层的酚醛树脂2123，在酚醛树脂2123结晶固化的同时将陶瓷粉末粘接成型。在CIP致密化处理过程中，陶瓷粉粒在PVA膜层的润光滑作用下易于位移、变形，减小粉末间距，形成较高密度的压坯，同时能保证坯体形状的完整。
与现有技术相比，本发明的有益效果为：(1)利用覆膜法对陶瓷粉末进行覆膜，粘接剂加入量少，成型的形坯强度比较高，在脱脂处理后，坯体中的孔隙少，最终烧结体的密度和强度较高；(2)利用双覆膜法，粘接剂和PVA分层分布，且分布均匀，材料稳定，不易发生偏聚现象造成后续处理过程中零件变形和破裂现象发生；(3)利用PVA的润滑作用，促进SLS形坯在CIP技术下的致密化，得到密度、强度更高的坯体；(4)利用PVA溶于水不溶于甲醇，酚醛树脂2123溶于甲醇的性质，采用普通的搅拌器、反应釜就可制得双覆膜粉体，工艺简单；(5)解决了传统的喷雾干燥法工艺复杂、成本较高、对材料和设备要求较高等难题。
附图说明
图1为本发明PF/PVA双覆膜陶瓷粉末结构及SLS/CIP成型原理示意图。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果，以下结合具体实施例进行进一步说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
一种用于激光3D打印/冷等静压复合成型的PF/PVA双覆膜陶瓷粉末的制备方法，具体包括以下步骤：
1)将陶瓷粉末(纳米级或亚微米级的氧化铝、碳化硅、氧化锆、高白土、氮化硅中的一种)、PEG(柔软剂)、分散剂(TMAH或TAC)，按一定比例加入反应釜中，再加入一定量去离子水，搅拌0.5～1h，制得陶瓷浆料。其中，分散剂的加入量为陶瓷粉末的0.1～0.5wt％，PEG的加入量为陶瓷粉末的0.3％～0.6wt％，去离子水的加入量要使得搅拌釜的搅拌头处于液面以下。
2)向陶瓷浆料中加入1wt％的PVA(聚乙烯醇)并搅拌1h左右，同时逐步加热至75℃左右，使PVA完全溶于离子水中，保温1～2h，自然冷却后将粉末聚集体烘干，再取出粉碎研磨过筛，得到PVA覆膜陶瓷粉末。
3)将PVA覆膜陶瓷粉末、酚醛树脂2123按照4-15:1的质量比加入反应釜中，加入足量的甲醇溶剂。一般需保证溶剂将混合粉末淹没，溶剂液面略高于粉末。由于甲醇有毒性，应将PVA覆膜陶瓷粉末、酚醛树脂2123加入到盛有甲醇的密闭环境中，通入保护气氦气，并将甲醇收集装置与密闭环境相连，甲醇挥发后通过收集装置收集。
4)在0.5～1h内将反应釜温度升至45℃，升温的同时进行机械搅拌，使得酚醛树脂2123完全溶于甲醇中，然后保温2～3h；再冷却至室温，取出覆膜粉末聚集体，将其烘干后粉碎研磨过筛，即得到酚醛树脂2123/PVA双覆膜陶瓷粉末。
实施例1
制备酚醛树脂2123/PVA碳化硅双覆膜粉末
(1)将SiC粉末(市售，平均粒径为0.74μm，纯度大于96％)、相当于SiC粉末0.5wt％的PEG(柔软剂)和0.5wt％分散剂TMAH加入反应釜中，再加入一定量去离子水，搅拌0.5～1h，制得碳化硅浆料。
(2)向浆料中加入1wt％的PVA(聚乙烯醇)搅拌1h左右，同时逐步加热至75℃左右，使PVA完全溶于去离子水中，然后保温1～2h。自然冷却后，将粉末聚集体烘干，再粉碎研磨过筛，得到PVA覆膜碳化硅粉末。
(3)将PVA覆膜碳化硅粉末、酚醛树脂2123按4:1的质量比加入反应釜中，加入足量的甲醇溶剂，一般使得溶剂将混合粉末淹没，溶剂液面略高于粉末。将反应釜和与之相连的甲醇挥发收集装置整体密封，通氦气保护。
(4)在0.5～1h内将反应釜温度升至45℃，升温的同时进行机械搅拌，使得酚醛树脂2123完全溶于甲醇中，然后保温2～3h。接着冷却至室温，取出覆膜粉末聚集体，将其烘干后粉碎研磨过筛，即得到酚醛树脂2123/PVA双覆膜碳化硅粉末。
实施例2
制备酚醛树脂2123/PVA氧化铝双覆膜粉末
(1)将氧化铝粉末(市售，平均粒径为0.74μm，纯度大于96％)、相当于氧化铝粉末0.5wt％的PEG(柔软剂)和0.5wt％分散剂TAC加入反应釜中，再加入一定量去离子水，搅拌0.5～1h，制得氧化铝浆料。
(2)向浆料中加入1wt％的PVA(聚乙烯醇)搅拌1h左右，同时逐步加热至75℃左右，使PVA完全溶于去离子水中，然后保温1～2h。自然冷却后，将粉末聚集体烘干，再粉碎研磨过筛，得到PVA覆膜氧化铝粉末。
(3)将PVA覆膜氧化铝粉末、酚醛树脂2123按15:1的质量比加入反应釜中，加入足量的甲醇溶剂，一般使得溶剂将混合粉末淹没，溶剂液面略高于粉末。将反应釜和与之相连的甲醇挥发收集装置整体密封，通氦气保护。
(4)在0.5～1h内将反应釜温度升至45℃，升温的同时进行机械搅拌，使得酚醛树脂2123完全溶于甲醇中，然后保温2～3h。接着冷却至室温，取出覆膜粉末聚集体，将其烘干后粉碎研磨过筛，即得到酚醛树脂2123/PVA双覆膜氧化铝粉末。
实施例3
制备酚醛树脂2123/PVA氧化锆双覆膜粉末
(1)将氧化锆粉末(市售，平均粒径为0.85μm，纯度大于98％)、相当于氧化锆粉末0.5wt％的PEG(柔软剂)和0.5wt％分散剂TAC加入反应釜中，再加入一定量去离子水，搅拌0.5～1h，制得氧化锆浆料。
(2)向浆料中加入1wt％的PVA(聚乙烯醇)搅拌1h左右，同时逐步加热至75℃左右，使PVA完全溶于去离子水中，然后保温1～2h。自然冷却后，将粉末聚集体烘干，再粉碎研磨过筛，得到PVA覆膜氧化锆粉末。
(3)将PVA覆膜氧化锆粉末、酚醛树脂2123按10:1的质量比加入反应釜中，加入足量的甲醇溶剂，一般使得溶剂将混合粉末淹没，溶剂液面略高于粉末。将反应釜和与之相连的甲醇挥发收集装置整体密封，通氦气保护。
(4)在0.5～1h内将反应釜温度升至45℃，升温的同时进行机械搅拌，使得酚醛树脂2123完全溶于甲醇中，然后保温2～3h。接着冷却至室温，取出覆膜粉末聚集体，将其烘干后粉碎研磨过筛，即得到酚醛树脂2123/PVA双覆膜氧化锆粉末。
Claims (9)
1.一种用于激光3D打印/冷等静压复合成型的PF/PVA双覆膜陶瓷粉末，其特征在于：该双覆膜陶瓷粉末包括陶瓷粉末基体和包覆在基体上的内层、外层，其中陶瓷粉末基体为氧化铝、碳化硅、氧化锆、高白土、氮化硅中的一种，内层为聚乙烯醇层，外层为酚醛树脂层。
2.一种用于激光3D打印/冷等静压复合成型的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于，包括以下步骤：
(a)首先将陶瓷粉末、柔软剂、分散剂与去离子水混合搅拌均匀，得到陶瓷浆料；
(b)向步骤(a)所得陶瓷浆料中加入聚乙烯醇并搅拌均匀，加热保温反应，反应完成后经干燥、粉碎得到PVA覆膜陶瓷粉末；
(c)将步骤(b)所得PVA覆膜陶瓷粉末与酚醛树脂、有机溶剂混合均匀，搅拌加热反应，反应完成后经干燥、粉碎得到PF/PVA双覆膜陶瓷粉末；
所述陶瓷粉末为纳米级或亚微米级的氧化铝、碳化硅、氧化锆、高白土、氮化硅中的一种。
3.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：所述柔软剂为聚乙二醇，所述分散剂为四甲基氢氧化铵或柠檬酸铵。
4.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：所述有机溶剂为甲醇，所述酚醛树脂型号为2123。
5.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：步骤(a)中柔软剂的加入量为陶瓷粉末的0.3-0.6wt％，分散剂的加入量为陶瓷粉末的0.1-0.5wt％。
6.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：步骤(b)中聚乙烯醇的加入量占陶瓷浆料的1wt％。
7.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：
步骤(c)中按照4-15:1的质量比将PVA覆膜陶瓷粉末、酚醛树脂混合，再加入足量有机溶剂。
8.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：
向陶瓷浆料中加入聚乙烯醇时，搅拌并升温至75℃保温反应1-2h。
9.根据权利要求2所述的PF/PVA双覆膜陶瓷粉末的制备方法，其特征在于：
将PVA覆膜陶瓷粉末、酚醛树脂以及有机溶剂混合均匀后，在0.5-1h升温至45℃，保温反应2-3h。
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