CN117897247A - 用于粉末床增材制造方法的颗粒原料配混物以及成型和烧结方法 - Google Patents
用于粉末床增材制造方法的颗粒原料配混物以及成型和烧结方法 Download PDFInfo
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- CN117897247A CN117897247A CN202280055475.3A CN202280055475A CN117897247A CN 117897247 A CN117897247 A CN 117897247A CN 202280055475 A CN202280055475 A CN 202280055475A CN 117897247 A CN117897247 A CN 117897247A
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Classifications
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Abstract
一种用于粉末床增材制造方法的颗粒原料配混物,包含a)分散在整个配混物颗粒中的最大粒度为200μm的可烧结非有机颗粒,和b)粘合剂组分,相对于所述粘合剂组分的体积,所述粘合剂组分包含b‑i)3‑70体积%的DSC熔体峰值温度TP低于160℃的热塑性聚酰胺,和b‑ii)30‑97体积%的滴点在20‑160℃范围内的蜡或蜡类材料。受能量束照射后,原料配混物颗粒可以在相对较低的温度下从固体转变为流体,并形成致密的生坯部件,而不影响相邻的原料配混物。
Description
本发明涉及包含可烧结非有机颗粒和粘合剂组分的颗粒原料配混物,以及包括合并多个颗粒原料配混物、脱粘和烧结的步骤的方法。该颗粒原料配混物特别适用于粉末床增材制造方法。
诸如增材制造、粉末注射成型或压制等方法可以快速高效地生成定制部件。增材制造涉及将材料添加在一起,例如将粉末颗粒熔合在一起,通常是逐层添加。一般来说,典型的增材制造方法包括以下步骤:形成第一材料层,并随后连续添加另外的材料层,其中每个新的材料层被添加到前面形成的材料层上,直到实现整个三维结构(3D对象)。
在激光束粉末床熔融(LB-PBF)中,通过高功率激光束扫描来烧结不含粘合剂的粉末化金属。为了省去高功率激光器,通过增材制造对涂有粘合剂的金属粉末进行成型。在后处理步骤中,去除粘合剂并烧结金属粉末。
WO 2018/197082公开了一种用于增材制造金属和/或玻璃型和/或陶瓷组件的方法。原料配混物颗粒由基质颗粒和至少两相粘合剂制备。通过电磁辐射将原料配混物颗粒选择性地分层熔化,从而增材制造模制部件。从未熔化的混合物中取出模制部件,然后连续除去该至少两相粘合剂。最后,对脱粘成型部件进行烧结。在第一步中,用溶剂萃取一个粘合剂相。残留的粘合剂作为保持形状的骨架,在烧结过程的同时和/或之前被去除。
然而,打印过程中的不同因素可能会影响部件相对于定义它的对象数据的尺寸精度。例如,通常难以制造具有锋利而精确的边缘并且具有低孔隙率的(生坯)部件。而且,成型步骤的改进不应给脱粘步骤带来缺陷或导致其恶化。
因此,本发明的一个目的是提供一种颗颗粒原料配混物,其能实现高维打印精度,并在使用该原料配混物的方法中以简单、经济的方式脱粘。
本发明涉及一种用于粉末床增材制造方法的颗粒原料配混物,基于颗粒原料配混物的总体积,其包含:
a)分散在整个配混物颗粒中的最大粒度为200μm的可烧结非有机颗粒,和
b)粘合剂组分,相对于该粘合剂组分的体积,该粘合剂组分包含
b-i)3-70体积%的DSC熔体峰值温度Tp低于160℃的热塑性聚酰胺,和
b-ii)30-97体积%的滴点在20-160℃范围内的蜡或蜡类材料。
本发明还涉及一种方法,其包括合并多个颗粒原料配混物、脱粘和烧结的步骤。
除非另有说明,以下描述涉及颗粒原料配混物和方法的优选实施方案。
颗粒原料配混物可用于粉末床增材制造方法,特别是基于烧结的粉末床增材制造方法,例如选择性激光增材制造方法或多射流熔合方法。
一般而言,增材制造方法的成型步骤涉及在构造空间中提供颗粒原料配混物的粉末床,其通常被加热到高温(例如,50-60℃)。粉末床中的颗粒原料配混物可以吸收能量,例如来自辐射源的能量束,如激光束,粉末材料的局部区域的温度因此升高。温度的局部增加允许选择性地致密化或熔化颗粒原料配混物,使得颗粒原料配混物以预定方式彼此结合。
已经发现,粘合剂的熔化行为对打印精度有很大影响。虽然希望在局部区域内在颗粒原料配混物之间形成牢固的结合,但是应当避免与相邻或毗邻的颗粒形成结合。含有非优化粘合剂成分的原料配混物可能将热散发到相邻的颗粒,这些颗粒会软化并粘附到部件的外表面,从而导致表面光洁度差。
对于本发明的粘合剂组分,从固体或半固体到流体的温度转变非常窄,导致在3D打印中对相邻原料配混物颗粒的影响较小。结果,受能量束照射的原料配混物颗粒可以在相对较低的温度下从固体转变为流体,并形成致密的生坯部件,而不影响相邻的原料配混物。
颗粒原料配混物
本发明的颗粒原料配混物含有如上所述的可烧结非有机颗粒(a)和粘合剂组分(b),并且可用于粉末床增材制造方法。
本文中,术语“颗粒”表示原料配混物由单个颗粒的集合(或多个单个颗粒)组成。单个颗粒可以具有任意形状,例如不规则形状、圆柱形、旋转椭球形或基本上球形。
一般而言,颗粒原料配混物的粒度分布使得至少80体积%、优选至少90体积%、更优选至少95体积%、最优选至少99体积%的颗粒原料配混物的最大粒径Bmax在0.005-0.3mm,优选0.008-0.2mm,更优选0.01-0.2mm,最优选0.015-0.15mm的范围内。
每个颗粒原料配混物包含多个可烧结非有机颗粒(a),在整个颗粒原料配混物中,可烧结非有机颗粒(a)分散在粘合剂组分(b)的基质内,并且通过粘合剂组分(b)保持在一起。每个原料配混物颗粒含有多个可烧结非有机颗粒(a)使得颗粒原料配混物的形状可以独立于可烧结非有机颗粒(a)的形状。因此,例如,可以生产基本上球形的颗粒原料配混物,而可烧结非有机颗粒(a)无需是球形的。这降低了生产成本,因为具有任意或不规则颗粒几何形状或更宽粒度分布的可烧结非有机颗粒(a)比具有特定(例如球形)颗粒几何形状的粉末更容易获得。
举例而言,颗粒原料配混物通过对可烧结非有机颗粒(a)和溶解有粘合剂组分(b)的溶剂(例如醇类溶剂)的悬浮液进行喷雾干燥来制备。或者,可以研磨粘合剂组分(b)的固结熔体,粘合剂组分(b)中分散有可烧结非有机颗粒(a)。较大颗粒的原料配混物也可以通过挤出机配混并随后造粒。
在一个实施方式中,颗粒原料配混物含有按体积计约0.70-0.99·φr、优选按体积计约0.75-0.98·φr、更优选按体积计约0.80-0.96·φr、最优选按体积计约0.82-0.95·φr,特别是按体积计约0.84-0.94·φr,特别是按体积计约0.86-0.93·φr的可烧结非有机颗粒(a),其中φr是按体积计的临界固体加载量。剩余部分包含粘合剂组分b)。
一般而言,术语“临界固体加载量”是指在临界极限下原料配混物中按体积计的可烧结非有机颗粒的量。当向原料配混物中添加可烧结非有机颗粒而导致原料配混物的相对粘度变得无穷大以至其变硬并且不流动时,就达到所述“临界极限”。物理上讲,“临界固体加载量”定义了颗粒的最紧堆积排列,同时仍保留连续材料,并且它是一个极限,超过该极限就不可能继续向粘合剂基质加载固体粉末。在本文中,术语“相对粘度”表示原料配混物的粘度相对于纯粘合剂的粘度,以便剔除可烧结非有机颗粒的影响。添加可烧结非有机颗粒后,原料配混物的粘度增加。
有多种方法可以确定临界固体加载量。例如,当向粘合剂中添加越来越多的金属粉末时,可以测定捏合机扭矩的峰值。达到临界固体加载量后,随着原料配混物变得更易碎,扭矩通常会再次降低。或者,可以采用比重计测量方法:直到临界固体加载量,理论密度与比重计测量的密度一致,而高于临界固体加载量时,测量的密度因为孔的影响而低于理论密度[另请参见:1990年,R.M.哲曼(German),粉末注射成型(Powder InjectionMolding),金属粉末工业联合会(Metal Powder Industries Federation)1990年,第129-130页]。也可采用流变测量方法,通过绘制φ·ηr:(ηr-1)-φ图估算临界固体加载量[J.S.庄(Chong),E.B.克里斯蒂安森(Christiansen),A.D.贝尔(Baer),应用高分子科学学报(J.Appl.Polym.Sci.),1971,15,2007-2021]。在本文中,φ表示加载量,ηr表示相对粘度。
或者,在一个实施方式中,颗粒原料配混物含有约20-90体积%、优选30-80体积%、更优选40-75体积%、最优选45-70体积%、特别是50-65体积%的可烧结非有机颗粒(a),以及
约10-80体积%、优选20-70体积%、更优选25-60体积%、最优选30-55体积%、特别是35-50体积%的粘合剂组分(b)。
可烧结非有机颗粒
可烧结非有机颗粒(a)包括常规已知的可烧结材料。一般而言,可烧结非有机颗粒(a)选自金属、合金、玻璃质颗粒和陶瓷颗粒。
在一个实施方式中,金属选自铁、不锈钢、钢、铜、青铜、铝、钨、钼、银、金、铂、钛、镍、钴、铬、锌、铌、钽、钇、硅、镁、钙及其组合。金属颗粒适合具有这样的粒度分布,使得至少85%、优选至少90%、更优选至少95%、最优选至少99%的颗粒具有在500nm至400μm、优选1μm至150μm、更优选3μm至50μm、最优选5μm至25μm范围内的最大粒度Amax。
合金适合选自钢[例如不锈钢(316L,17-4PH)]、铬镍钢、青铜、铜合金(例如Hovadur)、镍基合金(例如哈氏合金(Hastelloy)或铬镍铁合金(Inconel))、钴和钴-铬合金(例如司太立合金(stellite))、铝合金(例如铝6061)、钨重合金、钛合金(例如根据ASTM的1级经由5级(Ti-6AI-4V)到38级)。
在一个实施方式中,陶瓷颗粒选自氧化物,例如氧化铝、氧化硅、氧化锆、氧化钛、氧化镁、氧化钇;碳化物,例如碳化硅、碳化钨;氮化物,例如氮化硼、氮化硅、氮化铝;硅酸盐,例如块滑石(steatite)、堇青石、莫来石;及其组合。陶瓷颗粒适合具有这样的粒度分布,使得至少85%、优选至少90%、更优选至少95%、最优选至少99%的颗粒具有在200nm至25μm、优选300nm至10μm、更优选400nm至7μm、最优选500nm至3μm范围内的最大粒度Amax。
在一个实施方式中,玻璃质颗粒选自非氧化物玻璃,例如卤化物玻璃、硫族化合物玻璃;氧化物玻璃,例如磷酸盐玻璃、硼酸盐玻璃;硅酸盐玻璃,例如铝硅酸盐玻璃、铅硅酸盐玻璃、硼硅酸盐玻璃、钠钙硅酸盐玻璃、石英玻璃、碱金属硅酸盐玻璃等;及其组合。玻璃质颗粒适合具有这样的粒度分布,使得至少85%、优选至少90%、更优选至少95%、最优选至少99%的颗粒具有在200nm至25μm、优选300nm至10μm、更优选400nm至7μm、最优选500nm至3μm范围内的最大粒度Amax。
可烧结非有机颗粒(a)可适合包含如上所述的金属、合金、玻璃质颗粒和陶瓷颗粒中的多于一种的组合,例如硬质金属或金属基质复合材料(也称为金属陶瓷复合材料)。
热塑性聚酰胺
基于粘合剂组分(b)的总体积,粘合剂组分(b)包含3-70体积%、优选5-60体积%、更优选7-50体积%、最优选10-40体积%、特别是12-35体积%、特别是15-30体积%的热塑性聚酰胺(b-i)。
术语“聚酰胺”旨在涵盖聚酰胺和共聚酰胺。共聚酰胺包含至少两种不同类型的重复单元。选择共聚单体,使得共聚酰胺满足一种或多种特定熔融标准,包括例如DSC熔体峰值温度TP、熔体粘度和熔体体积流动速率。
热塑性聚酰胺的特征在于具有低于160℃的DSC熔体峰值温度TP。在确定的范围内的熔体峰值温度TP允许用尽可能少的附加能量(例如激光能量)实现选择性致密化或熔化,并且可以方便地使用低能量激光源。在一个实施方式中,热塑性聚酰胺优选具有低于150℃、更优选低于140℃、最优选低于130℃、特别是低于120℃的DSC熔融峰温度TP。
差示扫描量热法(DSC)可以测定材料的物理性质,例如玻璃化转变温度、熔融温度、熔融焓等。
熔融过程导致DSC曲线中出现吸热峰,熔融温度是指所述DSC曲线中吸热热流变化率最大时的熔融峰温度TP。
DSC曲线可包含单个熔融峰。或者,DSC曲线可包含几个熔融峰,即几个局部最大值。出于本文的目的,熔体峰值温度TP定义为全局最大值处的温度。热塑性聚酰胺优选表现出单一熔融峰。
本文中,TP是根据DIN EN ISO 11357-3在第一加热/冷却循环之后的第二次加热中测定的。为此,样品在第一个升温段加热,该第一个升温段从-20℃到比所有热事件完成时高出20K的温度,然后冷却到-20℃,最后在第二个升温段再次加热,该第二个升温段从-20℃到比所有热事件完成时高出20K的温度,每次加热和冷却的速率均为10K/min。出于本文的目的,“热事件”是指除分解以外的热事件,或者换句话说,基本上可逆的热事件。
优选地,热塑性聚酰胺的熔体粘度低于1500Pa·s,优选低于1300Pa·s,更优选低于1000Pa·s,最优选低于800Pa·s,特别是低于600Pa·s,特别是低于500Pa·s,特别是低于400Pa·s,特别是低于300Pa·s,特别是低于200Pa·s,特别是低于100Pa·s,根据ISO1133在160℃下以2.16kg条件测定。
优选地,热塑性聚酰胺的熔体粘度低于1500Pa·s,优选低于1300Pa·s,更优选低于1000Pa·s,最优选低于800Pa·s,特别是低于600Pa·s,特别是低于500Pa·s,特别是低于400Pa·s,特别是低于300Pa·s,特别是低于200Pa·s,特别是低于100Pa·s,根据ISO1133在190℃下以2.16kg条件测定。
优选地,热塑性聚酰胺的熔体体积流动速率为至少1cm3/10min,优选至少2cm3/10min,更优选至少3cm3/10min,最优选至少4cm3/10min,特别是至少5cm3/10min,特别是至少6cm3/10min,特别是至少7cm3/10min,特别是至少8cm3/10min,特别是至少9cm3/10min,特别是至少10cm3/10min,特别是至少20cm3/10min,特别是至少30cm3/10min,特别是至少40cm3/10min,特别是至少50cm3/10min,特别是至少60cm3/10min,特别是至少70cm3/10min,特别是至少80cm3/10min,特别是至少90cm3/10min,特别是至少100cm3/10min,特别是至少110cm3/10min,特别是至少120cm3/10min,特别是至少130cm3/10min,特别是至少140cm3/10min,特别是至少150cm3/10min,特别是至少160cm3/10min,特别是至少170cm3/10min,特别是至少180cm3/10min,特别是至少190cm3/10min,特别是至少200cm3/10min,根据ISO1133在160℃下以2.16kg条件测定。
优选地,热塑性聚酰胺的熔体体积流动速率为至少1cm3/10min,优选至少2cm3/10min,更优选至少3cm3/10min,最优选至少4cm3/10min,特别是至少5cm3/10min,特别是至少6cm3/10min,特别是至少7cm3/10min,特别是至少8cm3/10min,特别是至少9cm3/10min,特别是至少10cm3/10min,特别是至少20cm3/10min,特别是至少30cm3/10min,特别是至少40cm3/10min,特别是至少50cm3/10min,特别是至少60cm3/10min,特别是至少70cm3/10min,特别是至少80cm3/10min,特别是至少90cm3/10min,特别是至少100cm3/10min,特别是至少110cm3/10min,特别是至少120cm3/10min,特别是至少130cm3/10min,特别是至少140cm3/10min,特别是至少150cm3/10min,特别是至少160cm3/10min,特别是至少170cm3/10min,特别是至少180cm3/10min,特别是至少190cm3/10min,特别是至少200cm3/10min,根据ISO1133在190℃下以2.16kg条件测定。
在一个实施方式中,热塑性聚酰胺(b-i)是半结晶的。术语“半结晶”表征那些具有高度分子间和分子内有序度的聚合物。聚合物的半结晶性质可以通过差示扫描量热法(DSC)测定的一级转变或结晶熔点(Tm)来验证。优选地,热塑性聚酰胺(b-i)是半结晶的,因为它表现出分开流体状态和固结状态的急剧转变。另外,它的特征在于因固结时结晶化而强度增加。
合适的聚酰胺包括这样的聚酰胺,如聚酰胺12,共聚酰胺如Griltex2439A、Griltex 1796A、Griltex 1500A、Griltex D 2638A[可购自EMS化学股份有限公司(EMS-CHEMIE HOLDING AG)];Orgasol 3502D[可购自阿科玛(Arkema)]、UNI-REZ 2620、UNI-REZ2638、UNI-REZ 2656、UNI-REZ 2674、UNI-REZ 2720、UNI-REZ 2291[可购自科腾公司(Kraton Corporation)];
一般而言,聚酰胺可以通过羧酸和胺反应生成酰胺或通过羧酸和胺的部分/衍生物的反应来生产。聚酰胺均聚物可以通过一种单体(即具有4至25个碳原子的氨基酸或内酰胺)的反应来生产,例如通过ε-己内酰胺的开环聚合来生产聚酰胺6。聚酰胺可以通过具有4至25个碳原子的二胺与具有4至25个碳原子的二羧酸或其盐的缩聚反应来制备,例如通过己二胺与己二酸的缩聚反应或通过己二酸己二胺盐的反应来制备聚酰胺6.6。共聚酰胺可以通过不同的胺与不同的羧酸的缩聚反应来制备,优选具有4至25个碳原子的二胺,如己二胺,优选具有4至25个碳原子的二羧酸,如己二酸、壬二酸、十二烷二酸,优选具有4至25个碳原子的氨基羧酸,例如氨基十一烷酸,或者它们的盐。通过将不同单体混合并反应生成共聚酰胺三元、四元和多元体系,可调节共聚酰胺的性能,例如熔点和/或粘度和/或粘合力。例如,通过将PA6(ε-己内酰胺)、PA6.6(己二胺和己二酸或己二酸己二胺盐)和PA12(氨基月桂酸)单体混合在三元体系中,可以得到熔点为110-120℃的混合物,其包含20-40% PA6.6、20-40% PA6和30-50% PA12,而纯PA6.6、PA6和PA12的熔点分别为250℃、215℃和176℃。采用支化和/或芳族羧酸以及/或者支化和/或芳族胺以及进一步采用其他反应物例如醚、酯、弹性体等的反应本身是已知的。
Griltex 2439A(可购自EMS化学股份有限公司)是特别优选的热塑性聚酰胺。
蜡或蜡类材料
基于粘合剂组分(b)的总体积,粘合剂组分(b)还包含30-97体积%、优选40-95体积%、更优选50-93体积%、最优选60-90体积%、特别是65-88体积%、特别是70-85体积%的蜡或蜡类材料(b-ii)。
蜡或蜡类材料的特征在于根据DIN ISO 2176具有20-160℃范围内的滴点。更优选地,极性蜡的滴点在30-150℃的范围内,还更优选在35-140℃的范围内,特别是在40-130℃的范围内,特别是在40-120℃的范围内,特别是在40-110℃的范围内,特别是在40-100℃的范围内,并且最优选在40-90℃的范围内。
在所确定范围内的滴点与热塑性聚酰胺的DSC熔体峰值温度TP一起确保了粘合剂良好的整体熔融行为。
更优选地,蜡的熔体粘度低于30Pa·s,优选低于20Pa·s,更优选低于10Pa·s,最优选低于5Pa·s,特别是低于3Pa·s,特别是低于1Pa·s,特别是低于700mPa·s,特别是低于300mPa·s,特别是低于100mPa·s,特别是低于50mPa·s,根据DIN EN ISO 3104在160℃下测定。
更优选地,极性蜡的熔体粘度低于40Pa·s,优选低于30Pa·s,更优选低于20Pa·s,最优选低于10Pa·s,特别是低于5Pa·s,特别是低于3Pa·s,特别是低于1Pa·s,特别是低于700mPa·s,特别是低于300Pa·s,特别是低于100mPa·s,根据DIN EN ISO 3104在120℃下测定。
术语“蜡”是一组有机物质的技术统称,通常可以用其物理和技术性质来描述。具体而言,蜡的特征在于它们是固体,熔点高于环境温度(通常在50℃至160℃之间),熔体粘度低(在高于熔点10℃时低于10Pa·s)。蜡熔化而不分解。蜡还可分为化石来源的天然蜡,如石蜡、褐煤蜡;天然来源的天然蜡,例如蜂蜡、巴西棕榈蜡;半合成蜡(也称为化学改性天然蜡),例如亚乙基双硬脂酰胺;合成蜡,例如聚烯烃蜡。在本专利申请的上下文中,术语“蜡类材料”旨在包括蜡以及蜡类物质,例如酯型蜡、高级醇或多元醇、表现出蜡样性质的高级脂肪酸,以及它们的混合物。
合适的蜡类材料包括:
石蜡,例如微晶蜡;
酯型蜡,例如蜂蜡、小烛树蜡、巴西棕榈蜡;
有机酸的酯,例如磺酸或羧酸的酯,优选具有6至40个碳原子的脂肪酸的酯;或芳族羧酸的酯,例如苯甲酸、邻苯二甲酸或羟基苯甲酸的酯;
酰胺蜡,例如有机酸的酰胺,如磺酸或羧酸的酰胺,优选具有6至40个碳原子的脂肪酸的酰胺,如:油酰胺,如Deurex A 27P[可购自杜莱克斯公司(Deurex AG)],芥酸酰胺,如Deurex A 26P(可购自杜莱克斯公司),亚乙基双硬脂酰胺,如Deurex A 20K(可购自杜莱克斯公司);磺酰胺,如N-乙基甲苯-4-磺酰胺;
聚烯烃蜡,例如
聚乙烯蜡,如Deurex E 06K、Deurex E 08、Deurex E 09K、Deurex E10K(可购自杜莱克斯公司)、111、/>116、/>123、135[可购自因诺斯贝路纳公司(Innospec Leuna)];
氧化聚乙烯蜡,如Deurex EO 40K、Deurex EO 42、Deurex EO 44P、Deurex E 76K(可购自杜莱克斯公司)、252、/>262、/>271、2628(可购自因诺斯贝路纳公司);
聚烯烃的共聚蜡,优选乙烯乙酸乙烯酯,例如334、453(可购自因诺斯贝路纳公司),
聚丙烯蜡,例如Deurex P 36K、Deurex P 37K(可购自杜莱克斯公司);
氧化聚丙烯蜡;
费-托蜡(Fischer-Tropsch wax),例如VESTOWAX EH 100、VESTOWAX H 2050MG、VESTOWAX SH 105、Shell GTL Sarawax SX 105、Shell GTL Sarawax SX 80(可获自赢创工业集团公司);
高级有机酸,例如具有10-40个碳原子数的脂肪酸;
高级醇或多羟基醇,例如具有10-40个碳原子的醇;
聚乙二醇;
及其混合物。
为了适应不同的目的,蜡或蜡类材料可以是不同蜡或蜡类材料的混合物。
通常,石蜡(例如微晶蜡)源自石油。例如,微晶蜡是作为主要含有饱和脂肪族烃的固体的精制混合物而获得的,其通过对来自石油精炼过程的某些馏分进行脱油而产生。
通常,酯型蜡可以是天然存在的蜡或合成产生的蜡。天然存在的酯型蜡适合选自蜂蜡、小烛树蜡和巴西棕榈蜡;合成生产的酯型蜡适合选自羧酸的酯,优选具有5-34个碳原子的脂肪酸的酯,更优选具有10-28个碳原子的脂肪酸的酯,或羟基苯甲酸的酯。优选地,酯型蜡包含羟基苯甲酸的酯,例如4-羟基苯甲酸的酯。Loxiol 2472[4-羟基苯甲酸二十二烷醇酯,可购自埃默里油脂化学股份有限公司(Emery Oleochemicals GmbH)]是特别优选的。
通常,聚烯烃蜡可以通过热分解支化高分子量聚烯烃或直接聚合烯烃来生产。合适的聚烯烃蜡包括例如丙烯或更高级1-烯烃的均聚物,丙烯与乙烯或更高级1-烯烃的共聚物,或它们彼此的共聚物。更高级1-烯烃优选为具有4-20个、优选4-6个碳原子的直链或支化烯烃。这些烯烃可具有与烯属双键共轭的芳族取代基。它们的实例是1-丁烯、1-己烯、1-辛烯或1-十八碳烯以及苯乙烯。可以将聚烯烃蜡氧化。特别优选聚乙烯蜡,例如Deurex E06K(可购自杜莱克斯公司)。
通常,酰胺蜡,如磺酸或羧酸、优选脂肪酸的酰胺,可以通过酰胺(如乙二胺)与磺酸或羧酸(优选具有5-34个碳原子、优选10-28个碳原子的脂肪酸)的缩合反应来制备。特别优选油酰胺如Deurex A 27P(可购自杜莱克斯公司),芥酸酰胺如Deurex A 26P(可购自杜莱克斯公司),亚乙基双硬脂酰胺如Deurex A 20K(可购自杜莱克斯公司)。
综合考虑与热塑性聚酰胺的相容性和溶剂溶解性,蜡或蜡类材料优选选自极性蜡和极性蜡类材料。
本文中,术语“极性蜡”或“极性蜡类材料”是指其化学结构基本上由碳和氢原子形成或者甚至由碳和氢原子组成的蜡或蜡类材料,并且包含至少一个高电负性杂原子,例如氧、氮或硫原子。
优选地,极性蜡选自氧化聚烯烃蜡、酯型蜡、酰胺蜡、高级有机酸、高级醇或多元醇、聚乙二醇及其混合物。
优选地,酯型蜡包括有机酸的酯。优选地,酰胺蜡包括有机酸如磺酸或羧酸的酰胺。可商购的合适蜡的代表是上面提到的那些。
在又更优选的实施方式中,b-ii)是选自芳族酯和芳族磺酰胺的蜡类材料。芳族酯的醇可以是具有1-40个碳原子的醇。芳族磺酰胺可以在酰胺氮原子处携带至少一个具有1-40个碳原子的有机部分。
增塑剂
在一个实施方式中,粘合剂组分b-ii)是增塑蜡或蜡类材料。“增塑蜡或蜡类材料”是指蜡或蜡类材料与增塑剂的组合。一般而言,增塑剂是沸点一般高于180℃的高沸点液体,其与蜡或蜡类材料相容以降低其熔体粘度。技术人员将理解,热塑性聚酰胺、蜡或蜡类材料和增塑剂的三元组合形成均相。一般而言,增塑剂是极性化合物,这意味着它们的化学结构包含至少一种高电负性杂原子,例如氧原子或氮原子。
相对于增塑蜡或蜡类材料b-ii)的总体积,增塑蜡或蜡类材料b-ii)适合包含最多50体积%、优选最多40体积%、更优选最多30体积%、最优选最多20体积%、特别是最多15体积%、特别是最多10体积%的增塑剂。
合适的增塑剂包括
脂族羧酸的液体酯,例如癸二酸二甲酯、癸二酸二正辛酯、琥珀酸二甲酯、己二酸二甲酯、己二酸二丁酯、己二酸二辛酯、壬二酸二甲酯、壬二酸二辛酯、马来酸二正丁酯、马来酸二辛酯、油酸丁酯、己烷二酸二甲酯、月桂酸苄酯、月桂酸甲酯、肉豆蔻酸乙酯、柠檬酸二乙酰基三乙酯、柠檬酸乙酰基三丁酯;
芳族羧酸的液体酯,例如邻苯二甲酸二甲酯、2-羟基苯甲酸甲酯、4-羟基苯甲酸丁酯、苯甲酸丁酯、苯甲酸2-乙基己酯、对苯二甲酸双(2-乙基己基)酯;
烷基磺酸苯酯;
液体酰胺类,例如正丁基苯磺酰胺、N-乙基甲苯-2-磺酰胺、N-乙基-4-甲苯磺酰胺;
液体有机酸,例如羧酸,如脂肪酸,如辛酸、肉豆蔻油酸;
高级醇,如1-癸醇、2-癸醇、1-十八醇;
多元醇,如丁二醇、乙二醇、丙二醇;
及其混合物。
选自芳族酯和芳族磺酰胺的增塑剂通常是优选的。
可选的粘合剂组分
粘合剂组分(b)包含至少两种粘合剂组分成分:热塑性聚酰胺(b-i)和蜡或蜡类材料(b-ii)。任选地,考虑到良好的加工性能,粘合剂组分(b)可以包含另外的功能添加剂。
粘合剂组分(b)可以包含分散剂。构成例如蜡或蜡类材料(b-ii)的一种材料可以充当分散剂。或者,可以另外掺入外来分散剂。
通常,分散剂充当粘合剂组分(b-i)和/或(b-ii)之间的粘合促进剂和/或增容剂;和/或非有机颗粒(a)和粘合剂组分(b)之间的粘合促进剂和/或增容剂。
分散剂适合选自具有10-24个碳原子的脂肪酸,例如癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、山萮酸、木蜡酸或油酸,优选硬脂酸。
外来分散剂适合选自脂肪酸的金属盐。通常,金属可以选自碱金属、碱土金属或过渡金属,例如锂、钠、钾、镁、钙、锶、钡和锌。脂肪酸可适合选自如上所述具有5-34个碳原子、优选10-28个碳原子的脂肪酸。优选的脂肪酸金属盐选自硬脂酸钠、硬脂酸镁、硬脂酸锌或油酸镁。
由于粘合剂组分(b)的粘度在前文所述范围内,粘合剂组分(b)在熔融状态下变得均匀地分布在可烧结非有机颗粒(a)之间,并且将各可烧结非有机颗粒(a)或者各颗粒原料配混物接合在一起。
为了调节粘合剂组分(b)的粘度,可能需要掺入稀释剂或增稠剂。增稠剂用于增加粘合剂组分熔融时的粘度。这种提高的粘度防止可烧结非有机颗粒下垂,并促进颗粒的均匀流动,赋予抗离析和抗沉降性能。使用稀释剂来降低粘合剂组分的整体粘度。稀释剂可充当增塑剂,以实现对热塑性聚酰胺(b-i)或者蜡或蜡类材料(b-ii)的流变性质和流动性的控制。
增稠剂或稀释剂适合选自蜡和/或热塑性聚合物,例如聚烯烃和聚烯烃蜡、聚酰胺和酰胺蜡、石蜡、酯型蜡;乙烯基酯类,例如乙烯乙酸乙烯酯;松香酯/盐;己二酸酯/盐;烷基磺酸酯/盐;胺和酰胺,例如甲酰胺、羟烷基甲酰胺、胺、二胺;壬二酸酯/盐;苯甲酸酯/盐;柠檬酸酯/盐;氯化石蜡;醚酯类增塑剂;戊二酸酯/盐;烃油;异丁酸酯/盐;马来酸酯/盐;油酸酯/盐;磷酸酯/盐;邻苯二甲酸酯/盐;磺酰胺;油性液体,例如花生油、鱼油、蓖麻油;及其混合物。140℃下粘度<40mPa·s的聚乙烯蜡Deurex E 09K可适合用作稀释剂,而140℃下粘度为4000mPa·s的Deurex E 25或者甚至分子量更高的聚烯烃类化合物可以用作增稠剂。
在一个实施方式中,基于粘合剂组分(b)的总体积,增稠剂或稀释剂和/或分散剂可以0-15体积%、优选0.01-10体积%、更优选0.02-8体积%、最优选0.5-6体积%的量存在。
溶剂脱粘
热塑性聚酰胺(b-i)和蜡或蜡类材料(b-ii)在溶剂中的溶解度不同。所述溶剂优选选自醇类,例如乙醇或丙醇;芳族化合物,例如苯、甲苯或二甲苯;酯类,例如乙酸乙酯;醚类,例如乙醚或四氢呋喃;酮类,例如丙酮;烷烃,例如己烷或庚烷;卤代烃,例如正丙基溴、三氯乙烯、全氯乙烯、正甲基吡咯烷;及其混合物;水;以及超临界状态的气体。
不同的溶解度允许选择性脱粘。在选择性脱粘步骤中,去除一种粘合剂组分,同时另一种粘合剂组分保留在待制造的部件内,将可烧结非有机颗粒保持在一起。这种脱粘方法(例如溶剂脱粘)本身是已知的。
在溶剂脱粘方法中,可适合通过将一种粘合剂组分溶解在溶剂中来从生坯部件中选择性地去除所述粘合剂组分,其中第二粘合剂组分保留在生坯部件内。因此,各粘合剂组分需要在例如分子量或极性方面有所不同,以在溶剂中表现出不同的溶解性。
方法
本发明还涉及一种方法,包括以下步骤:
–合并多个颗粒原料配混物以获得生坯部件,以及
–通过选择性地去除蜡或蜡类材料(b-ii)对生坯部件进行部分脱粘,以获得褐坯部件,其包含通过热塑性聚酰胺(b-i)彼此结合的可烧结非有机颗粒(a),以及
–烧结该褐坯部件以获得烧结部件。
在一个实施方式中,该方法选自粉末床增材制造方法,特别是基于烧结的粉末床增材制造方法,例如选择性激光增材制造方法或多射流熔合方法。
在本专利申请的上下文中,如果该方法选自增材制造方法,则术语“合并”是指“选择性地熔化和固结”。
通过仔细选择组分和工艺参数,可获得优选不具有任何裂纹的组件。例如,当脱粘进行得太快或在恶劣条件下进行时,就会产生这种裂纹。因此,宜对组分和工艺参数加以选择,以避免有害条件。
通常,在利用来自激光阵列、辐射加热元件等的辐射的增材制造方法中,例如,在惠普公司(HP Inc.)的激光增材制造方法或多射流熔合方法中,逐层施加颗粒原料配混物,然后进行致密化和固结,例如通过冷却进行。在致密化过程中,包含在颗粒原料配混物中的粘合剂组分(b)通过电磁辐射(例如激光)选择性地逐层熔融。
在一个优选的实施方式中,合并多个颗粒原料配混物的步骤包括以下步骤:
-提供第一层原料配混物颗粒;
-选择性地使第一层原料配混物颗粒致密化,以将配混物颗粒以预定方式彼此粘合,从而产生第一成型部件层;
-在第一成型部件层上提供至少一个另外的原料配混物颗粒层;以及
-选择性地使所述另外的原料配混物颗粒层致密化,以将原料配混物颗粒以预定方式彼此粘合,从而产生至少一个另外的成型部件层,
所述第一成型部件层和所述另外的成型部件层形成生坯部件。
优选地,选择性地使所述第一配混物颗粒层和所述另外的配混物颗粒层致密化涉及选择性地用电磁辐射、优选激光束照射所述第一配混物颗粒层和所述另外的配混物颗粒层中的至少一者。
构建室被配置为接收颗粒原料配混物。在选择性致密化后,例如通过激光增材制造方法,原料配混物颗粒以预定方式彼此结合,从而产生第一成型部件层。然后,将至少一个另外的原料配混物颗粒层选择性地致密化在第一成型部件层上,以将原料配混物颗粒以预定方式彼此粘合,从而产生接合到第一成型部件层上的至少一个另外的成型部件层。第一成型部件层和另外的成型部件层共同形成整体式部件。然后,可以将整体式部件从构建室中取出,并去除未结合的颗粒原料配混物。
在该方法中,粘合剂组分(b)分布在可烧结非有机颗粒(a)之间,并在固结后将它们保持在一起。生坯部件制成后,将其从未熔化的层或模具中取出。
通过溶剂处理来部分去除临时有机粘合剂。
适合选择性去除蜡或蜡类材料(b-ii),而不去除热塑性聚酰胺(b-i)。脱粘步骤后得到的部件称为褐坯部件。褐坯部件包含通过热塑性聚酰胺(b-i)和任选的剩余蜡或蜡类材料(b-ii)彼此结合的可烧结非有机颗粒(a)。
保留在褐坯部件中的剩余粘合剂组分提供了稳定且足够坚固的褐坯部件,以在脱粘和烧结步骤之间处理和运输。
在溶剂处理过程中,将生坯部件浸入合适的溶剂中。适合选择溶剂,使得热塑性聚酰胺(b-i)在溶剂中具有比蜡或蜡类材料(b-ii)更低的溶解度,或者优选地,热塑性聚酰胺(b-i)基本上不溶于溶剂,而蜡或蜡类材料(b-ii)可溶于溶剂。合适的溶剂选自醇类,例如乙醇或丙醇;芳族化合物,例如苯、甲苯或二甲苯;酯类,例如乙酸乙酯;醚类,例如乙醚或四氢呋喃;酮类,例如丙酮;烷烃,例如己烷或庚烷;卤代烃,例如正丙基溴、三氯乙烯、全氯乙烯、正甲基吡咯烷;水;超临界状态的气体;及其混合物。在溶剂处理过程中,溶剂的温度TL优选保持在20℃-100℃、优选25℃-80℃、更优选30℃-60℃的范围内。
粘合剂组分(b-ii)的部分去除导致褐坯部件的多孔结构。可烧结非有机颗粒(a)通过热塑性聚酰胺(b-i)保持在一起。
烧结步骤
在一个实施方式中,该方法还包括烧结褐坯部件以获得烧结部件的步骤。
为此目的,在脱粘步骤之后,适合对褐坯部件进行烧结步骤。在烧结步骤中,去除热塑性聚酰胺(b-i),并对脱粘部件(褐坯部件)进行烧结,得到烧结部件。一般来说,在进一步去除粘合剂和随后烧结褐坯部件时,会发生收缩。
剩余粘合剂适合在第一温度T1下被驱除,该第一温度T1在100℃-750℃、优选150℃-700℃、更优选200℃-650℃、最优选300℃-600℃的范围内。合适的温度T1还可以取决于气氛。优选地,根据剩余粘合剂组分来选择第一温度T1。在温度T1下去除热塑性聚酰胺(b-i)进行一段时间Δt1,该时间取决于部件的几何形状,特别与待生产的部件的壁厚的平方成比例。优选地,对时间段Δt1加以选择,使得去除至少95%、优选至少99%、更优选至少99.9%、最优选100%的粘合剂组分(b-i)和(b-ii)。未去除的粘合剂不作为部件中的聚合物粘合剂使用,而是会扩散,例如作为碳进入金属部件并增加金属部件中的碳含量。热脱粘可以在多个温度T1下进行,例如在温度T1a下去除一部分热塑性聚酰胺(b-i)进行一段时间Δt1a,并且在温度T1b下去除剩余的热塑性聚酰胺(b-i)进行一段时间Δt1b。
可烧结非有机颗粒(a)部分地形成烧结颈,使得尽管去除了剩余的粘合剂组分,该部件仍保持在一起。由于部件的微孔结构,热粘合剂的去除发生得快速且均匀。
可以通过惰性气体气氛或还原气氛或高真空来避免热粘合剂去除过程中不期望的化学反应。惰性气体气氛特别包含至少一种惰性气体,该惰性气体可适合选自例如氮气、氦气和氩气。还原气氛可以包括诸如氢气、二氧化碳和/或一氧化碳的气体。
烧结适合在第二温度T2下进行,第二温度T2在600℃-2000℃、优选800℃-1800℃、更优选900℃-1500℃的范围内。在陶瓷和/或玻璃质部件的生产中,第二温度T2优选在600-2400℃、更优选800-2200℃、最优选1100-2000℃的范围内。在任何情况下,烧结温度T2低于可烧结非有机颗粒的熔化温度。在第二温度T2下的烧结进行一段时间Δt2,该时间取决于部件的几何形状和待烧结的材料。优选地,时间Δt2足够长,使得通过随后的进一步烧结不能造成部件孔隙率的显著变化。烧结可以在多于一个温度T2下进行,例如在温度T2a下的烧结步骤进行一段时间Δt2a,并且在温度T2b下的另一烧结步骤进行一段时间Δt2b。
在该烧结步骤期间,模制部件将收缩,但基本上不影响模制部件的形状。粉末颗粒将熔合在一起并且粉末颗粒之间的开放空间消失。因此,在烧结过程中,产品的密度增加并且产品收缩。取决于产品的材料和随后的用途,当产品达到制成粉末的固体的约90-100体积%的密度时,烧结步骤通常完成。
优选地,在烧结步骤之后,该部件完全不含粘合剂。结果,该部件形成高密度的整体式结构。
下面参考附图和实施例详细描述本发明。
图1显示了由表3中的原料配混物获得的圆柱形测试样品(生坯部件):1-F(图1A)、2-F(图1B)和3-F(图1C)。
图2显示了由表3中1-F的原料配混物获得的带缺口的样品的侧视图和俯视图。
图3显示了由表3中2-F的原料配混物获得的带缺口的样品的侧视图和俯视图。
图4显示了由表3中3-F的原料配混物获得的带缺口的样品的侧视图和俯视图。
实施例
方法
DSC测量
使用耐驰(NETZSCH)DSC 214Polyma设备进行DSC测量。样品在购自耐驰公司的带有穿孔盖的铝制Concavus盘(坩埚)中制备。为此,将样品在第一个升温段从-20℃加热至160℃(在实施例2-B和3-B中:180℃),然后冷却至-20℃,最后在第二个升温段再次从-20℃加热至160℃(在实施例2-B和3-B中:180℃),每次加热和冷却速率均为10K/min。使用质量为5.0级的氮气作为吹扫气体进行测量,气流为40mL/min。
熔体指数流动速率
熔体质量流动速率,MFR,通常也称为熔体指数,描述了塑料在规定的温度下的流动特性。该特性是通过在规定的温度和压力下将热塑性聚合物熔体挤出已知尺寸的毛细管来测量的,根据重量确定。结果是每单位时间挤出的质量,以g/10min表示。如果熔体密度已知,则可以根据熔体体积流动速率MVR确定MFR。在此测量过程中,聚合物切片的称重被挤出体积的连续测量所代替。MVR值的结果以cm3/10min表示。
实验根据DIN ISO 1133-1在Goettfert熔体流动指数测试仪上进行,条件为2.16kg、190℃。测试前样品在80℃下干燥6小时。
材料
下表显示了在随后的实施例中使用的热塑性聚酰胺的性能。
表1:用作材料(b i)的组分的DSC熔体峰值温度TP、熔体体积流动速率MVR和熔体粘度值。
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[1]数据来自EMS化学公司提供的产品数据表
[2]数据来自A.D.K.Katta,选择性激光烧结过程中PA6粉末老化分析(Analysisof PA6 Powder Ageing During the Selective Laser Sintering process)(硕士论文),阿伦(Aalen),2019年。
*比较例
制备实施例
根据表2制备粘合剂组分1-B至6-B。根据表3制备粘合剂组分1-B至6-B的原料配混物1-F至6-F。
表2:粘合剂组分1-B至6-B;相对于粘合剂组分(b)的总体积的体积%。
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[1]DSC熔融范围为115-125℃的共聚酰胺,可购自EMS化学股份有限公司
[2]4-羟基苯甲酸二十二烷醇酯,可购自埃默里油脂化学股份有限公司
[3]硬脂酸,可购自埃默里油脂化学股份有限公司
[4]DSC熔融范围为150-160℃的共聚酰胺,可购自EMS化学股份有限公司
[5]共聚酰胺,可购自阿科玛
[6]N-乙基甲苯-4-磺酰胺,可购自西格玛奥德里奇公司
[7]油酰胺,可购自杜莱克斯公司
[8]聚酰胺6,可购自索尔维工程塑料公司(Solvay Engineering Plastics)
*比较例
表3:原料配混物1-F至6-F(体积%,相对于颗粒原料配混物的总体积)。
[1]经气体雾化,粒度90%:22μm,可购自山特维克奥斯普莱有限公司(SandvikOsprey Ltd.)
*比较例
制造生坯部件
激光增材制造
圆柱形测试样品是使用Formiga P110(可购自EOS股份有限公司)通过激光增材制造方法生产的。使用表3的原料配混物1-F至3-F作为起始材料。
图1显示了由表3中的原料配混物获得的圆柱形测试样品(生坯部件):1-F(图1A)、2-F(图1B)和3-F(图1C)。
对于原料配混物1-F至3-F,激光输出为25W,激光速度为4450mm/s,粉末床表面温度为60℃。改变扫描间距(0.13mm和0.07mm),导致不同的能量输入:0.13mm的扫描间距导致42.3mJ/mm2的能量输入;0.07毫米的扫描间距导致78.5mJ/mm2的能量输入。
加工比较原料配混物6-F需要比Formiga P110所能提供的能量输入更多的能量输入。但即便如此,边缘和面仍然模糊,生坯部件密度也不足。
将表3中的原料配混物1-F至3-F用作起始材料,使用如上所述的Formiga P110通过激光增材制造方法生产带缺口的样品(参见“圆柱形测试样品”)。本文中,术语“带缺口的样品”表示包括一个或多个缺口的长方体,其中缺口可以具有不同的宽度。图2至图4中以侧视图和俯视图描绘了这种有缺口的样品。
在图2中,原料配混物1-F用作起始材料,激光输出为25W,激光速度为4450mm/s,扫描间距为0.13mm,得到的能量输入为42.3mJ/mm2。
在图3中,原料配混物2-F用作起始材料,激光输出为25W,激光速度为4450mm/s,扫描间距为0.07mm,得到的能量输入为78.5mJ/mm2。
在图4中,原料配混物3-F用作起始材料,激光输出为25W,激光速度为4450mm/s,扫描间距为0.07mm,得到的能量输入为78.5mJ/mm2。
这种带缺口的样品的生产旨在获得高密度样品,即部件,同时,它能高度表现目标部件的几何形状,颗粒原料配混物也很少结块,优选在低激光能量输入下也如此。结果如图2至图4所示:图2所示带缺口的样品在42.3mJ/mm2的低激光能量输入下密度高,几何形状表现力强且结块少。相反,图3和图4中带缺口的样品不那么致密和/或缺口形状不太好,因为在78.5mJ/mm2的能量输入下结块。尽管如此,图3和图4中带缺口的样品在要求不太严格的应用中仍然有用。
制造烧结部件
根据DIN EN ISO 22068使用拉伸试件进行拉伸测试。采用表3中的原料配混物1-F,用如上所述的Formiga P110对所述拉伸测试件进行增材制造,获得生坯部件。然后对所述生坯部件进行溶剂脱粘步骤和烧结步骤。对于溶剂脱粘,将原料配混物1-F的生坯部件在40℃的温度下浸入丙酮中16小时。进行烧结循环,加热和冷却速率为5K/min,保温时间为380℃下2小时,600℃下1小时,1100℃下30分钟,1380℃的最终烧结温度下2小时。根据DINEN ISO 22068进行五次拉伸测试;结果如表4所示。
表4:1-T至5-T拉伸测试。
[1]横截面面积
[2]弹性模量
[3]Rp0.2屈服强度
[4]拉伸强度
[5]最大强度(全局)
[6]断裂伸长率
[7]断裂伸长率(手动)
[8]断裂收缩(fracture constriction)(手动)
Claims (15)
1.一种用于粉末床增材制造方法的颗粒原料配混物,其包含:
a)分散在整个配混物颗粒中的最大粒度为200μm的可烧结非有机颗粒,和
b)粘合剂组分,相对于该粘合剂组分的体积,该粘合剂组分包含:
b-i)3-70体积%的DSC溶体峰值温度Tp低于160℃的热塑性聚酰胺,和
b-ii)30-97体积%的滴点在20-160℃范围内的蜡或蜡类材料。
2.根据权利要求1所述的颗粒原料配混物,其中所述热塑性聚酰胺的DSC熔体峰值温度TP低于150℃、优选低于140℃、更优选低于130℃、最优选低于120℃。
3.根据权利要求1或2所述的颗粒原料配混物,其中所述热塑性聚酰胺的熔体体积流动速率为至少1cm3/10min,根据ISO 1133在2.16kg和160℃条件下测量。
4.根据前述权利要求中任意一项所述的颗粒原料配混物,其中所述蜡或蜡类材料选自极性蜡和极性蜡类材料。
5.根据权利要求4所述的颗粒原料配混物,其中所述蜡或蜡类材料选自芳族酯和芳族磺酰胺。
6.根据前述权利要求中任意一项所述的颗粒原料配混物,其中所述粘合剂组分还包含增塑剂,优选选自芳族酯和芳族磺酰胺的增塑剂。
7.根据前述权利要求中任意一项所述的颗粒原料配混物,其中所述粘合剂组分还包含分散剂。
8.根据权利要求7所述的颗粒原料配混物,其中所述分散剂选自具有10-24个碳原子的脂肪酸,优选硬脂酸。
9.根据前述权利要求中任意一项所述的颗粒原料配混物,其中所述可烧结非有机颗粒(a)选自金属、合金、玻璃质颗粒和陶瓷颗粒。
10.根据前述权利要求中任意一项所述的颗粒原料配混物,其含有按体积计约0.70-0.99·φr、优选按体积计约0.75-0.98·φr、更优选按体积计约0.80-0.96·φr、最优选按体积计约0.82-0.95·φr、特别是按体积计约0.84-0.94·φr、特别是按体积计约0.86-0.93·φr的可烧结非有机颗粒(a),其中φr是按体积计的临界固体加载量。
11.根据权利要求1至9中任意一项所述的颗粒原料配混物,其中
可烧结非有机颗粒a)的量为约20-90体积%、优选30-80体积%、更优选40-75体积%、最优选45-70体积%、特别是50-65体积%,并且
粘合剂组分b)的量为约10-80体积%、优选20-70体积%、更优选25-60体积%、最优选30-55体积%、特别是35-50体积%。
12.根据前述权利要求中任意一项所述的颗粒原料配混物,其所具有的粒度分布使得至少80体积%的颗粒原料配混物的最大粒度Bmax在0.005-0.3mm的范围内。
13.一种方法,其包括以下步骤:
-合并多个根据权利要求1至12中任意一项所述的颗粒原料配混物,以获得生坯部件,
-通过选择性地去除蜡或蜡类材料b-ii)对生坯部件进行部分脱粘,以获得褐坯部件,该褐坯部件包含通过热塑性聚酰胺b-i)彼此结合的可烧结非有机颗粒a),以及
-烧结该褐坯部件以获得烧结部件。
14.根据权利要求13所述的方法,其中合并多个颗粒原料配混物的步骤包括以下步骤:
-提供第一原料配混物颗粒层;
-选择性地使第一原料配混物颗粒层致密化,以将配混物颗粒以预定方式彼此粘合,从而产生第一成型部件层;
-在第一成型部件层上提供至少一个另外的原料配混物颗粒层;以及
-选择性地使所述另外的原料配混物颗粒层致密化,以将原料配混物颗粒以预定方式彼此粘合,从而产生至少一个另外的成型部件层,所述第一成型部件层和所述另外的成型部件层形成生坯部件。
15.根据权利要求14所述的方法,其中选择性地使所述第一配混物颗粒层和所述另外的配混物颗粒层致密化涉及选择性地用电磁辐射、优选激光束照射所述第一配混物颗粒层和所述至少一个另外的配混物颗粒层中的至少一者。
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US7063815B2 (en) * | 2003-12-05 | 2006-06-20 | Agency For Science, Technology And Research | Production of composite materials by powder injection molding and infiltration |
DE102005027216A1 (de) | 2005-06-13 | 2006-12-21 | Basf Ag | Vorrichtung und Verfahren zum kontinuierlichen katalytischen Entbindern mit verbesserten Strömungsbedingungen |
JP6447983B2 (ja) | 2014-07-08 | 2019-01-09 | エメリー オレオケミカルズ ゲーエムベーハー | 3d印刷デバイス用の焼結可能な供給原料 |
EP3257661B1 (en) * | 2016-06-17 | 2019-02-27 | UPM-Kymmene Corporation | A composite material for additive manufacturing of a three-dimensional composite product |
US11155676B2 (en) * | 2016-06-20 | 2021-10-26 | Sabic Global Technologies B.V. | Polymer composition for selective sintering |
DE102017207210A1 (de) | 2017-04-28 | 2018-10-31 | Skz-Kfe Ggmbh | Verfahren zur additiven Herstellung eines Bauteils sowie additiv hergestelltes Bauteil |
WO2020072746A1 (en) * | 2018-10-04 | 2020-04-09 | Arkema Inc. | 3-d printed semi-crystalline and amorphous polymer articles |
WO2020200426A1 (en) * | 2019-04-02 | 2020-10-08 | Emery Oleochemicals Gmbh | Sinterable feedstock for use in 3d printing devices |
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2022
- 2022-08-19 WO PCT/EP2022/073227 patent/WO2023021198A1/en active Application Filing
- 2022-08-19 CN CN202280055475.3A patent/CN117897247A/zh active Pending
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