CN108472939B - 经表面处理的聚合物颗粒、包含其的浆料及其用途 - Google Patents

经表面处理的聚合物颗粒、包含其的浆料及其用途 Download PDF

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CN108472939B
CN108472939B CN201680077313.4A CN201680077313A CN108472939B CN 108472939 B CN108472939 B CN 108472939B CN 201680077313 A CN201680077313 A CN 201680077313A CN 108472939 B CN108472939 B CN 108472939B
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particles
treated
particle
fibers
layer
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CN108472939A (zh
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J.M.格里芬
K.K.C.何
J.F.普拉特
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Cytec Industries Inc
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Cytec Industries Inc
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Abstract

经表面处理的聚合物颗粒，这些颗粒可分散在水或水溶液中而无需借助于任何表面活性剂。进行疏水的聚合物颗粒的表面处理以增加表面能并使这些颗粒的表面亲水，由此消除为了将这些聚合物颗粒分散在水或水溶液中而对表面活性剂的需要。这样，可以由这些经表面处理的颗粒形成无表面活性剂的浆料用于制造纤维增强的热塑性复合结构。

Description

经表面处理的聚合物颗粒、包含其的浆料及其用途
附图说明
图1是示出与去离子水相比，作为时间的函数测量的，分散在水中的未处理的和经表面处理的PEKK粉末的表面张力测量值的图。
图2是示出由经轻度处理的氟氧化的PEKK粉末生产的经固结的PEKK层压体的截面视图的光学显微照片图像。
图3是示出由经高度处理的氟氧化的PEKK粉末生产的经固结的PEKK层压体的截面视图的光学显微照片图像。
具体实施方式
本披露涉及经表面处理的聚合物颗粒，这些颗粒可分散在水或水溶液中而无需借助于任何表面活性剂。已经发现疏水的聚合物颗粒(或粉末)的表面处理增加表面能并且使这些颗粒的表面亲水消除了为了将粉末分散在水中而对表面活性剂的需要。这样，可以由这些经表面处理的颗粒形成无表面活性剂的浆料用于制造纤维增强的热塑性复合结构。无表面活性剂的浆料的使用改进了制造工艺的效率并且产生没有表面活性剂污染的复合结构。
这些经表面处理的聚合物颗粒是由对疏水的或不溶于水的聚合物(特别是热塑性聚合物)的颗粒进行表面处理来生产的，以便增加这些颗粒外表面的亲水性或润湿性。“亲水性”是展现对水的亲和力的材料特征。这样，经表面处理的颗粒的亲水表面可被与这些表面接触的水性液体(即包含水的液体)润湿。这些颗粒的亲水性与它们的分散表面能有关，该分散表面能可以通过反相气相色谱法(IGC)仪器测量。在一些实施例中，这些经表面处理的聚合物颗粒具有小于50mJ/m2，特别地从约30mJ/m2至约49mJ/m2，包括从约33mJ/m2至约46mJ/m2的分散表面能。
每个经表面处理的聚合物颗粒可被描述为具有疏水或不溶于水的聚合物的芯和亲水的外表面。该疏水的芯构成整个颗粒的按体积计至少80％，例如80％-99％。
在此披露的经表面处理的聚合物颗粒可以具有如通过激光衍射在湿的分散体中测量的约100μm或更小，例如在约1μm至约100μm范围内的平均粒径(d50)。例如，可以使用Malvern Mastersizer 2000粒径分析仪测量d50粒径，该分析仪在0.002纳米-2000微米的范围内运行。“d50”表示粒径分布的中值，或可替代地是使得50％的颗粒具有该值或更小的粒径的分布值。对于球形颗粒(纵横比为约1:1)，平均粒径是指其直径。对于非球形颗粒，平均粒径是指颗粒的最大横截面尺寸。关于颗粒，术语“纵横比”是指颗粒的最大横截面尺寸与颗粒的最小横截面尺寸的比率。
在表面处理前，未处理的颗粒是疏水的或不溶于水的热塑性聚合物的微粒形式，这些热塑性聚合物选自：聚芳醚酮(PAEK)；聚酰胺，包括半芳香族聚酰胺例如聚邻苯二甲酰胺(PPA)；热塑性聚烯烃；聚苯醚(PPO)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚酰亚胺；聚醚酰亚胺(PEI)；聚酰胺-酰亚胺；聚芳基砜，包括PES、PEES；聚苯硫醚(PPS)、聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸乙二酯二醇(polyethylene terephthalate glycol)(PETG)；聚甲醛(POM)；液晶聚酯(LCP)；聚甲基丙烯酸甲酯(PMMA)；聚乳酸或聚丙交酯；聚左旋乳酸或聚左旋丙交酯；聚乙醇酸；共聚物及其组合。
在一些实施例中，在表面处理前的起始疏水颗粒是聚芳醚酮(PAEK)颗粒。PAEK是包含单元-Ar-O-Ar-C(＝O)-的聚合物，其中Ar是芳香族部分。它们的特征为通过醚、羰基(酮)、砜或酰亚胺基团连接的芳基。
在PAEK聚合物重复单元中的每个芳香族部分(Ar)可以独立地选自取代的和未取代的单核芳香族部分(即亚苯基)以及取代的和未取代的多核芳香族部分。术语“多核”被认为包括稠合的芳环例如萘，以及非稠合的环例如联苯等。在一些实施例中，Ar是亚苯基(Ph)，如未取代的亚苯基。
亚苯基和多核芳香族部分(即“Ar”)可以包含在芳环上的取代基。此类取代基是熟练人员容易理解的，并且不应在任何显著程度上抑制或以其他方式干扰聚合反应。典型的取代基可以包括例如，苯基、卤素(如F、Cl、Br、I)、酯、硝基、氰基等。
在其中Ar被取代的情况下，取代基优选地侧接于链上，而不是在主链上，即不与酮键联的羰基碳原子或醚键联的氧原子键合。因此，在一个实施例中，这些酮键联(即羰基的碳原子)直接附接到碳原子上，特别是附接到相邻芳香族基团的碳原子(即附接到芳香族碳)上。类似地，醚键联的氧原子优选地附接到碳原子上，特别是附接到相邻芳香族基团的芳香族碳原子上。
包括以上重复单元的均聚物或以上重复单元彼此(如PEKK-PEKEKK-PEKK)以及与酰亚胺或砜单元的共聚物。共聚物包括交替的、周期性的、统计的、无规的和嵌段的共聚物。
PAEK的具体实例可包括但不限于聚(醚酮)(PEK)、聚(醚醚酮)(PEEK)、聚(醚酮酮)(PEKK)、聚(醚醚酮酮)(PEEKK)，以及聚(醚酮醚酮酮)(PEKEKK)、聚(醚醚酮醚酮)(PEEKEEK)、聚(醚二苯基酮)(PEDK)、聚(醚二苯基醚酮)(PEDEK)、聚(醚二苯基醚酮酮)(PEDEKK)、聚(醚酮醚萘)(PEKEN)。
在一个实施例中，PAEK聚合物或其共聚物的经表面处理的颗粒包含经氟氧化的外表面。在另一个实施例中，PAEK聚合物或其共聚物的这些经表面处理的颗粒包含在其外表面上的选自羰基和羟基的极性官能团，并且可以进一步包含在外表面上的氟原子。
使疏水/不溶于水的颗粒的表面亲水的表面处理可选自常规方法，例如气态氧化，包括使用各种气氛或在真空下的氟氧化、等离子体或电晕处理、使用酸或碱的化学氧化或还原(湿化学)、使用离子束或其他辐射源的辐照以及化学接枝。
对于通过等离子体进行的表面处理，可以使用包含氧，例如纯氧、空气、水蒸气或其混合物的等离子体气体。含氧等离子体处理可以附接由羟基、羰基、羧基及其混合物组成的化学基团，从而使底物更具极性和亲水。此外，氧化试剂，例如臭氧、过氧化物、氧-氟(O2/F2)或空气氟混合物等可以使颗粒表面更具极性和亲水。用等离子体气体使底物更具极性和亲水、同时在表面上产生自由基的处理可以例如通过非还原气体如氩气或氩气和氨的混合物来进行。
如在此使用的术语“等离子体”是指部分或完全离子化的气体的状态。等离子体由带电离子(正或负)、带负电的电子以及中性物种、自由基和受激物种组成。如本领域已知的，等离子体可以例如通过功率源如交流(AC)、直流(DC)、低频(LF)、音频(AF)、射频(RF)和微波功率源产生。等离子体处理可以包括将这些聚合物颗粒定位在具有主区域和余辉区域的气体等离子体的余辉区域中。
等离子体处理条件可以包括从约1瓦特至约1000瓦特，包括约5瓦特至约500瓦特的功率水平。暴露时间可以是约5秒至12小时，包括约1分钟至2小时，以及约5分钟至约30分钟。
在一个实施例中，等离子体处理被用来改性PAEK颗粒的表面。等离子体形成气体可选自下组，该组由以下各项组成：氧气、氢气、氮气、空气、氦、氖、氩、二氧化碳和一氧化碳、甲烷、乙烷、丙烷、四氟化碳和六氟乙烷或其组合。在一个实施例中，等离子体处理用作PAEK颗粒，如PEKK颗粒的表面处理。用于处理PAEK颗粒表面的优选的等离子体形成气体是含氧气体、或者是单独的氧气或氧气与一种或多种额外的等离子体形成气体的混合物。
在另一个实施例中，氟氧化方法被用于改性PAEK颗粒的表面，其通常具有大于约50mJ/m2，如51mJ/m2至60mJ/m2的分散表面能。氟氧化可以通过同时或顺序地将这些聚合物颗粒暴露于反应性氟气体源和氧化源来进行。在优选的实施例中，该反应性气体是包含氟(F2)和氧气(O2)以及惰性载体例如氮气(N2)的混合物。氟和氧气的相对浓度可以在反应性气体组合物中变化。绝对浓度取决于各自的体积百分比浓度和气体压力二者。例如，在1.0大气压下具有按体积计12％F2的气态组合物的反应性大约等于在0.5大气压下具有按体积计24％F2的气态组合物或在3.0大气压下具有按体积计4％F2的气态组合物的反应性。
氟氧化也可以在低压或冷等离子体中进行，该等离子体可以包含F2/O2、CF4/O2、NF3/O2的气态混合物，与氧气或空气混合的其他氟碳化合物，或在等离子体中产生氟和氧自由基或活性物种的含氟化合物或其混合物。
本领域普通技术人员可以选择加工条件例如温度、压力、氟和氧的浓度以及暴露时间，以便实现期望的亲水性和分散表面能。接触时间通常由所需的表面改性程度决定。
无表面活性剂的浆料
可以将本披露的经表面处理的聚合物颗粒分散在水或水溶液中而无需借助于任何表面活性剂，从而形成无表面活性剂的浆料。分散颗粒的无表面活性剂的浆料可被用来浸渍增强纤维层以便形成复合材料，特别是热塑性预浸料。
为了形成适合用于浸渍增强纤维的分散聚合物颗粒的浆料，这些颗粒可以以基于该浆料的总重量按重量计约0.5％至约60％的量存在。该分散颗粒的浆料可任选地除水之外包含/或替换为与水可混溶的有机溶剂，例如烷基醇，如甲醇，和丙酮。如果存在，溶剂的量可以基于浆料的总重量在约0.1％至约50％的范围内。
复合结构及其制造
该分散聚合物颗粒的无表面活性剂的浆料可以与增强纤维组合，以制造纤维增强的复合材料和结构。在不必使用表面活性剂来分散这些聚合物颗粒的情况下，更安全且更经济的制造方法是可能的。
根据一个实施例，用于制造热塑性复合层压体(或结构)的方法包括：
(a)将以上所述的无表面活性剂的浆料施加到第一增强纤维层上，以将颗粒分布到这些纤维上，形成第一经颗粒涂覆的层；
(b)在该第一经颗粒涂覆的层上放置附加的增强纤维层；
(c)将该无表面活性剂的浆料施加到该附加的增强纤维层上，以将这些颗粒分布到这些纤维上，形成随后的经颗粒涂覆的层；
(d)将这些经颗粒涂覆的层干燥；以及
(e)通过施加热量和压力将这些经颗粒涂覆的层固结。
可以重复步骤(b)和(c)以在(d)干燥之前构建具有所需厚度的层压体。固结后，所得的复合结构是包含嵌入聚合物基质中的增强纤维层的一体式层压体。
可以将该分散颗粒的浆料通过浇注、喷涂、铺展、刷涂或任何常规涂覆技术施加到增强纤维层上，以便将分散颗粒分布到这些纤维的暴露的表面上。
固结包括将经颗粒涂覆的纤维层的叠层放置在预加热的模具或压机中，并使该叠层经受热量和压力持续可观的时间，该时间足以使聚合物/热塑性材料流动并将待层压的材料层结合在一起，并且允许该模具或压机充分冷却以避免在从该模具/压机中移除该层压体前模制结构的变形。
在一个实施例中，热塑性预浸料可以通过将经表面处理的热塑性颗粒的无表面活性剂的浆料施加到增强纤维层上、将该经浆料处理的纤维层干燥、并通过施加热量和压力使其固结来制造。该增强纤维层可以是呈连续单向对齐的纤维、织造织物、非织造织物、多轴织物或无规排列纤维的非织造垫的形式。所得预浸料包含嵌入热塑性聚合物基质中的增强纤维。
用于制造复合结构和预浸料的增强纤维可以采取短纤维、连续纤维、长丝、丝束、束、非织造或织造织物层、无规排列纤维的非织造垫及其组合的形式。连续纤维可以进一步采用单向(在一个方向对齐)、多向(在不同方向对齐)纤维的任一种。连续纤维可以呈丝束的形式，每个丝束由多根长丝(例如数千根长丝)构成。单向纤维丝束可以通过交叉丝束针法保持在适当的位置。增强纤维层可以是多轴的非卷曲织物(NCF)层。NCF由非卷曲的纤维层组成，这些纤维层通过缝合纱线连接。NCF的每个纤维层由连续的单向纤维组成，这些纤维取向的方向与另一相邻纤维层中的纤维不同。该增强纤维组合物包括但不限于玻璃(包括电气或E-玻璃)、碳、石墨、芳香族聚酰胺、聚酰胺、高模量聚乙烯(PE)、聚酯、聚-对亚苯基-苯并噁唑(PBO)、硼、石英、玄武岩、陶瓷及其组合。
为了制造高强度复合材料，如用于航空航天和汽车应用，优选的是增强纤维具有大于3500MPa的拉伸强度。碳、玻璃和芳纶纤维特别适合作为此类增强纤维。
在某些实施例中，复合层压体、结构或预浸料中增强纤维的含量是基于该层压体、结构或预浸料的总重量按重量计至少50％，例如按重量计约50％至约80％。
实例
实例1
PEKK颗粒的氟氧化
尽管PEKK(聚醚酮酮)分子的每一个重复单元在结构中具有两个C＝O和一个C-O-C基团，仍然认为PEKK粉末在本质上是疏水的，并且在不借助于表面活性剂的情况下不容易分散在水中。进行氟氧化(FO)过程以通过在聚合物颗粒表面引入极性基团来增强PEKK聚合物颗粒的润湿性或亲水性。
将PEKK聚合物(来自氰特工业公司(Cytec Industries Inc.)的CypekTMFC(峰值熔点＝338℃))研磨以形成粒径(D50)为约17微米的粉末。将该PEKK粉末暴露于两个不同水平的氟氧化处理，以产生经轻度处理的经氟氧化的粉末和经高度处理的经氟氧化的粉末。使用如下所述的多种技术分析所得经氟氧化的PEKK粉末以及未处理的粉末(作为对照)。
反相气相色谱法(IGC)
将多个PEKK粉末样品(每个0.3g)填充到单独的预硅烷化玻璃柱(300mm×4mm ID)中，其中在每一端填充硅烷化玻璃棉以防止移动。使用SMS-iGC2000系统(表面测量系统，伦敦，英国)进行实验。使用五种正烷烃(庚烷、辛烷、壬烷、癸烷和十一烷)测量表面能的色散分量。使用乙酸乙酯和二氯甲烷作为极性探针测量极性组分。这两种探针通常用作单极性酸/碱探针。
X射线光子光谱(XPS)
在配备有Mg Kα阳极和电荷中和器的Kratos AXIS HSi仪器上记录X射线光电子能谱。对于高分辨率扫描使用11.75eV的分析仪通过能量，并且对于宽扫描使用187.85eV的分析仪通过能量，两者均具有400W的X射线功率。使用来自宽扫描中的适当响应因子确定元素组成。使用CasaXPS对背景扣除的光谱进行光谱去卷积。官能团结合能的比较参考值取自NIST标准参考数据库[Naumkin AV,Kraut-Vass A,Gaarenstroom W,Powell CJ.“NISTStandard Reference Database[NIST标准参考数据库]20，版本4.1”]。
表面张力
表面张力测量是在Processor-Tensiometer K100上通过克鲁斯先进表面科学(Kruss Advancing Surface Science)在22℃下同时遵循标准ISO 1409进行的。
粒径
使用Malvern Mastersizer 2000测量未处理的PEKK对照粉末和经轻度以及高度处理的PEKK粉末的粒径。
测量这些经表面处理的和未处理的PEKK粉末的分散表面能并且结果报告在表1中。
表1
Figure BDA0001714453650000081
测量到经氟氧化的PEKK粉末的分散表面能的下降。较低的测量到的分散表面能可以归因于对气态形式的有机溶剂作出响应的能量位点数目较少。这与以下预测一致：氟氧化处理将羰基和羟基官能团引入颗粒表面上，这反过来与有机气态环境不相容。分散表面的减少表明在该表面上存在的非极性基团的增加。相比之下，较高的特定酸/碱比能量，并且特别是外推的酸性组分表明由于氟氧化处理而存在更多的酸性官能团。
通过XPS研究了氟氧化对PEKK粉末的影响。PEKK聚合物的化学组成在表2中呈现。
表2
样品 C1s N1s O1s F1s Si2p Cl2p O:C
对照 86.9 - 12.7 - 0.37 - 0.15
轻FO处理的 63.3 0.96 20.6 14.3 0.75 0.07 0.32
高FO处理的 58.9 0.95 21.6 17.7 0.81 - 0.37
原始的未处理的PEKK粉末(对照)含有相对量的杂原子含量(主要是氧)以及少量表面硅杂质，但完全不含氧。氟氧化处理导致整个表面组成的显著变化并且特别是引入另外的杂原子，可能是通过氟和氧的共混物。轻度处理PEKK后，氟含量从0％迅速增加至14.3％。高度氟氧化处理(轻度处理持续时间的两倍)后，尽管表面氟水平进一步增加3.4％以达到17.7％，但表面氧和氮在很大程度上保持不变。表面极性/疏水性变化的测量也可以通过检查整个系列中O:C比率的演变来获得。这示出最长的氟氧化处理后的从0.15急剧增加至0.37，与表面亲水性急剧增加一致，这决定了为什么经处理的PEKK粉末可容易地分散在去离子水中而无需借助于任何表面活性剂。
XPS光谱显示，PEKK粉末的氟氧化处理引起表面羟基羰基化。XPS光谱还显示PEKK粉末的处理导致亲水R-Ox基团引入。总体而言，数据示出氟氧化处理导致PEKK粉末表面能的变化。
实例2
分散颗粒的无表面活性剂的浆料
当将未处理的PEKK粉末添加到去离子(DI)水中(没有搅拌)时，在水的表面上形成白色泡沫，其中PEKK粉末位于顶部，而水的主体保持透明。相比之下，当将实例1中描述的经氟氧化的PEKK粉末(经轻度和高度处理的)加入DI水中时，聚合物立即沉降到水中。此外，在搅拌1分钟和5分钟后，悬浮液可以被描述为视觉上更稳定并且与对于作为时间的函数测量的表面张力报告的测量结果一致。
图1示出与去离子水相比，作为时间的函数测量的，分散在水中的未处理的和经表面处理的PEKK粉末的表面张力。测量的去离子水上的表面张力是72mN/m。包含5wt％未处理的PEKK颗粒(#140731)的浆料测量的表面张力接近40mN/m。与未处理的颗粒相比，在5wt％的浆料浓度下，经轻度处理(“轻FO”)和高度处理(“高FO”)的PEKK颗粒二者表现出更高的表面张力，这表明性质上更亲水。其结果是，经轻度和高度处理的PEKK颗粒二者都可容易地分散在DI水中而无需借助于任何表面活性剂。
实例3
制造的热塑性层压体
将40g实例1中披露的经轻度处理的经氟氧化的PEKK粉末分散到80g去离子(DI)水中，形成具有按重量计33％PEKK的无表面活性剂的浆料。将该浆料分成15g每份。从面积重量为280gsm(g/m2)的织造碳织物(来自氰特碳纤维公司，南卡罗莱纳州，美国(CytecCarbon Fiber,South Carolina,USA)的T300 desized 5HS织物)切割七个(19cm×9cm)织物层。将第一织物层放置在模具上并且将一部分浆料沉积在该织物层上以涂覆整个层的顶表面。将其他六个织物层的每一个铺设在前一层的顶部并且用一部分浆料涂覆。通过FEP真空袋将经颗粒涂覆的织物的湿的叠层封闭并将其放置在110℃的风扇烘箱中2小时以蒸发掉水。然后将该经干燥的叠层转移到2mm厚的防粘涂布(release coated)不锈钢框架中并预加热至375℃持续15分钟。之后，对该叠层施加5吨压力并在375℃下保持20分钟以将该叠层固结。然后将所得固结的层压体冷却至250℃，同时在从模具中取出该层压体前保持该压力。
图2是示出由经轻度处理的氟氧化的PEKK粉末生产的经固结的PEKK层压体的截面视图的光学图像。
使用实例1中披露的经高度处理的经氟氧化的PEKK粉末重复上述制造过程。图3是示出由经高度处理的经氟氧化的PEKK粉末生产的经固结的PEKK层压体的截面视图的光学图像。
这些显微照片显示，经固结的PEKK层压体似乎没有孔隙，这表明已经发生了良好程度的固结。总体而言，数据显示，如果PEKK粉末已经过表面处理以增加表面亲水性和分散能量，则可以在没有表面活性剂的情况下将PEKK粉末分散在水中。表面张力测量结果也支持此结论。因此，然后有可能制造没有缺陷的PEKK复合层压体。
术语、定义和缩写
在本披露中，与数量关联使用的修饰语“大约”和“约”包括所述值并且具有上下文指示的含义(例如，包括与具体数量的测量相关的误差度)。例如，“约”后面的数字可以意指所列举的数字加上或减去所列举的数字的0.1％至1％。如在此使用的后缀“(s)”旨在包括其所修饰的术语的单数和复数二者，从而包括一种或多种该术语(例如，金属(metal(s))包括一种或多种金属)。在此所披露的范围包括端点以及这些范围的所有中间值，例如“1％至10％”包括1％、1.5％、2％、2.5％、3％、3.5％等。

Claims (25)

1.经表面处理的聚合物颗粒，每个颗粒包含聚芳醚酮(PAEK)聚合物或其共聚物的芯，以及包含氟和氧原子的亲水的外表面，所述亲水的外表面具有通过反相气相色谱法(IGC)测量的小于50mJ/m2的分散表面能。
2.根据权利要求1所述的经表面处理的聚合物颗粒，其中，每个经表面处理的聚合物颗粒的该芯构成该颗粒的按体积计至少80％。
3.根据权利要求1或2所述的经表面处理的聚合物颗粒，其中，这些经表面处理的聚合物颗粒具有通过激光衍射测量的100μm或更小的平均粒径(d50)。
4.根据权利要求1所述的经表面处理的聚合物颗粒，其中，所述亲水的外表面具有通过反相气相色谱法(IGC)测量的30mJ/m2至49mJ/m2的分散表面能。
5.根据权利要求3所述的经表面处理的聚合物颗粒，其中，这些经表面处理的聚合物颗粒具有通过激光衍射测量的1μm至100μm的平均粒径(d50)。
6.聚芳醚酮(PAEK)聚合物或其共聚物的经表面处理的颗粒，每个颗粒包含亲水的经氟氧化的外表面。
7.如权利要求1或6所述的经表面处理的颗粒，其中，该亲水的外表面通过将这些颗粒暴露于包含氧和氟的气态气氛而获得。
8.聚芳醚酮(PAEK)聚合物或其共聚物的经表面处理的颗粒，这些颗粒包含亲水的经氟氧化的外表面，这些亲水的外表面包含选自羰基和羟基的极性官能团。
9.如权利要求8所述的经表面处理的颗粒，其中，这些亲水的外表面进一步包含氟原子。
10.根据权利要求6、8或9中任一项所述的经表面处理的颗粒，其中，这些颗粒具有通过反相气相色谱法(IGC)测量的小于50mJ/m2的分散表面能。
11.根据权利要求10所述的经表面处理的颗粒，其中，这些颗粒具有通过反相气相色谱法(IGC)测量的30mJ/m2至49mJ/m2的分散表面能。
12.根据权利要求6、8或9中任一项所述的经表面处理的颗粒，其中，这些经表面处理的聚合物颗粒具有通过激光衍射测量的100μm或更小的平均粒径(d50)。
13.根据权利要求12所述的经表面处理的颗粒，其中，这些经表面处理的聚合物颗粒具有通过激光衍射测量的1μm至100μm的平均粒径(d50)。
14.一种无表面活性剂的浆料，该浆料包括：
分散在水溶液或水中的根据权利要求1至5中任一项所述的经表面处理的聚合物颗粒或根据权利要求6至13中任一项所述的经表面处理的颗粒，
其中，该浆料不含任何表面活性剂。
15.如权利要求14所述的无表面活性剂的浆料，其中，这些经表面处理的颗粒以基于该浆料的总重量按重量计0.5％至60％的量存在。
16.一种用于制造热塑性复合结构的方法，该方法包括：
(a)将如权利要求14或15所述的无表面活性剂的浆料施加到第一增强纤维层上以将这些颗粒分布到这些纤维上，形成第一经颗粒涂覆的层；
(b)在该第一经颗粒涂覆的层上放置附加的增强纤维层；
(c)将如权利要求14或15所述的无表面活性剂的浆料施加到该附加的增强纤维层上以将这些颗粒分布到这些纤维上，形成随后的经颗粒涂覆的层；
(d)将这些经颗粒涂覆的层干燥；以及
(e)通过施加热量和压力将这些经颗粒涂覆的层固结。
17.如权利要求16所述的方法，进一步包括：
重复(b)和(c)以在(d)干燥之前构建层压体厚度。
18.一种用于制造热塑性复合结构的方法，该方法包括：
(a)将疏水的热塑性聚合物的颗粒暴露于使这些颗粒的外表面亲水的表面处理，以获得根据权利要求1所述的经表面处理的聚合物颗粒；
(b)在不添加任何表面活性剂的情况下形成包含这些经表面处理的颗粒的水性浆料；
(c)将该水性浆料施加到第一增强纤维层上以将这些颗粒分布到这些纤维上，形成第一经颗粒涂覆的层；
(d)在该第一经颗粒涂覆的层上放置附加的增强纤维层；
(e)将该水性浆料施加到该附加的增强纤维层上以将这些颗粒分布到这些纤维上，形成随后的经颗粒涂覆的层；
(f)将这些经颗粒涂覆的层干燥；以及
(g)通过施加热量和压力将这些经颗粒涂覆的层固结。
19.如权利要求18所述的方法，进一步包括：
重复(d)和(e)以在(f)干燥之前构建复合层压体。
20.一种用于制造热塑性预浸料的方法，该方法包括：
(a)将疏水的热塑性聚合物的颗粒暴露于使这些颗粒的外表面亲水的表面处理，以获得根据权利要求1所述的经表面处理的聚合物颗粒；
(b)在不添加任何表面活性剂的情况下形成包含这些经表面处理的颗粒的水性浆料；
(c)将该水性浆料施加到增强纤维层上，以将这些颗粒分布到这些纤维上；
(d)将在其上带有这些颗粒的该增强纤维层干燥；以及
(e)通过施加热量和压力将该经干燥的层固结。
21.根据权利要求16至20中任一项所述的方法，其中，这些增强纤维是呈连续单向对齐的纤维、织造织物、非织造织物或无规排列纤维的非织造垫的形式。
22.根据权利要求16至20中任一项所述的方法，其中，这些增强纤维选自碳纤维、芳纶纤维、玻璃纤维及其组合。
23.根据权利要求18至20中任一项所述的方法，其中，在(a)中的这些疏水的热塑性聚合物的颗粒是PAEK聚合物或其共聚物的颗粒，并且该表面处理是通过将这些颗粒暴露于包含氧和氟的气态气氛进行。
24.一种热塑性复合结构，其通过根据权利要求16至19中任一项所述的方法生产。
25.一种热塑性预浸料，其通过根据权利要求20所述的方法生产。
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