CN112351966A - 制备包含至少一种增强纤维的烧结粉末颗粒(sp)的方法 - Google Patents

制备包含至少一种增强纤维的烧结粉末颗粒(sp)的方法 Download PDF

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CN112351966A
CN112351966A CN201980038336.8A CN201980038336A CN112351966A CN 112351966 A CN112351966 A CN 112351966A CN 201980038336 A CN201980038336 A CN 201980038336A CN 112351966 A CN112351966 A CN 112351966A
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powder particles
continuous
sintered powder
sintering
thermoplastic polymer
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C·加布里埃尔
T·迈尔
N·B·J·赫勒
L·韦尔贝伦
S·乔苏佩特
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BASF SE
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BASF SE
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Abstract

一种制备烧结粉末颗粒(SP)的方法，其包括以下步骤：a)提供至少一根连续长丝，b)用至少一种热塑性聚合物涂覆步骤a)中提供的所述至少一根连续长丝，以获得包含涂覆有所述至少一种热塑性聚合物的所述至少一根连续长丝的连续丝束，其中所述丝束的平均横截面直径为10‑300μm，和c)对步骤b)中提供的连续丝束进行尺寸减小，以获得烧结粉末颗粒(SP)，其中烧结粉末颗粒(SP)的平均长度为10‑300μm。本发明进一步涉及通过所述方法获得的烧结粉末颗粒(SP)、所述烧结粉末颗粒(SP)在基于粉末的增材制造方法中的用途和具有基本上圆柱形形状的烧结粉末颗粒(SP)，以及通过烧结粉末颗粒(SP)的激光烧结或高速烧结来制备成型体的方法。

Description

制备包含至少一种增强纤维的烧结粉末颗粒(SP)的方法
本发明涉及一种制备烧结粉末颗粒(SP)的方法。烧结粉末颗粒(SP)包含至少一种增强纤维，所述增强纤维涂覆有至少一种聚合物。本发明进一步涉及一种通过本发明的方法获得的烧结粉末颗粒(SP)、所述烧结粉末颗粒(SP)在基于粉末的增材制造方法中的用途和具有基本上圆柱形形状的烧结粉末颗粒(SP)，以及通过烧结粉末颗粒(SP)的激光烧结或高速烧结来制备成型体的方法。
原型的快速提供是近来经常发生的问题。一种特别适于这种所谓的“快速原型”的方法是选择性激光烧结(SLS)。这包括选择性地将室中的聚合物粉末暴露于激光束。粉末熔融，熔融颗粒聚结并再次凝固。重复施加聚合物粉末和随后用激光照射有利于三维成型体的建模。
专利说明书US 6,136,948和WO 96/06881详细描述了用于由粉状聚合物制备成型体的选择性激光烧结方法。
为了改善通过基于粉末的增材制造方法制备的成型体的机械性能，在一些情况下使用包含增强材料的烧结粉末。
WO 2018/019728公开了一种包含聚酰胺聚合物和纤维增强剂的烧结粉末。所述烧结粉末通过在研磨机中研磨聚酰胺和纤维增强剂来制备。因此，聚酰胺和纤维增强剂可在挤出机中配混，随后在研磨机中研磨。也可将聚酰胺和纤维增强剂分别引入到研磨机中，以便获得烧结粉末。总体上，WO 2018/019728中描述的烧结粉末在烧结时产生显示出良好机械性能的成型体。然而，如果将纤维增强剂与聚酰胺干混并随后研磨，则在一些情况下通过激光烧结获得的成型体显示出缺陷。据推测，这些缺陷是由激光烧结工艺中纤维增强剂被聚酰胺的不充分润湿引起的。此外，在研磨机中研磨期间，在一些情况下，损失了显著量的纤维增强剂。纤维增强剂在研磨工艺之后的损失是由于细料与聚合物粉末的分离所致。由于细料的分离，增强纤维碎片也从聚合物粉末中除去。此外，在一些情况下，难以精确地控制烧结粉末颗粒的颗粒形貌。
因此，本发明的目的是提供一种制备烧结粉末颗粒(SP)的方法，其即使有也仅以减小的程度具有现有技术所述方法的上述缺点。该方法应简单且廉价地实施。
该目的通过一种制备烧结粉末颗粒(SP)的方法来实现，其包括以下步骤：
a)提供至少一根连续长丝，
b)用至少一种热塑性聚合物涂覆步骤a)中提供的所述至少一根连续长丝，以获得包含涂覆有所述至少一种热塑性聚合物的所述至少一根连续长丝的连续丝束，其中所述丝束的平均横截面直径为10-300μm，和
c)对步骤b)中提供的连续丝束进行尺寸减小，以获得烧结粉末颗粒(SP)，其中烧结粉末颗粒(SP)的平均长度为10-300μm。
令人惊讶地发现，如果在基于粉末的增材制造工艺中使用通过本发明方法获得的烧结粉末颗粒(SP)，则产生具有改善的机械性能的成型体。此外，已发现本发明的方法导致具有相当均匀形状的烧结粉末颗粒(SP)。此外，烧结粉末颗粒(SP)的制备方法简单并且可以以具有成本效益的方式进行。
步骤a)
在步骤a)中，提供至少一根连续长丝。在本发明的上下文中，“连续长丝”是长度为至少1000米，优选至少10000米的纤维材料。在本发明上下文中，在特别优选的实施方案中，“连续长丝”是实际上无限的纤维，如DIN 60001 T2(1974年12月)中所定义。
连续长丝是现有技术所已知的。连续长丝通常在纺丝工艺中制备。在步骤a)中，可以以任何合适的方式提供所述至少一根连续长丝。所述至少一根连续长丝通常可从辊上退绕。在另一实施方案中，所述至少一根连续长丝可直接从纺丝工艺中取出。还可提供呈纤维粗纱、编织纤维和织造纤维形式的所述至少一根连续长丝，从其中分离出所述至少一根连续长丝。在一个实施方案中，所述至少一根连续长丝覆盖有上浆剂以改善所述至少一根长丝与所述至少一种热塑性聚合物之间的粘合。合适的上浆剂可选自水基聚合物分散体，其包含乙酸乙烯酯聚合物、聚酯聚合物、环氧树脂、硅烷(例如氨基硅烷)和/或聚氨酯聚合物。
在优选的实施方案中，所述至少一根连续长丝选自连续碳纤维、连续硼纤维、连续玻璃纤维、连续二氧化硅纤维、连续玄武岩纤维和连续芳族聚酰胺纤维。在更优选的实施方案中，所述至少一根连续长丝选自连续碳纤维、连续玻璃纤维和连续芳族聚酰胺纤维。在甚至更优选的实施方案中，所述至少一根连续长丝选自连续碳纤维和连续玻璃纤维。
因此，本发明的另一目的是一种方法，其中连续长丝选自连续碳纤维、连续硼纤维、连续玻璃纤维、连续二氧化硅纤维、连续玄武岩纤维和连续芳族聚酰胺纤维。
所述至少一根连续长丝的横截面直径通常为3-30μm，优选为4-25μm，更优选为5-20μm，特别优选为6-18μm。横截面直径是垂直于所述至少一根连续长丝的纵向轴线测量的。
因此，本发明的另一目的是一种方法，其中连续长丝的横截面直径为3-30μm。
根据本发明，“至少一根连续长丝”意指正好一根连续长丝或者两根或更多根连续长丝。步骤a)中提供的连续长丝的数量首先取决于连续长丝的横截面直径，其次取决于步骤b)中获得的丝束的横截面直径。步骤a)中提供的连续长丝的数量受到连续丝束的尺寸限制。步骤a)中提供的所有连续长丝的体积必须不超过步骤b)中获得的连续丝束的体积。通常，步骤a)中提供的所有连续长丝的总体积为至多90体积％。优选为至多70体积％，特别优选为至多50体积％，在每种情况下均相对于步骤b)中获得的连续丝束的总体积。优选地，步骤a)中提供的连续长丝的总体积为至少10体积％。优选为20体积％，尤其优选为至少30体积％，在每种情况下均相对于步骤b)中所含的连续丝束的总体积。
例如，如果步骤a)中连续长丝的横截面直径为3μm，并且步骤b)中获得的丝束的横截面直径为10μm，则在步骤a)中提供至多三根连续长丝，优选两根连续长丝，更优选仅一根连续长丝。如果连续长丝的横截面直径例如为10μm，并且步骤b)中获得的丝束的横截面直径为300μm，则在步骤a)中提供优选至多25根，更优选至多20根，特别优选至多10根连续长丝。
通常，在步骤a)中，提供1-50根，更优选1-30根，甚至更优选1-25根，特别优选1-20根连续长丝。
步骤b)
在步骤b)中，用至少一种热塑性聚合物涂覆步骤a)中提供的所述至少一根连续长丝，以获得包含涂覆有所述至少一种热塑性聚合物的所述至少一根连续长丝的连续丝束。
在步骤b)中，可使用所有已知的热塑性聚合物。合适的热塑性聚合物可为无定形热塑性聚合物或半结晶热塑性聚合物。半结晶热塑性聚合物具有熔点。无定形热塑性聚合物不具有熔点，但具有软化点。优选半结晶热塑性聚胺。
如果使用半结晶热塑性聚合物，则步骤b)通常在比所述至少一种半结晶热塑性聚合物的熔点高10-100℃，更优选20-80℃，特别优选30-70℃的温度下进行。如果使用半结晶热塑性聚合物的混合物，则步骤b)在上述温度范围内进行，其中聚合物混合物中半结晶热塑性聚合物的最高熔点用作参考。
如果使用无定形热塑性聚合物，则步骤b)通常在比所述至少一种无定形热塑性聚合物的玻璃化转变温度(TG)高50-200℃，更优选70-150℃，特别优选90-130℃的温度下进行。如果使用无定形热塑性聚合物的混合物，则步骤b)在上述温度范围内进行，其中聚合物混合物中无定形热塑性聚合物的最高玻璃化转变温度(TG)用作参考。
如果使用半结晶热塑性聚合物和无定形热塑性聚合物的混合物，则步骤b)在上述温度范围内进行，其中聚合物混合物中半结晶热塑性聚合物的最高熔点用作参考。
在优选的实施方案中，步骤b)在30-400℃，更优选100-350℃，特别优选200-350℃的温度下进行。
换言之，在步骤b)中，使步骤a)中提供的所述至少一根连续长丝与所述至少一种热塑性聚合物的熔体接触，以便涂覆所述至少一根长丝。该工艺也称为“润湿”。在优选的实施方案中，所述至少一种热塑性聚合物的熔体具有如上所定义的实施步骤b)的温度范围。
根据步骤b)的涂覆可在任何合适的装置中进行。优选地，步骤b)在开放或封闭的模头中进行，其中优选封闭的模头。在甚至更优选的实施方案中，步骤b)在拉挤装置中进行。换言之，步骤b)作为拉挤工艺进行，其中借助输送单元将步骤b)中获得的丝束输送出封闭的模头。输送单元优选将丝束输送到步骤c)中所用的尺寸减小装置中。
为了在步骤b)中涂覆所述至少一根连续长丝，在优选的实施方案中，将所述至少一根连续长丝和所述至少一种热塑性聚合物同时输送通过优选的封闭模头。
随后，在离开模头之后，通常将丝束冷却，以使得热塑性聚合物的熔体可以凝固，从而获得包含涂覆有所述至少一种热塑性聚合物的所述至少一根连续长丝的连续丝束，其具有10-300μm的横截面直径。横截面直径在23℃的温度下垂直于连续丝束的纵向轴线测量。
在优选的实施方案中，连续丝束具有10-300μm，更优选20-200μm，特别优选30-150μm的横截面直径。
通常以大于1m/分钟的速度将该丝束(也称为“拉挤物”)拉出(输送出)模头。特别优选地，出料速度大于1.5m/分钟，特别优选大于0.2m/分钟。最大速度优选为至多100m/分钟。
根据本发明，“至少一种热塑性聚合物”意指正好一种热塑性聚合物或者两种或更多种热塑性聚合物的混合物。
合适的热塑性结晶聚合物选自聚酰胺、聚乙烯、聚丙烯、聚醚酮、聚甲醛、聚苯硫醚、聚酯、其共聚物及其组合。
熔点和玻璃化转变温度用差示扫描量热法(DSC)测量，其中使用10K/分钟的加热速率，并且其中熔点和玻璃化转变温度(TG)在第二加热轮中测定。
因此，本发明的另一目的是一种方法，其中在步骤c)中，将步骤b)中获得的丝束切割成10-300μm的长度。
合适的聚乙烯包括低密度聚乙烯、中密度聚乙烯、高密度聚乙烯及其组合。合适的聚丙烯包括全同立构的异丙烯、间同立构聚丙烯、其支化和线性变体及其组合，以及聚丙烯共聚物。
合适的聚酯包括聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯。
合适的热塑性无定形聚合物选自聚苯乙烯、聚砜(PSU)、聚醚砜(PESU)、聚苯醚砜(PPSU)、PA 6I/6T、PA 6/3T、聚碳酸酯、聚苯乙烯丙烯腈、聚丁二烯和聚甲基丙烯酸甲酯(PMMA)。
在优选的实施方案中，所述至少一种热塑性聚合物选自聚酰胺聚合物。
例如，以下聚酰胺适合用作至少一种热塑性聚酰胺聚合物：AB聚合物：
Figure BDA0002823559600000061
AA/BB聚合物：
Figure BDA0002823559600000062
Figure BDA0002823559600000071
优选地，所述至少一种热塑性聚合物选自PA 4、PA 6、PA 7、PA 8、PA 11、PA12、PA46、PA 66、PA 69、PA 610、PA 612、PA 613、PA 6T、PA MXD6、PA 6I/6T、PA 6T/6I、PA 6/6l、PA 6/6T、PA 6/66、PA 6/12、PA 66/6/610、PA 6l/6T/PACM和PA 6/6I6T及其混合物。
因此，优选所述至少一种热塑性聚合物选自PA 6、PA6I/6T、PA 6.6、PA 6.10、PA6.12、PA 6.36、PA 6/6.6、PA 6/6I6T、PA 6/6T和PA 6/6I及其混合物。
尤其优选地，所述至少一种热塑性聚合物选自PA 6、PA 6I/6T、PA 6.10、PA 6.6/6、PA 6/6T和PA 6.6。更优选地，所述至少一种热塑性聚合物选自PA 6和PA 6/6.6。最优选地，所述至少一种热塑性聚合物为PA 6、PA 6I/6T及其混合物。
因此，本发明还提供了一种方法，其中所述至少一种热塑性聚合物选自PA 6、PA6I/6T、PA 6.6、PA 6.10、PA 6.12、PA 6.36、PA 6/6.6、PA 6/6I6T、PA 6/6T和PA 6/6I及其混合物。
所述至少一种热塑性聚合物通常具有70-350mL/g，优选70-240mL/g的粘数。根据本发明，粘数由0.5重量％的组分(A)的96重量％硫酸溶液在25℃下根据ISO 307测定。
所述至少一种热塑性聚合物优选具有500-2 000 000g/mol，更优选5000-500000g/mol，尤其优选10 000-100 000g/mol的重均分子量(MW)。重均分子量(MW)根据ASTMD4001测定。
所述至少一种热塑性聚合物可包含至少一种添加剂。合适的添加剂是本领域技术人员所已知的。合适的添加剂例如选自抗成核剂、稳定剂、端基官能化试剂和染料。
步骤c)
在步骤c)中，减小步骤b)中提供的连续丝束的尺寸，以获得烧结粉末颗粒(SP)。
尺寸减小步骤c)可通过研磨、粉碎、断裂或切割来进行。优选地，步骤c)中的尺寸减小通过切割进行。
因此，本发明的另一目的是一种方法，其中在步骤c)中，将步骤b)中获得的丝束切割成10-300μm的长度。
在进行尺寸减小步骤c)之前，在一个实施方案中，将步骤b)中获得的连续丝束聚集成包含多股连续丝束的粗纱。
粗纱可包含至多50000股，优选至多25000股，更优选至多20000股连续丝束。优选地，粗纱包含至少50股，更优选至少100股，甚至更优选至少1000股，特别优选至少5000股连续丝束。
在该实施方案中，将包含多股连续丝束的粗纱输送至切割装置，其中进行尺寸减小步骤c)。如果将单股连续丝束输送到切割装置，则每次切割都获得一个烧结粉末颗粒(SP)。如果将包含多股连续丝束的粗纱输送到切割装置，则每次切割都获得多个烧结粉末颗粒(SP)，其中在每个切割步骤中获得的烧结粉末颗粒(SP)的数量等于粗纱中所含的连续丝束的数量。
优选地，在步骤c)中，将步骤b)中获得的丝束(优选呈粗纱形式)切割成10-300μm的长度。
烧结粉末颗粒(SP)通常具有基本上圆柱形的形状。烧结粉末颗粒(SP)的横截面直径等于步骤b)中获得的丝束的横截面直径。烧结粉末颗粒的横截面直径垂直于具有基本上圆柱形形状的烧结粉末颗粒(SP)的纵向轴线测量。
因此，另一目的是一种烧结粉末，其具有基本上圆柱形的形状，具有10-300μm的平均横截面直径，并且具有10-300μm的平均长度，其包含处于基本上圆柱形颗粒的芯中的至少一根增强纤维以及形成该圆柱形颗粒的侧表面的至少一种热塑性聚合物的涂层。
烧结粉末颗粒(SP)的平均长度与烧结粉末颗粒(SP)的平均横截面直径之间的平均比值通常为1:1至30:1，优选为1:1至25:1，更优选为5:1至20:1。
因此，本发明的另一目的是一种方法，其中烧结粉末颗粒(SP)的平均长度与烧结粉末颗粒(SP)的平均横截面直径之间的平均比值为1:2至30:1。
在优选的实施方案中，烧结粉末颗粒(SP)的至少70％，更优选80％、甚至更优选90％，特别优选95％具有基本上圆柱形的形状，在每种情况下均相对于颗粒(SP)的总量。
因此，本发明的另一目的是一种方法，其中至少70％的烧结粉末颗粒(SP)具有基本上圆柱形的形状。
本发明的术语“基本上圆柱形”优选意指烧结粉末颗粒的形状基本上具有任何三维圆柱形，例如直圆柱形或斜圆柱形。基本上圆柱形的烧结粉末颗粒的底部可以是多边形、圆形、椭圆形或三角形。
在另一优选实施方案中，术语“基本上圆柱形”可定义如下：“基本上圆柱形”定义为烧结粉末颗粒(SP)占据烧结粉末颗粒(SP)所拟合的假想最佳拟合圆柱形的内部体积的至少60％，优选至少70％，更优选至少80％，特别优选90％。
本发明的另一目的是通过上述方法获得的烧结粉末颗粒(SP)。烧结粉末颗粒(SP)可用于基于粉末的增材制造方法中。优选的增材制造方法选自选择性激光烧结、选择性抑制烧结和高速烧结。优选地，烧结粉末颗粒(SP)用于选择性激光烧结和高速烧结。
本发明的另一目的是具有基本上圆柱形形状、具有10-300μm的平均横截面直径且具有10-300μm的平均长度的烧结粉末颗粒(SP)，其包含处于基本上圆柱形颗粒的芯中的至少一根连续长丝和形成圆柱形颗粒的侧表面的至少一种热塑性聚合物的涂层。对于上述烧结粉末颗粒(SP)，相应地适用上文对烧结粉末颗粒(SP)的制备方法所述的描述和优选方案。
烧结粉末颗粒(SP)可与不同于烧结粉末颗粒(SP)的其他烧结粉末颗粒混合。因此，本发明的另一目的是一种烧结粉末，其包含10-90重量％的烧结粉末颗粒(SP)和90-10重量％的不同于烧结粉末颗粒(SP)的其他烧结粉末颗粒，基于烧结粉末的总重量。
其他烧结粉末颗粒可通过上述用于制备烧结粉末颗粒的方法来形成，其中使用不同的热塑性聚合物或不同的连续长丝。然而，优选地，其他烧结粉末颗粒选自通过常规方法如研磨或沉淀制备的烧结粉末颗粒。在优选的实施方案中，其他烧结粉末颗粒不含增强剂。
如上所述，通过烧结粉末颗粒(SP)或包含烧结粉末颗粒(SP)与其他烧结粉末颗粒的混合物的烧结粉末的激光烧结或高速烧结而获得的成型体显示出改善的机械性能。因此，本发明的另一目的是一种通过粉末颗粒(SP)的激光烧结或高速烧结来制备成型体的方法
本发明的另一目的是一种通过烧结粉末的选择性激光烧结或高速烧结来制备成型体的方法。
烧结粉末颗粒的平均横截面直径通过光学显微镜确定。因此，通过光学显微镜随机测量100个样品以确定平均横截面直径。分别测定烧结粉末颗粒的平均长度。

Claims (15)

1.一种制备烧结粉末颗粒(SP)的方法，其包括以下步骤：
a)提供至少一根连续长丝，
b)用至少一种热塑性聚合物涂覆步骤a)中提供的所述至少一根连续长丝，以获得包含涂覆有所述至少一种热塑性聚合物的所述至少一根连续长丝的连续丝束，其中所述丝束的平均横截面直径为10-300μm，和
c)对步骤b)中提供的连续丝束进行尺寸减小，以获得烧结粉末颗粒(SP)，其中烧结粉末颗粒(SP)的平均长度为10-300μm。
2.根据权利要求1所述的方法，其中所述连续长丝的横截面直径为3-30μm。
3.根据权利要求1或2所述的方法，其中所述连续长丝选自连续碳纤维、连续硼纤维、连续玻璃纤维、连续二氧化硅纤维、连续玄武岩纤维和连续芳族聚酰胺纤维。
4.根据权利要求1-3中任一项所述的方法，其中烧结粉末颗粒(SP)的平均长度与烧结粉末颗粒(SP)的平均横截面直径之间的平均比值为1:2至10:1。
5.根据权利要求1-4中任一项所述的方法，其中在步骤c)中，将步骤b)中获得的丝束切割成10-300μm的长度。
6.根据权利要求1-5中任一项所述的方法，其中所述至少一种热塑性聚合物选自聚酰胺、聚乙烯、聚丙烯、聚醚酮、聚甲醛、聚四氟乙烯、聚苯硫醚、聚酯、其共聚物及其组合。
7.根据权利要求1-6中任一项所述的方法，其中至少70％的烧结粉末颗粒(SP)具有基本上圆柱形的形状。
8.根据权利要求1-7中任一项所述的方法，其中所述至少一种聚合物选自聚酰胺聚合物。
9.根据权利要求1-8中任一项所述的方法，其中所述至少一种热塑性聚合物选自PA 4、PA 6、PA 7、PA 8、PA 11、PA 12、PA 46、PA 66、PA 69、PA 610、PA 612、PA 613、PA 6T、PAMXD6、PA 6I/6T、PA 6T/6I、PA 6/6l、PA 6/6T、PA 6/66、PA 6/12、PA 66/6/610、PA 6l/6T/PACM和PA 6/6I6T及其混合物。
10.通过根据权利要求1-9中任一项所述的方法获得的烧结粉末颗粒(SP)。
11.根据权利要求10所述的烧结粉末颗粒(SP)在基于粉末的增材制造方法中的用途，所述基于粉末的增材制造方法选自选择性激光烧结、选择性抑制烧结和高速烧结。
12.烧结粉末颗粒(SP)，其具有基本上圆柱形的形状，具有10-300μm的平均横截面直径，并且具有10-300μm的平均长度，其包含处于基本上圆柱形的颗粒的芯中的至少一种增强纤维和形成圆柱形颗粒的侧表面的至少一种热塑性聚合物的涂层。
13.一种烧结粉末，其包含10-90重量％的根据权利要求10或12所述的烧结粉末颗粒(SP)和90-10重量％的不同于烧结粉末颗粒(SP)的其他烧结粉末颗粒，基于所述烧结粉末的总重量。
14.一种通过激光烧结或高速烧结根据权利要求9或12所述的烧结粉末颗粒(SP)来制备成型体的方法。
15.一种通过选择性激光烧结或高速烧结根据权利要求13所述的烧结粉末来制备成型体的方法。
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