CN109071802B - 用于制造三维物体的方法 - Google Patents

用于制造三维物体的方法 Download PDF

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Publication number
CN109071802B
CN109071802B CN201780025808.7A CN201780025808A CN109071802B CN 109071802 B CN109071802 B CN 109071802B CN 201780025808 A CN201780025808 A CN 201780025808A CN 109071802 B CN109071802 B CN 109071802B
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acid
group
mixture
polyamide
support material
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CN109071802A (zh
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N.J.辛格尔特里
S.乔尔
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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Abstract

本发明涉及一种用增材制造系统制造三维物体的方法，所述增材制造系统例如为基于挤出的增材制造系统、选择性激光烧结系统、和/或基于电子摄影术的增材制造系统，该方法包括提供包含大于50％wt.的半结晶聚酰胺[聚酰胺(A)]的支撑材料，该聚酰胺具有如根据ASTM D3418确定的至少250℃的熔点并且具有通过浸入23℃的水中的至少2％wt.的饱和吸水率。

Description

用于制造三维物体的方法
相关申请
本申请要求于2016年4月1日提交的美国临时申请号62/316,835的优先权，出于所有目的将所述申请的全部内容通过援引方式并入本申请。
技术领域
本披露涉及用于打印三维(3D)零件和支撑结构的增材制造系统。特别地，本披露涉及在增材制造系统中的使用的支撑材料、在增材制造系统中使用这些支撑材料以及组件来打印3D零件的方法。
背景技术
增材制造系统被用于使用一种或多种增材制造技术从3D零件的数字表示打印或以其他方式构建3D零件。商业可用的增材制造技术的实例包括基于挤出的技术、喷射、选择性激光烧结、粉末/粘合剂喷射、电子束熔炼和立体光刻工艺。对于这些技术的每一种，3D零件的数字表示最初被切成多个水平层。对于每一个切片层，然后生成工具路径，其为具体的增材制造系统提供打印给定层的指令。
例如，在基于挤出的增材制造系统中，3D零件可以通过挤出可流动的零件材料以逐层的方式从3D零件的数字表示来打印。该零件材料通过该系统的打印头携带的挤出尖端挤出，并且作为一系列道路沉积在x-y平面的压板上。挤出的零件材料熔融至预先沉积的零件材料，并在温度下降时固化。然后打印头相对于基板的位置沿着z-轴(垂直于x-y平面)增加，并且然后重复该过程以形成类似于数字表示的3D零件。起始于长丝的基于挤出的增材制造系统的实例被称为熔丝制造(FFF)或熔融沉积成型(FDM)。
在通过沉积零件材料层制造3D零件中，支撑层或结构典型地被构建在正在建造的3D零件的悬伸部分下方或腔内，这些零件不被零件材料本身支撑。可以利用沉积零件材料的相同的沉积技术构建支撑结构。主计算机生成额外的几何形状，其充当正在形成的3D零件的悬伸或自由空间段的支撑结构，并且在一些情况下，充当正在形成的3D零件的侧壁的支撑结构。在制造期间支撑材料黏附到零件材料上，并且当打印过程完成时，该支撑材料可以从已完成的3D零件上去除。
通常，可溶的/可浸出的材料被用作支撑材料，使得因此一旦3D零件被构建，能够将支撑零件从最终的3D零件上溶解，使得浸泡和冲洗后处理在回收零件上是有效的。
在这种情况下，WO 99/60508(斯特拉塔西斯公司(STRATASYS,INC.))11/25/1999披露了具有下式的聚(2-乙基-2-噁唑啉)材料：
Figure BDA0001841416720000021
(PEO)作为熔融长丝成形技术的支撑材料的用途，包括通过浸泡和冲洗将其去除。这些PEO材料可以与聚乙二醇增塑剂混配，并且增塑的配制品尤其可以进一步用不超过35％wt.的量的聚酰胺配制，所述聚酰胺可能是尼龙12，以及对苯二甲酸、间苯二甲酰胺和六亚甲基二胺的无定形共聚物、无定形尼龙6/尼龙12共聚物等。
类似地，US 20150028523(斯特拉塔西斯公司)1/29/2015披露了聚乙醇酸(PGA)支撑材料用于增材制造系统的用途，其可以通过浸泡在水性介质中去除。根据某些实施例，PGA可以包含聚酰胺类型、脂肪族或芳香族类型的连接嵌段，特别是当与聚酰胺零件材料联合使用时。
然而，水溶性聚合物的选择相对有限；水溶性聚合物化合物可能不足以支撑某些需要高加工温度的聚合物的打印，并且然而在一些情况下浸泡/冲洗分离技术仍然非常繁重，至少因为它需要对大量废水进行后处理，以处置和/或回收水溶性支撑聚合物。在其他情况下，可溶性聚合物作为支撑材料的使用是生成零件材料的中空结构的唯一途径。
在联合高温零件材料，例如聚砜、聚醚砜、聚苯砜、聚芳醚酮、聚醚酰亚胺、聚酰胺酰亚胺、聚邻苯二甲酰胺、聚苯硫醚等制造3D零件中，在高温零件材料所需的较高操作条件下，需要支撑材料提供竖直和/或横向的支撑，并且所述支撑材料不应该在这些较高的操作条件下软化太多：否则变形会使得它们作为支撑结构材料无效。
然而，存在对改进的支撑材料的持续的寻找，所述支撑材料同时响应在增材制造技术中用作支撑材料的要求，特别是与高温零件材料组合，并且可以通过容易的技术将其容易地从3D成型零件上去除。
发明内容
本披露的一个方面针对一种用增材制造系统制造三维物体的方法，例如基于挤出的增材制造系统、选择性激光烧结系统、和/或基于电子摄影术的增材制造系统，该方法包括提供包含大于50％wt.的半结晶聚酰胺[聚酰胺(A)]的支撑材料，该聚酰胺具有如根据ASTM D3418确定的至少250℃的熔点并且具有通过浸入23℃的水中的至少2％wt.的饱和吸水率。
该方法还包括提供零件材料，由所提供的支撑材料打印支撑结构的层，并且与打印这些支撑结构的层协调来由所提供的零件材料打印三维物体的层，其中该支撑结构的至少一部分打印层支撑该三维物体的打印层。
该方法进一步包括从三维物体中去除至少一部分支撑结构以获得该三维物体。
本申请人已经发现，选择主要由具有至少250℃的熔化温度并且具有吸水行为(如上所规定)的半结晶聚酰胺构成的支撑材料是使得能够从需要例如300℃或更高加工温度的高温工程塑料打印零件材料，并且提供在暴露于水分时经受足够溶胀和变形的支撑零件，以能够有效和迅速地从打印零件上分离。
具体实施方式
表述‘聚酰胺’在此根据其通常意义使用，即用于表示基本上由具有以下式中的任一个的重复单元构成的聚合物：
-NH-R1-C(O)- (I)
-NH-R2-NH-C(O)-R3-C(O)- (II)
其中R1、R2、R3，彼此相同或不同，是二价的烃链，并且可以是脂肪族、脂环族、环脂肪族、芳香族的或其组合，其中R1、R2、R3可以包含一个或多于一个选自由O、N、S、P组成的组的杂原子。
通常聚酰胺(A)的重复单元(I)和(II)的特征在于每个酰胺基的基团R1、或R2和R3中的碳原子数有利地小于8。
确切地，该聚酰胺(A)是至少一种选自以下项的混合物的缩合产物：
-包含至少一种二酸[酸(DA)](或其衍生物)和至少一种二胺[胺(NN)](或其衍生物)的混合物(M1)；
-包含至少一种内酰胺[内酰胺(L)]的混合物(M2)；
-包含至少一种氨基羧酸[氨基酸(AN)]的混合物(M3)；以及
-其组合。
酸(DA)衍生物尤其包括盐、酸酐、酯以及酰基卤，其能够形成酰胺基；类似地，胺(NN)衍生物尤其包括同样能够形成酰胺基的其盐。
所述酸(DA)可以是包含两个反应性羧酸基团的芳香族二羧酸[酸(AR)]或包含两个反应性羧酸基团的脂肪族二羧酸[酸(AL)]。出于本发明的目的，当二羧酸包含一个或多于一个芳香族基团时，它被认为是“芳香族的”。
酸(AR)的非限制性实例尤其是苯二甲酸(包括间苯二甲酸(IA)和对苯二甲酸(TA))、2,5-吡啶二羧酸、2,4-吡啶二羧酸、3,5-吡啶二羧酸、2,2-双(4-羧苯基)丙烷、双(4-羧苯基)甲烷、2,2-双(4-羧苯基)六氟丙烷、2,2-双(4-羧苯基)酮、4,4’-双(4-羧苯基)砜、2,2-双(3-羧苯基)丙烷、双(3-羧苯基)甲烷、2,2-双(3-羧苯基)六氟丙烷、2,2-双(3-羧苯基)酮、双(3-羧基苯氧基)苯、萘二羧酸(包括2,6-萘二羧酸、2,7-萘二羧酸、1,4-萘二羧酸、2,3-萘二羧酸、1,8-萘二羧酸)和联苯基-4,4’-二羧酸。
在酸(AL)之中，尤其可以提及草酸(HOOC-COOH)、丙二酸(HOOC-CH2-COOH)、琥珀酸[HOOC-(CH2)2-COOH]、戊二酸[HOOC-(CH2)3-COOH]、2,2-二甲基-戊二酸[HOOC-C(CH3)2-(CH2)2COOH]、己二酸[HOOC-(CH2)4-COOH]、2,4,4-三甲基-己二酸[HOOC-CH(CH3)-CH2-C(CH3)2-CH2-COOH]、庚二酸[HOOC-(CH2)5-COOH]、辛二酸[HOOC-(CH2)6-COOH]、壬二酸[HOOC-(CH2)7-COOH]、癸二酸[HOOC-(CH2)8-COOH]、十一烷二酸[HOOC-(CH2)9-COOH]、十二烷二酸[HOOC-(CH2)10COOH]、十三烷二酸[HOOC-(CH2)11-COOH]、十四烷二酸[HOOC-(CH2)12-COOH]、十八烷二酸[HOOC-(CH2)16-COOH]。
然而，可以使用的酸(AL)包括含有环脂肪族基团的酸，尤其包括1,4-环己烷二羧酸、1,3-环己烷二羧酸，作为顺式或反式非对映异构体，可能呈混合物形式。
根据某些实施例，可以使用包含可电离基团的酸(DA)[酸(IDA)]作为聚酰胺(A)的缩聚单体；在这些可电离基团中，尤其可以提及酚羟基、磺酸基(通常为芳香族磺酸基)、膦酸基、鎓基(包括鏻和铵基)等。可以在本发明的框架内使用的这种类型的酸(IDA)的非限制性实例尤其是4-羟基间苯二甲酸、5-羟基间苯二甲酸、2-羟基对苯二甲酸，2,5-二羟基对苯二甲酸、4,6-二羟基间苯二甲酸、5-磺基间苯二甲酸(及其盐，例如Li、K、Na、Ag盐)和2-磺基对苯二甲酸(及其盐，例如Li、K、Na、Ag盐)。
包括可电离基团的酸(IDA)可与如上详述的酸(AR)和/或酸(AL)组合使用。
该胺(NN)通常选自由以下各项组成的组：脂肪族二胺、芳香族二胺以及其混合物。
所述脂肪族二胺典型地是具有2至18个碳原子的脂肪族二胺。
所述脂肪族二胺有利地选自由以下各项组成的组：1,2-二氨基乙烷、1,2-二氨基丙烷、亚丙基-1,3-二胺、1,3-二氨基丁烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,5-二氨基-2-甲基戊烷、1,4-二氨基-1,1-二甲基丁烷、1,4-二氨基-1-乙基丁烷、1,4-二氨基-1,2-二甲基丁烷、1,4-二氨基-1,3-二甲基丁烷、1,4-二氨基-1,4-二甲基丁烷、1,4-二氨基-2,3-二甲基丁烷、1,2-二氨基-1-丁基乙烷、1,6-二氨基己烷、1,7-二氨基庚烷、1,8-二氨基-辛烷、1,6-二氨基-2,5-二甲基己烷、1,6-二氨基-2,4-二甲基己烷、1,6-二氨基-3,3-二甲基己烷、1,6-二氨基-2,2-二甲基己烷、1,9-二氨基壬烷、1,6-二氨基-2,2,4-三甲基己烷、1,6-二氨基-2,4,4-三甲基己烷、1,7-二氨基-2,3-二甲基庚烷、1,7-二氨基-2,4-二甲基庚烷、1,7-二氨基-2,5-二甲基庚烷、1,7-二氨基-2,2-二甲基庚烷、1,10-二氨基癸烷、1,8-二氨基-1,3-二甲基辛烷、1,8-二氨基-1,4-二甲基辛烷、1,8-二氨基-2,4-二甲基辛烷、1,8-二氨基-3,4-二甲基辛烷、1,8-二氨基-4,5-二甲基辛烷、1,8-二氨基-2,2-二甲基辛烷、1,8-二氨基-3,3-二甲基辛烷、1,8-二氨基-4,4-二甲基辛烷、1,6-二氨基-2,4-二乙基己烷、1,9-二氨基-5-甲基壬烷、1,11-二氨基十一烷以及1,12-二氨基十二烷、1,13-二氨基十三烷、2,5-双(氨基甲基)四氢呋喃、N-甲基-双-六亚甲基-三胺。
该脂肪族二胺优选包含至少一种选自由以下各项组成的组的二胺：1,6-二氨基己烷、1,8-二氨基-辛烷、1,10-二氨基癸烷、1,12-二氨基十二烷以及其混合物。更优选地，该脂肪族亚烷基二胺包含至少一种选自由以下各项组成的组的二胺：1,6-二氨基己烷、1,10-二氨基癸烷以及其混合物。甚至更优选地，该脂肪族亚烷基二胺是1,6-二氨基己烷。
该芳香族二胺优选地选自由以下各项组成的组：间苯二胺、间苯二甲胺以及对苯二甲胺。
根据其他实施例，胺(NN)中的至少一种是环脂肪族二胺，即包含环脂肪族基团的二胺[胺(cNN)]；胺(cNN)通常选自由以下各项组成的组：异佛尔酮二胺、双(3,5-二烷基-4-氨基环己基)甲烷、双(3,5-二烷基-4-氨基环己基)乙烷、双(3,5-二烷基-4-氨基环己基)丙烷、双(3,5-二烷基-4-氨基环己基)丁烷、双(3-甲基-4-氨基环己基)甲烷、对-双(氨基环己基)甲烷，异亚丙基二(环己胺)、4,4’-二氨基-3,3'-二甲基二环己基甲烷和1,4-二氨基环己烷。
根据某些其他实施例，可以使用包含醚键的至少一种胺(NN)[胺(NNE)]作为聚酰胺(A)的缩聚单体；胺(NNE)(另外称为聚醚二胺)的示例性实施例尤其是包含具有下式的部分的二胺：-(OCH2-CHRJ)n-，其中RJ是H或C1-C3烷基，优选-CH3，并且n是1至15的整数，以及包含具有下式的部分的二胺：-O-C(R’J)(R”J)-O-，其中R’J和R”J，彼此相同或不同并且每次出现时，是H或C1-C3烷基，优选–CH3。
其示例性的实施例是具有以下式中的任一个的胺(NNE)：
1)
Figure BDA0001841416720000061
其中x和z是0或整数，其中y是整数，前提是x+y+z是1至15的整数；
2)
Figure BDA0001841416720000062
其中q是1至15的整数；
3)
Figure BDA0001841416720000063
其中每个x，彼此相同或不同，是1至6的整数；
4)
Figure BDA0001841416720000064
其中R*和R’*，彼此相同或不同，独立地是氢、C1-C3烷基；A是烷基、烯基、链烯烃(alkenene)、亚烷基-杂-亚烷基、亚烷基-杂环-亚烷基、亚烷基、亚烷基-氧基-亚烷基、1,4-烷基取代的哌嗪、羰基、硫代羰基；B是烷基、烯基、链烯烃、亚烷基-杂-亚烷基、亚烷基-杂环-亚烷基、亚烷基、亚烷基-氧基-亚烷基、1,4-烷基取代的哌嗪、羰基、硫代羰基；R2是氢、烷基、氨基烷基、烷基-氨基-烷基、环烷基、杂环烷基、烯基、芳基、或杂芳基；符合该结构式的胺尤其在WO 2013/007128(艾达索高新材料无锡有限公司(ADESSO ADVANCED MATERIALSWUXI CO.LTD))1/17/2013中披露。
通常，优选的胺(NNE)的分子量将是至多400g/mol、更优选至少200g/mol、甚至更优选至多150g/mol。如上详述的胺(NNE)尤其是以商品名Jeffamine或Elastamine从亨斯迈化学品公司(Huntsmann Chemicals)可获得的。其具体实例尤其包括2,2’-氧基二乙胺、2,2’-(亚乙二氧基)双(乙胺)、乙二醇双(3-氨基丙基)醚。
适合用于制造聚酰胺(A)的内酰胺(L)可以是β-内酰胺或ε-己内酰胺、十二内酰胺中的任一种。
适合用于制造聚酰胺(A)的氨基酸(AN)可以选自由以下各项组成的组：6-氨基-己酸、9-氨基壬酸、10-氨基癸酸、11-氨基十一烷酸、12-氨基十二烷酸、13-氨基十三酸。
仍在本发明范围内的是将一种或多于一种包含多于两个羧酸基团和胺基团的多官能酸/胺单体(例如，具有三个或更多个羧酸基团的多元羧酸、具有三个或更多个胺基团的多元胺、包括两个羧酸基团和一个或多个胺基团的多官能二酸、包括两个胺基团和一个或多个羧酸基团的多官能二胺)添加到混合物(M1)、(M2)、(M3)以及其组合中的任一种。结合所述多官能酸/胺单体通常导致支链结构，星状或树状的，如尤其在WO 97/24388(尼尔提克意大利公司(NYLTECH ITALIA)10/7/1997和WO 99/64496(尼尔提克意大利公司)12/16/1999中描述的那些。
还应进一步理解的是可以将一种或多于一种封端剂[试剂(M)]加入用于制造聚酰胺(A)的混合物(M1)、(M2)、(M3)以及其组合中的任一种，而这不背离本发明的范围。该试剂(M)通常选自由以下各项组成的组：仅包含一个反应性羧酸基团的酸[酸(MA)]和仅包含一个反应性胺基团的胺[试剂(MN)]。
酸(MA)优选地选自由以下各项组成的组：乙酸、丙酸、丁酸、戊酸、己酸、辛酸、月桂酸、硬脂酸、环己烷羧酸、苯甲酸、3-磺基苯甲酸(及其盐，例如Li、K、Na、Ag盐)、4-磺基苯甲酸(及其盐，例如Li、K、Na、Ag盐)，优选地选自乙酸和苯甲酸。
胺(MN)优选地选自由以下各项组成的组：甲胺、乙胺、丁胺、己胺、辛胺、苄胺、苯胺、甲苯胺。
本领域普通技术人员将通过常规实验选择如上详述的混合物(M1)、(M2)或(M3)，这些混合物是使得提供如上详述的具有所提及的熔点和所提及的吸水行为的聚酰胺(A)。
优选的混合物(M1)选自：
(a)1,6-二氨基己烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺66；
(b)1,4-二氨基丁烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺46；
(c)1,5-二氨基戊烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺56；
(d)己二酸、对苯二甲酸和1,6-二氨基己烷的混合物，其中相对于酸(DA)的摩尔，对苯二甲酸的量是至少25％摩尔；
(e)对苯二甲酸、间苯二甲酸和1,6-二氨基己烷的混合物，其中相对于酸(DA)的摩尔，对苯二甲酸的量是至少55％摩尔；
(f)己二酸、对苯二甲酸、间苯二甲酸和1,6-二氨基己烷的混合物，其中相对于酸(DA)的摩尔，对苯二甲酸的量是至少55％摩尔；
(g)对苯二甲酸(可能进一步包含相对于该酸(DA)的少量的间苯二甲酸和/或己二酸)和至少一种如上详述的胺(NNE)的混合物，可能与一种或多于一种如上详述的脂肪族二胺组合；
(h)己二酸(可能进一步包含相对于该酸(DA)的少量的间苯二甲酸和/或对苯二甲酸)和至少一种如上详述的胺(NNE)的混合物，可能与一种或多于一种如上详述的脂肪族亚烷基二胺组合；
(I)己二酸和至少一种如上所述的酸(IDA)(优选5-磺基-间苯二甲酸，或其盐)以及1,6-二氨基己烷的混合物，所述酸(IDA)占总的酸(DA)摩尔的至多15％、优选至多10％、更优选至多5％摩尔；
(j)对苯二甲酸和至少一种如上所述的酸(IDA)(优选5-磺基-间苯二甲酸，或其盐)以及1,6-二氨基己烷的混合物，所述酸(IDA)占总的酸(DA)摩尔的至多15％、优选至多10％、更优选至多5％摩尔；
(k)1,4-环己烷二羧酸(顺式、反式或顺式/反式混合物)和至少一种如上详述的胺(NNE)的混合物，可能与一种或多于一种如上详述的脂肪族二胺组合；
(l)1,4-环己烷二羧酸(顺式、反式或顺式/反式混合物)和至少一种如上所述的酸(IDA)(优选5-磺基-间苯二甲酸，或其盐)(所述酸(IDA)占总的酸(DA)摩尔的至多15％、优选至多10％、更优选至多5％摩尔)以及至少一种如上详述的胺(NNE)的混合物，可能与一种或多于一种如上详述的脂肪族二胺组合。
如上详述，通过浸入23℃的水中，聚酰胺(A)的饱和吸水率是至少2％wt、优选5％wt。该吸水率可以通过以其干燥状态(水分含量小于0.2％wt)提供根据ISO527成形的样品，将其浸入23℃的去离子水中直至达到恒定重量来确定。根据以下公式计算吸水率：
Figure BDA0001841416720000091
其中W前是处于其原始干燥状态的成形样品的重量并且W后是吸水后该成形样品的重量。
根据某些实施例，聚酰胺(A)是在大气压下在低于100℃的温度下具有至少1％wt的水溶解度的聚酰胺。
该实施例的聚酰胺(A)在大气压下在低于100℃的温度下在水和脂肪醇(尤其包括甲醇、乙醇、异丙醇、乙二醇)的混合物中通常具有至少1％wt、优选5％wt的溶解度。
该实施例的可溶性聚酰胺(A)通常是由如上详述的混合物(M1)制备的聚酰胺，其中所述混合物(M1)包含一种或多于一种如上详述的胺(NNE)。更具体地，该实施例的可溶性聚酰胺(A)有利地选自由如上定义的混合物(g)、(h)、(i)、(j)、(k)、(l)组成的组。
根据某些实施例，本发明的支撑材料包含至少一种不同于聚酰胺(A)的水溶性聚合物添加剂。该聚合物添加剂的选择不是特别关键，前提是它具有足够的热稳定性以与聚酰胺(A)混合，并且它是可溶于水的，也就是说在大气压下在低于100℃的温度下在水中具有至少1％的溶解度。可以有利地使用聚电解质如多元酸(及其盐)和多元胺(及其盐)，以及具有水溶解度的不可电离的聚合物；该添加剂通常选自由以下各项组成的组：聚乙二醇(PEG)聚合物；聚乙烯吡咯烷酮(PVP)聚合物；聚亚甲基萘磺酸盐(通过萘的磺化、与甲醛缩合并且中和得到)聚合物；具有-SO3Xa基团的苯乙烯磺酸盐类聚合物(其中Xa是H或金属，例如Na、K、Li)，包括聚苯乙烯磺酸盐以及苯乙烯-共-苯乙烯磺酸盐的共聚物；具有-SO3Xa基团的磺化砜聚合物(其中Xa是H或金属)，包括磺化聚砜、磺化聚苯砜、磺化聚醚砜；聚琥珀酰亚胺和盐；聚天冬氨酸和盐；聚(甲基)丙烯酸和盐(如Na、K、Li)；聚乙烯基磺酸和盐(如Na、K、Li)；聚乙烯醇等。
当存在时，相对于支撑材料的总重量，所述水溶性聚合物添加剂以至少1％wt、优选至少2％wt、更优选至少5％wt和/或通常至多30％wt、优选至多25％wt、更优选至多20％wt的量添加到该支撑材料中的聚酰胺(A)中。
不受该理论的束缚，本申请人认为聚酰胺(A)的亲水行为(可能通过水溶性聚合物添加剂的存在而增强)对于实现支撑材料从三维物体上的充分分离是有效的。
本发明的支撑材料还可以包括不同于聚酰胺(A)和水溶性聚合物添加剂的其他添加剂；这些添加剂选自通常已知的用于聚酰胺的那些，并且尤其包括填料、着色剂、增塑剂、稳定剂、及其组合。
在包括填料的实施例中，相对于支撑材料的总重量，该支撑材料中填料的优选浓度范围从1％wt至30％wt。合适的填料包括碳酸钙、碳酸镁、玻璃纤维、石墨、炭黑、碳纤维、滑石、硅灰石、云母、氧化铝、二氧化硅、二氧化钛、高岭土、碳化硅、钨酸锆、及其组合。
本发明的支撑材料总体上由以下项组成：
-从55％wt至100％wt的如上详述的聚酰胺(A)；
-从0至30％wt的如上详述的水溶性聚合物添加剂；以及
-从0至30％wt的其他添加剂，
相对于该支撑材料的总重量。
优选地，本发明的支撑材料有利地由以下项组成：
-从75％wt至100％wt的如上详述的聚酰胺(A)；
-从0至20％wt的如上详述的水溶性聚合物添加剂；以及
-从0至20％wt的如上详述的其他添加剂,
相对于该支撑材料的总重量。
本发明的支撑材料被用于在增材制造系统(例如基于挤出的增材制造系统，以及基于喷射的增材制造)中打印牺牲支撑结构。
该支撑材料通常以干燥状态提供；为此目的，该支撑材料通常在被运送至增材制造系统并在该增材制造系统中使用前被干燥。
如此，相对于支撑材料的总重量，提供给增材制造系统的支撑材料优选地具有小于0.5％wt、优选小于0.2％wt的水分含量。可能需要初步的干燥步骤以通过在大气温度(在空气或氮气下)或在真空下在60℃至200℃之间加热支撑材料持续期望量的时间来达到此低水分含量。
本发明方法中提供的零件材料通常是需要至少300℃或更高的加工温度的材料。在本发明的方法中通常与如上详述的支撑材料相关联的零件材料尤其是聚砜、聚醚砜、聚苯砜、聚芳醚酮(包括聚醚醚酮)、聚醚酰亚胺、聚酰胺酰亚胺、聚苯硫醚、聚亚苯基、液晶聚合物、聚碳酸酯、芳香族和半芳香族的聚酰胺，尤其包括间苯二甲胺己二酸盐(MXD6)等。
通常，因此从零件材料打印三维物体的层的步骤在至少300℃、优选至少350℃的温度下在熔融状态下打印零件材料来进行。
根据某些优选的实施例，本发明的方法是用基于挤出的增材制造系统制造三维物体的方法，另外也称为熔丝制造技术。
以长丝的形式提供根据这些实施例的支撑材料。该长丝可以具有圆柱形或基本上圆柱形的几何形状，或者可以具有非圆柱形几何形状，例如带状长丝几何形状；此外，长丝可以具有中空几何形状，或者可以具有核-壳几何形状，其中本发明的支撑材料用于形成核或壳。
然而，根据这些实施例的支撑材料也可以以粉末形式提供，例如用于通过螺旋泵打印头进料。
当该方法是基于挤出的增材制造系统时，由所提供的支撑材料打印牺牲支撑结构的层的步骤包括：
a)将该支撑材料进料到排放头构件(discharge head member)，该构件具有以排放尖端(discharge tip)结尾的通孔和熔化该通孔中的材料的圆周加热器；
b)在所述通孔中用活塞压缩该支撑材料，例如用未熔化的长丝充当活塞，而同时熔化该排放头构件中的支撑材料，以便从该排放尖端挤出支撑材料带；并且
c)在将支撑材料排放在接收平台上的同时确保该排放尖端和所述接收平台在x和y方向上的相对运动，以形成该牺牲支撑结构的横截面形状；并且
d)在将支撑材料排放在所述接收平台上的同时确保该排放尖端和该接收平台在z方向上的相对运动，以在高度上形成该牺牲支撑结构。
根据这些实施例，与打印这些牺牲支撑结构的层协调来由所提供的零件材料打印三维物体的层的步骤有利地进一步包括：
a’)将该零件材料进料到排放头构件，该构件具有以排放尖端结尾的通孔和熔化该通孔中的材料的圆周加热器；
b’)在所述通孔中用活塞压缩该零件材料，例如用未熔化的长丝充当活塞，而同时熔化该排放头构件中的零件材料，以便从该排放尖端挤出零件材料带；并且
c)在将支撑材料排放在所述接收平台和所述牺牲支撑结构上的同时确保该排放尖端和承载该牺牲支撑结构的接收平台在x和y方向上的相对运动，以形成该三维物体的横截面形状，并且
d)在将零件材料排放在所述接收平台和所述牺牲支撑结构上的同时确保该排放尖端和该接收平台在z方向上的相对运动，以在高度上形成该三维物体。
本发明的方法包括步骤(iv)：从组件中去除至少一部分牺牲支撑结构，以便获得三维物体。
该方法通常涉及将组件暴露于水蒸气和/或水。
当暴露于液态水时，可以使用纯水。然而，可以使用暴露于通过向具有极性质子性溶剂(例如乙醇、异丙醇、乙二醇)的水混合物中添加一种或多种酸或碱进行酸化或碱化的水溶液；暴露于包含电解质(例如氯化钠、氯化锂)的水溶液。通常，水以至少30％wt、优选至少50％wt的浓度存在于用于该暴露的液体介质中。
该暴露可以以任何方式实现。
根据某些实施例，步骤(iv)包括在暴露的温度下将组件暴露于潮湿空气，例如暴露于具有至少70％、优选至少80％、优选至少85％的相对湿度(RH)的空气。该暴露于潮湿空气可以在室温下(即约20℃-25℃下)进行，但通常优选将组件在至少50℃、优选至少60℃的温度下和/或通常在至多90℃、优选至多80℃的温度下暴露于潮湿空气。
根据其他实施例，步骤(iv)包括使组件与水(即液态水)接触/浸入其中。在这种情况下，尽管同样可以使用更高的温度(最高约100℃)，但是浸渍/接触的水温通常约为室温，即20℃至25℃的温度。
暴露于水蒸气和/或水的持续时间没有特别限制，并且至少1小时的暴露时间可能是有效的。
然而应理解，当步骤(iv)包括将组件暴露于潮湿空气时，暴露的持续时间优选至少24个小时、优选30个小时。
作为步骤(iv)的结果，从组件中去除牺牲支撑结构；所述牺牲支撑结构可以有利地从三维物体上分离并且以其固体形式去除。然而，对于其中使用如上详述的可溶于水的聚酰胺(A)的实施例，可以通过在水中至少部分溶解来实现牺牲支撑结构的去除。
如果通过援引方式并入本申请的任何专利、专利申请、以及公开物的披露内容与本申请的说明相冲突到了可能导致术语不清楚的程度，则本说明应该优先。
实例
原材料
A1.来自塞拉尼斯公司(Celanese)的具有Tm＝285℃的聚苯硫醚(PPS)Fortron(R)0317，其具有通过浸入23℃的水中的0.1％wt.的饱和吸水率。
A2.根据在WO 2010/112602(苏威公司(SOLVAY S.A.))10/7/2010中描述的程序合成的具有Tm＝220℃的聚乙醇酸(PGA)。
A3.来自苏威公司的具有Tm＝317℃的半结晶聚邻苯二甲酰胺(PPA)Amodel(R)A-1004(PA 6T/6I/6665/25/10mol/mol)。通过浸入23℃的水中的饱和吸水率为：6.5％。
A4.来自可乐丽公司(Kuraray)的具有Tm＝306℃的半结晶聚邻苯二甲酰胺PA 9T，GenestarTM 9T GC61010。通过浸入23℃的水中的饱和吸水率为：3％。
A5.根据专利WO 2015/007918实例3中的方法合成的具有Tm＝253℃的半结晶共聚酰胺PA 66/6AISNa 95/5mol/mol。通过浸入23℃的水中的饱和吸水率为：12％。
A6.来自苏威公司的具有Tm＝260℃的半结晶聚酰胺66(PA 66)Stabamid(R)27AE1。通过浸入23℃的水中的饱和吸水率为：8％。
添加剂
B1.在西格玛-奥德里奇公司(Sigma-Aldrich)购买的聚乙烯吡咯烷酮(PVP)1,300kDa
样品制备
通过若干不同的方法制备支撑材料测试形状。
E1.通过注射模制制备具有2mm厚度(尺寸：长度＝7.5cm；宽度＝5cm)的纯树脂的基板。
E2.通过经由扁平模口熔融挤出而不进行任何拉伸来制备具有大于100微米厚度的薄膜样品。
使用双螺杆挤出机(熔体温度为350℃)通过熔融挤出制备化合物。
表1中给出了每种化合物的具体条件。
测试
使用具有0.8mm直径的模口并且在400℃(机筒温度)下加热的立式挤出机并且以10mm/s速度生产聚醚醚酮(PEEK)KetaSpire(R)KT-880(Tm＝340℃)的熔融长丝。在模口的出口处，PEEK热长丝被置于与放置在距该模口1mm之间的距离处的薄膜/基板接触，并制备具有约0.25平方英寸的表面积的单层薄膜。在打印过程结束后，将样品置于室温下冷却。
检查如此获得的打印组件以便尤其检测支撑材料的任何熔化/变形现象，并测试支撑材料与零件材料之间的粘合性，以及分离/分开支撑材料和零件材料的能力。归属于以下等级：
0.支撑材料表面在零件材料打印期间已经在表面完全熔化。
1.支撑材料表面没有熔化也没有显示任何变形迹象；显著的内聚力将支撑材料表面粘附到零件材料上，使得分离引起支撑材料和零件材料的完整性破坏/劣化，其中支撑材料的残余物粘附到零件材料上，反之亦然。
2.支撑材料表面没有熔化也没有显示任何变形迹象；在支撑材料表面与打印材料之间没有显著的粘合，使得可以使用基本上不显著的分离力来分开支撑材料和零件材料。分离导致完全分开，其中零件材料上没有支撑材料的残余物，反之亦然。
表1
Figure BDA0001841416720000141
我们首先观察到当PEEK熔融长丝与PGA薄膜(Tm＝220℃)和PA 66/6AISNa 95/5薄膜(Tm＝253℃)接触时，PEEK熔融长丝熔化PGA，这使得PGA不适合作为打印PEEK的支撑材料，不同于具有更高熔点的PA 66/6AISNa 95/5。很明显，该支撑材料的熔点需要高于250℃。
如预期的，具有高于PA 66/6AISNa或PA 66(Tm＝260℃)的熔点的PPS(Tm＝280℃)可以用PEEK热长丝打印而不会引起任何表面的熔化或变形。出乎意料的是，PEEK对PPS薄膜或基板的粘附性如此强以至于不可能在不破坏PPS薄膜或基板并且在没有一块PPS黏到PEEK上的情况下从PPS薄膜或基板上去除PEEK。
令人惊讶的是，所有具有均高于250℃的不同熔点的聚酰胺像PA 66、PPA、PA 66/6AISNa和PA 9T在打印过程中表现出对PEEK的良好的粘附性，但是可以在冷却后比PPS更容易与PEEK分离，前提是它们在23℃下的吸水率为至少2％wt。
此外，具有更高吸湿性的聚酰胺在暴露于水后示出令人感兴趣的行为，因为它们比具有较低吸湿性的聚酰胺(PA 9T)更容易分离。
制备实例8：从对苯二甲酸和2,2′-(亚乙二氧基)双(乙胺)合成亲水的高熔化温度的聚酰胺
在装备有搅拌器、压力释放阀和冷凝器的反应器中，引入9g(0.054mol)的对苯二甲酸、8g(0.054mol)的2,2′-(亚乙二氧基)双(乙胺)、0.0052g H3PO3和11g的去离子水。密封该反应器，将压力释放阀设定为20巴，并在1小时内将反应混合物加热至335℃。将反应混合物在335℃下保持15分钟，并且然后在1小时内冷却至200℃，并且然后冷却至室温。在从反应器释放压力后，打开反应器并移出固体聚合物并通过DSC分析：发现熔点等于256℃，并且发现熔化焓是29J/g。在90℃下在大气压下将聚合物置于50/50wt/wt的水/乙醇混合物中，并且发现在3个小时暴露后该聚合物经受至少部分溶解(水性醇溶液是混浊的)。鉴于其高熔点和其在醇水溶液中的溶解，该聚酰胺特别适合用作本发明的支撑材料中的聚酰胺(A)。水溶解度对于构建具有复杂几何形状和/或凹槽的零件特别有意义，使得该支撑材料除了通过溶解之外不能被去除。
制备实例9：由1,4-环己烷二羧酸和2,2′-(亚乙二氧基)双(乙胺)合成亲水的高熔化温度的聚酰胺
向装备有搅拌器和冷凝器的反应器中引入9.08g(0.053mol)的1,4-环己烷二羧酸、7.86g(0.053mol)的2,2′-(亚乙二氧基)双(乙胺)，0.0052g H3PO3和11g的去离子水。密封该反应器，将压力释放阀设定为20巴，并在1小时内将反应混合物加热至335℃。将反应混合物在335℃下保持15分钟，并且然后在1小时内冷却至200℃，并且然后冷却至室温。在从反应器释放压力后，打开反应器并回收固体聚合物并通过DSC分析：发现熔点等于302℃，并且发现熔化焓是20J/g。在90℃下在大气压下将聚合物置于50/50wt/wt的水/乙醇混合物中，并在仅2小时暴露后完全溶解(水性醇溶液是混浊的)。鉴于其高熔点和其在醇水溶液中的溶解，该聚酰胺特别适合用作本发明的支撑材料中的聚酰胺(A)。水溶解度对于构建具有复杂几何形状和/或凹槽的零件特别有意义，使得该支撑材料除了通过溶解之外不能被去除。

Claims (31)

1.一种用增材制造系统制造三维物体的方法，该方法包括：
- 提供包含大于50% wt.的半结晶聚酰胺即聚酰胺（A）的支撑材料，该聚酰胺具有根据ASTM D3418确定的至少250℃的熔点并且具有通过浸入23℃的水中的至少2% wt的饱和吸水率；
- 提供零件材料；
- 由所提供的支撑材料打印支撑结构的层，并且与该打印支撑结构的层协调来由所提供的零件材料打印该三维物体的层，其中该支撑结构的至少一部分打印层支撑该三维物体的打印层；并且
- 从该三维物体去除至少一部分该支撑结构，以便获得该三维物体。
2.如权利要求1所述的方法，其中，该聚酰胺（A）符合以下式中的任一个：
-NH-R1-C(O)- （I）
-NH-R2-NH-C(O)-R3-C(O)- （II）
其中R1、R2、R3，彼此相同或不同，是二价的烃链，并且是脂肪族、脂环族、环脂肪族、芳香族的或其组合，其中R1、R2、R3包含一个或多于一个选自由O、N、S、P组成的组的杂原子，其中，该聚酰胺（A）的重复单元（I）和（II）的特征在于每个酰胺基（-C(O)NH-）的基团R1、或R2和R3中的碳原子数小于8。
3.如权利要求1-2中任一项所述的方法，其中，该聚酰胺（A）是至少一种选自以下项的混合物的缩合产物：
- 包含至少一种二酸即酸（DA）或其衍生物和至少一种二胺即胺（NN）或其衍生物的混合物（M1）；
- 包含至少一种内酰胺即内酰胺 (L)的混合物（M2）；
- 包含至少一种氨基羧酸即氨基酸（AN）的混合物（M3）；以及
- 其组合。
4.如权利要求3所述的方法，其中，该酸（DA）包含至少一种包含可电离基团的二酸即酸（IDA），所述可电离基团选自酚羟基、磺酸基、膦酸基、鏻鎓基和铵基；和/或其中，该酸（DA）包括以下中的至少一种：4-羟基间苯二甲酸、5-羟基间苯二甲酸、2-羟基对苯二甲酸、2,5-二羟基对苯二甲酸、4,6-二羟基间苯二甲酸、5-磺基间苯二甲酸及其盐、以及2-磺基对苯二甲酸及其盐。
5.如权利要求4所述的方法，其中磺酸基为芳香族磺酸基。
6.如权利要求4所述的方法，其中，5-磺基间苯二甲酸和2-磺基对苯二甲酸的盐为其Li、K、Na或Ag盐。
7.如权利要求4所述的方法，其中，该胺（NN）中的至少一种包含醚键，即为胺 (NNE)，并且包含具有下式的部分：-(OCH2-CHRJ)n-，其中RJ是H或C1-C3烷基，并且n是1至15的整数，以及包含具有下式的部分的二胺：-O-C(R’J)(R”J)-O-，其中R’J和R”J，彼此相同或不同并且在每次出现时，是H或C1-C3烷基。
8.如权利要求7所述的方法，其中，在式-(OCH2-CHRJ)n-中，RJ是-CH3。
9.如权利要求7所述的方法，其中，在式-O-C(R’J)(R”J)-O-中，R’J和R”J，彼此相同或不同并且在每次出现时，是–CH3。
10.如权利要求4所述的方法，其中，该聚酰胺（A）是通过选自下组的混合物（M1）的缩聚获得的，该组由以下各项组成：
(a) 1,6-二氨基己烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺66；
(b) 1,4-二氨基丁烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺46；
(c) 1,5-二氨基戊烷和己二酸的混合物，也就是说所得的缩聚产物是聚酰胺56；
(d) 己二酸、对苯二甲酸和1,6-二氨基己烷的混合物，其中相对于该酸（DA）的摩尔，对苯二甲酸的量是至少25%摩尔；
(e) 对苯二甲酸、间苯二甲酸和1,6-二氨基己烷的混合物，其中相对于该酸（DA）的摩尔，对苯二甲酸的量是至少55%摩尔；
(f) 己二酸、对苯二甲酸、间苯二甲酸和1,6-二氨基己烷的混合物，其中相对于该酸（DA）的摩尔，对苯二甲酸的量是至少55%摩尔；
(g) 对苯二甲酸，任选包含相对于该酸（DA）的少量的间苯二甲酸和/或己二酸，和至少一种如在权利要求7中定义的胺 (NNE) 的混合物，任选与一种或多于一种脂肪族二胺组合；
(h) 己二酸，任选包含相对于该酸（DA）的少量的间苯二甲酸和/或对苯二甲酸，和至少一种如在权利要求7中定义的胺 (NNE) 的混合物，任选与一种或多于一种脂肪族二胺组合；
（i） 己二酸和至少一种如在权利要求4中定义的酸（IDA）以及1,6-二氨基己烷的混合物，所述酸（IDA）占总的酸（DA）摩尔的至多15%；
(j) 对苯二甲酸和至少一种如在权利要求4中定义的酸（IDA）以及1,6-二氨基己烷的混合物，所述酸（IDA）占总的酸（DA）摩尔的至多15%；
(k) 1,4-环己烷二羧酸的顺式、反式或顺式/反式混合物和至少一种如在权利要求7中定义的胺 (NNE)的混合物，任选与一种或多于一种脂肪族二胺组合；
(l) 1,4-环己烷二羧酸的顺式、反式或顺式/反式混合物和至少一种在权利要求4中定义的酸（IDA），所述酸（IDA）占总的酸（DA）摩尔的至多15%，以及至少一种如在权利要求7中定义的胺 (NNE) 的混合物，任选与一种或多于一种脂肪族二胺组合。
11.如权利要求10所述的方法，其中，（i）、 (j) 和 (l) 中的至少一种如在权利要求4中定义的酸（IDA）为5-磺基-间苯二甲酸或其盐，且所述酸（IDA）占总的酸（DA）摩尔的至多10%。
12.如权利要求11所述的方法，其中，所述酸（IDA）占总的酸（DA）摩尔的至多5%摩尔。
13.根据权利要求1-2中任一项所述的方法，其中，该支撑材料包含至少一种不同于聚酰胺（A）的水溶性聚合物添加剂，该添加剂选自由以下各项组成的组：聚乙二醇（PEG）聚合物；聚乙烯吡咯烷酮（PVP）聚合物；通过萘的磺化、与甲醛缩合并且中和得到的聚亚甲基萘磺酸盐聚合物；具有-SO3Xa基团的苯乙烯磺酸盐类聚合物，其中Xa是H或金属；具有-SO3Xa基团的磺化砜聚合物，其中Xa是H或金属；聚琥珀酰亚胺和盐；聚天冬氨酸和盐；聚（甲基）丙烯酸和盐；聚乙烯基磺酸和盐；和聚乙烯醇。
14.如权利要求13所述的方法，其中，具有-SO3Xa基团的苯乙烯磺酸盐类聚合物包括聚苯乙烯磺酸盐或苯乙烯-共-苯乙烯磺酸盐的共聚物。
15.如权利要求13所述的方法，其中，具有-SO3Xa基团的磺化砜聚合物包括磺化聚砜、磺化聚苯砜或磺化聚醚砜。
16.如权利要求1-2中任一项所述的方法，其中，该支撑材料以干燥状态提供，相对于该支撑材料的总重量，具有小于0.5% wt的水分含量。
17.如权利要求16所述的方法，其中，该支撑材料以干燥状态提供，相对于该支撑材料的总重量，具有小于0.2% wt的水分含量。
18.如权利要求1-2中任一项所述的方法，其中，该零件材料选自由以下各项组成的组：聚砜，聚醚砜，聚苯砜，聚芳醚酮，包括聚醚醚酮，聚醚酰亚胺，聚酰胺酰亚胺，聚苯硫醚，聚亚苯基，液晶聚合物，聚碳酸酯，芳香族和半芳香族聚酰胺。
19.如权利要求18所述的方法，其中，该零件材料包括间苯二甲胺己二酸盐（MXD6）。
20.根据权利要求1-2中任一项所述的方法，该方法是用基于挤出的增材制造系统制造三维物体的方法。
21.如权利要求20所述的方法，该方法为熔丝制造技术。
22.如权利要求20所述的方法，其中，由所提供的支撑材料打印牺牲支撑结构的层的步骤包括：
a) 将该支撑材料进料到排放头构件，该构件具有以排放尖端结尾的通孔和熔化该通孔中的材料的圆周加热器；
b) 在所述通孔中用活塞压缩该支撑材料，而同时熔化该排放头构件中的支撑材料，以便从该排放尖端挤出支撑材料带；并且
c) 在将支撑材料排放在所述接收平台上的同时确保该排放尖端和所述接收平台在x和y方向上的相对运动，以形成该牺牲支撑结构的横截面形状；并且
d) 在将支撑材料排放在所述接收平台上的同时确保该排放尖端和该接收平台在z方向上的相对运动，以在高度上形成该牺牲支撑结构。
23.如权利要求22所述的方法，其中，在步骤b）中用未熔化的长丝充当活塞。
24.如权利要求22所述的方法，其中，与该打印牺牲支撑结构的层协调来由所提供的零件材料打印该三维物体的层的步骤有利地进一步包括：
a’) 将该零件材料进料到排放头构件，该构件具有以排放尖端结尾的通孔和熔化该通孔中的材料的圆周加热器；
b’) 在所述通孔中用活塞压缩该零件材料，而同时熔化该排放头构件中的零件材料，以便从该排放尖端挤出零件材料带；并且
c) 在将支撑材料排放在所述接收平台和所述牺牲支撑结构上的同时确保该排放尖端和承载该牺牲支撑结构的接收平台在x和y方向上的相对运动，以形成该三维物体的横截面形状，并且
d) 在将零件材料排放在所述接收平台和所述牺牲支撑结构上的同时确保该排放尖端和该接收平台在z方向上的相对运动，以在高度上形成该三维物体。
25.如权利要求24所述的方法，其中，在步骤b）中用未熔化的长丝充当活塞。
26.如权利要求22所述的方法，该方法包括步骤 (iv)：从组件中去除该牺牲支撑结构的至少一部分以便获得该三维物体，涉及将该组件暴露于水蒸气和/或水。
27.如权利要求26所述的方法，其中，步骤 (iv) 包括将该组件在暴露温度下暴露于具有至少70%的相对湿度（RH）的空气或步骤 (iv) 包括使该组件与液体水接触/浸入其中。
28.如权利要求27所述的方法，其中，步骤 (iv) 包括将该组件在暴露温度下暴露于具有至少80%的相对湿度（RH）的空气或步骤 (iv) 包括使该组件与液体水接触/浸入其中。
29.如权利要求28所述的方法，其中，步骤 (iv) 包括将该组件在暴露温度下暴露于具有至少85%的相对湿度（RH）的空气或步骤 (iv) 包括使该组件与液体水接触/浸入其中。
30.如权利要求22所述的方法，其中，将该牺牲支撑结构从该组件中去除，并且其中，将所述牺牲支撑结构从该三维物体上分离并以其固体形式或通过至少部分溶解去除。
31.如权利要求1所述的方法，其中根据以下公式计算所述聚酰胺（A）的吸水率：
Figure DEST_PATH_IMAGE001
其中W前是处于原始干燥状态的成形样品的重量并且W后是吸水后该成形样品的g重量。
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2989059C (en) 2015-06-19 2020-04-07 Stratasys, Inc. Water dispersible polymer for use in additive manufacturing
CN109071802B (zh) 2016-04-01 2021-07-13 索尔维特殊聚合物美国有限责任公司 用于制造三维物体的方法
JP6921669B2 (ja) * 2016-08-05 2021-08-18 花王株式会社 三次元物体前駆体処理剤組成物
US11326020B2 (en) * 2016-08-05 2022-05-10 Kao Corporation Composition for treating three-dimensional object precursor
WO2018197157A1 (en) 2017-04-25 2018-11-01 Solvay Specialty Polymers Usa, Llc Method of making a three-dimensional object using a poly(ether ether ketone) polymeric component
WO2019063740A1 (en) * 2017-09-28 2019-04-04 Rhodia Operations METHOD FOR MANUFACTURING THREE-DIMENSIONAL OBJECT USING POLYAMIDE-BASED SUPPORT MATERIAL
WO2019063741A1 (en) * 2017-09-28 2019-04-04 Rhodia Operations METHOD FOR MANUFACTURING THREE-DIMENSIONAL OBJECT USING DIMENSIONALLY STABLE POLYAMIDE SUPPORT MATERIAL AND WATER SOLUBLE
WO2019075107A1 (en) * 2017-10-10 2019-04-18 Stratasys, Inc. WATER-DISPERSIBLE THERMOPLASTIC MATERIAL COMPRISING A SULFINATED COPOLYMER FOR USE IN ADDITIVE MANUFACTURE
JP7416694B2 (ja) 2017-12-27 2024-01-17 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー ３次元物体を製造する方法
JP7284189B2 (ja) 2018-04-12 2023-05-30 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー 窒化物を用いた３次元物体の製造方法
WO2019219866A1 (en) 2018-05-17 2019-11-21 Solvay Specialty Polymers Usa, Llc Method of making a three-dimensional object using a poly(aryl ether sulfone) (paes) polymer of low polydispersity
CN113099720B (zh) 2018-06-18 2023-04-11 索尔维特殊聚合物美国有限责任公司 使用聚(芳基醚砜)(paes)聚合物制造三维物体的方法
CN109320716B (zh) * 2018-09-10 2021-12-10 湖南华曙高科技有限责任公司 一种应用于选择性激光烧结的尼龙粉末材料制备方法
CN109517370B (zh) * 2018-09-10 2021-07-02 湖南华曙高科技有限责任公司 一种用于选择性激光烧结的尼龙粉末材料制备方法
WO2020077127A1 (en) 2018-10-10 2020-04-16 Stratasys, Inc. Water dispersible sulfonated thermoplastic copolymer for use in additive manufacturing
CA3119537A1 (en) * 2018-11-12 2020-05-22 Technische Universitat Munchen Method for treatment of elements obtained by an additive manufacturing process
CN115943075A (zh) 2019-05-22 2023-04-07 索尔维特殊聚合物美国有限责任公司 用于制造三维物体的增材制造方法
JP7370455B2 (ja) * 2020-03-31 2023-10-27 三井化学株式会社 半芳香族ポリアミド樹脂組成物、およびその成形体
WO2022002590A1 (en) 2020-06-29 2022-01-06 Solvay Specialty Polymers Usa, Llc High melt temperature soluble semi-crystalline polyamides
US11999862B2 (en) * 2020-08-27 2024-06-04 Xerox Corporation Polymer filaments comprising an aqueous-soluble imide polymer and use thereof as a sacrificial printing material in additive manufacturing
WO2022112194A1 (en) 2020-11-30 2022-06-02 Solvay Specialty Polymers Usa, Llc Additive manufacturing method for making a three-dimensional object
US11135771B1 (en) 2021-04-09 2021-10-05 Curiteva, Inc. System and method of manufacturing a medical implant
DE102021125715A1 (de) 2021-10-04 2023-04-06 84J GmbH & Co. KG Verfahren zur trennung von polymerelementen, die durch ein additives fertigungsverfahren hergestellt wurden, mittels granularer mittel
WO2023129660A1 (en) * 2021-12-31 2023-07-06 Evolve Additive Solutions, Inc. Additive manufacturing support material with particulates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552017A (zh) * 2001-05-11 2004-12-01 三维造型的材料和方法
WO2015012862A1 (en) * 2013-07-26 2015-01-29 Hewlett-Packard Development Company, L.P. Composite support material for three-dimensional printing
CN104890240A (zh) * 2015-05-23 2015-09-09 哈尔滨工业大学 纳米粉末激光选择性熔化增材制造系统与方法

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2259345T3 (es) 1995-12-29 2006-10-01 Rhodia Engineering Plastics Srl Poliamida y procedimiento de fabricacion de la misma.
US6070107A (en) 1997-04-02 2000-05-30 Stratasys, Inc. Water soluble rapid prototyping support and mold material
US6228923B1 (en) * 1997-04-02 2001-05-08 Stratasys, Inc. Water soluble rapid prototyping support and mold material
FR2779730B1 (fr) 1998-06-11 2004-07-16 Nyltech Italia Polyamides a fluidite elevee, son procede de fabrication, compositions comprenant ce copolyamide
US7314591B2 (en) * 2001-05-11 2008-01-01 Stratasys, Inc. Method for three-dimensional modeling
GB9927127D0 (en) * 1999-11-16 2000-01-12 Univ Warwick A method of manufacturing an item and apparatus for manufacturing an item
CA2411022A1 (en) 2000-05-19 2001-11-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Dispensing head and method for dispensing solidifying material
US20040062834A1 (en) * 2002-09-26 2004-04-01 Casematic, S.A. De C.V. Polyamide-based sausage casing
US6956099B2 (en) * 2003-03-20 2005-10-18 Arizona Chemical Company Polyamide-polyether block copolymer
US7261542B2 (en) 2004-03-18 2007-08-28 Desktop Factory, Inc. Apparatus for three dimensional printing using image layers
JP5374089B2 (ja) * 2007-09-27 2013-12-25 豊田合成株式会社 エアバッグ用コート基布
FR2939075B1 (fr) 2008-12-01 2010-12-17 Rhodia Operations Realisation d'article par fusion selective de couches de poudre de polymere
TWI385197B (zh) * 2008-12-16 2013-02-11 Taiwan Textile Res Inst 碳黑聚醯胺母粒及其製備方法
FR2944021B1 (fr) 2009-04-02 2011-06-17 Solvay Poly(hydroxyacide) ramifie et procede pour sa fabrication
US8801990B2 (en) 2010-09-17 2014-08-12 Stratasys, Inc. Method for building three-dimensional models in extrusion-based additive manufacturing systems using core-shell semi-crystalline consumable filaments
EP2688955B1 (en) 2011-07-08 2018-07-11 Adesso Advanced Materials Wuxi Co., Ltd. Reinforced composite and method for recycling the same
WO2014012240A1 (en) * 2012-07-20 2014-01-23 Rhodia Operations Novel polyamide, preparation process therefor and uses thereof
EP2914433B1 (en) * 2012-11-05 2018-03-28 Stratasys Ltd. System and method for direct inkjet printing of 3d objects
US9744722B2 (en) * 2012-11-21 2017-08-29 Stratasys, Inc. Additive manufacturing with polyamide consumable materials
US9527242B2 (en) 2012-11-21 2016-12-27 Stratasys, Inc. Method for printing three-dimensional parts wtih crystallization kinetics control
US9592530B2 (en) * 2012-11-21 2017-03-14 Stratasys, Inc. Additive manufacturing with polyamide consumable materials
FR3008704B1 (fr) 2013-07-19 2015-08-21 Rhodia Operations Barriere a la vapeur adaptative
US9714318B2 (en) 2013-07-26 2017-07-25 Stratasys, Inc. Polyglycolic acid support material for additive manufacturing systems
KR20160094397A (ko) * 2013-12-04 2016-08-09 오발론 테라퓨틱스 인코퍼레이티드 위 내 장치를 위치시키고 및/또는 특징화하는 시스템 및 방법
JP6081401B2 (ja) * 2014-03-25 2017-02-15 アイ−スクウェアード・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング サポート部形成用の光硬化性樹脂組成物
US11472929B2 (en) * 2014-04-30 2022-10-18 Institute Of Chemistry, Chinese Academy Of Sciences Nylon powder composition for 3D printing, and preparation method and application thereof
WO2016037563A1 (en) * 2014-09-09 2016-03-17 Jf Polymers (Suzhou) Co., Ltd. Polymeric composition for use as a temporary support material in extrusion based additive manufacturing
US10668682B2 (en) * 2014-10-15 2020-06-02 Shaoxing Ou Ai Di Medical Technology Co., Ltd. Support and method for additive fabrication of foot orthotics
US20160110479A1 (en) * 2014-10-15 2016-04-21 Yong Li System and method for constructing customized foot orthotics
CN105238041B (zh) 2015-10-22 2019-09-06 深圳光韵达光电科技股份有限公司 一种用于选择性激光烧结的尼龙粉末材料及其制备方法
WO2017112689A1 (en) * 2015-12-24 2017-06-29 Stratasys, Inc. Water soluble support materials for high temperature additive manufacturing applications
CN109071802B (zh) 2016-04-01 2021-07-13 索尔维特殊聚合物美国有限责任公司 用于制造三维物体的方法
US10350100B2 (en) * 2016-04-12 2019-07-16 Obalon Therapeutics, Inc. System for detecting an intragastric balloon
JP2018024850A (ja) * 2016-07-28 2018-02-15 花王株式会社 三次元造形用可溶性材料
US20180111337A1 (en) * 2016-10-25 2018-04-26 Stratasys, Inc. Water dispersible polymer composition for use in 3d printer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552017A (zh) * 2001-05-11 2004-12-01 三维造型的材料和方法
WO2015012862A1 (en) * 2013-07-26 2015-01-29 Hewlett-Packard Development Company, L.P. Composite support material for three-dimensional printing
CN104890240A (zh) * 2015-05-23 2015-09-09 哈尔滨工业大学 纳米粉末激光选择性熔化增材制造系统与方法

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