CN102583222B - 形成具有纳米颗粒的材料的方法以及具有纳米颗粒的材料 - Google Patents

形成具有纳米颗粒的材料的方法以及具有纳米颗粒的材料 Download PDF

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CN102583222B
CN102583222B CN201110463167.8A CN201110463167A CN102583222B CN 102583222 B CN102583222 B CN 102583222B CN 201110463167 A CN201110463167 A CN 201110463167A CN 102583222 B CN102583222 B CN 102583222B
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predetermined pattern
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magnetic field
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CN102583222A (zh
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H·C·罗伯茨三世
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Abstract

本发明公开了形成具有纳米颗粒(104)的材料的方法以及具有纳米颗粒(104)的材料。该方法包括在基体材料(108)内将纳米颗粒(104)排列成预定图案(302)。该材料包含在基体材料(108)中形成预定图案(302)的经排列的纳米颗粒(104)。

Description

形成具有纳米颗粒的材料的方法以及具有纳米颗粒的材料
技术领域
本发明涉及材料以及形成材料的方法。更具体地，本发明涉及形成包含纳米颗粒的材料的方法以及包含纳米颗粒的材料。
发明背景
随着工业产品用于更多极端环境和极限用途，材料性能的局限也越来越被关注。作为回应，材料的性能被不断地改进。颗粒在材料内排列成预定图案可以提供所需的性能。
已知的材料是通过将纳米颗粒与基体混合形成增强混合物来强化的。增强混合物包含增大的粘度和更高的强度。然而，增强混合物成本昂贵并能导致不期望的性能如脆性。此外，增强混合物可能包含遍布的随机定向的纳米颗粒，并且不能用于需要有序纳米颗粒的应用。
一种已知的方法通过拉伸基体并将纳米颗粒放置在由基体拉伸而产生的空穴中以将有序纳米颗粒定位在基体中。纳米颗粒在基体的空穴中通常始终排列成行。这种方法的缺点是纳米颗粒的大小必须基本一致，由此导致了额外的成本。另外，纳米颗粒的排列成行是无法预见的，由于其受到基体中形成空穴的位置的限制从而防止纳米颗粒的排列。
在另一种已知的方法中，将纳米纤维定位在预定位置并与基体结合以形成具有期望的纳米纤维设计的平面层(flatply)。将该平面层切成图案，与其他的平面层堆叠，和/或弯曲以形成期望的形状。这种方法的缺点是其导致了由于修剪造成的纤维末端无法预见的破裂、由于修剪造成的空穴无法预料的破裂、分层、不期望的纳米纤维移动以及不期望的纳米纤维碎片。
微米纤维的排列是已知的。本文中使用的术语“微米纤维”涉及具有直径在约15微米到约100微米之间的视觉上可见的纤维。过去，人们通过使纤维定向的机械系统以及通过施加磁场来排列微米纤维。例如，在一种已知的方法中，通过施加磁场以排列一些具有约20微米直径和约1微米厚度的圆盘形的铁磁薄片。这些薄片有足够的尺寸以在视觉上可见，并且有足够的尺寸以被分离成基本一致的尺寸。微米纤维不能提供纳米颗粒可得的性能。
包含以预定的图案排列的纳米颗粒的材料和以预定的图案排列纳米颗粒的方法在本技术领域中是令人期望的。
发明简述
根据一个示例性实施方案，一种形成产品的方法包括提供基体材料和多个纳米颗粒，并通过施加场在基体材料中将多个纳米颗粒排列成预定图案。
根据另一个示例性实施方案，利用一种方法形成了一种产品，该方法通过向包含多个纳米颗粒的基体材料施加磁场从而排列多个纳米颗粒以形成预定图案。
根据另一个示例性实施方案，一种产品包含一种基体材料和基体材料上的一种预定图案，该预定图案包含多个纳米颗粒。
通过下文结合附图经由示例阐述了本发明原理的优选实施方案的更详细的描述，本发明其他的特性和优点将变得明显。
附图简要说明
图1示意性地表示了根据本公开的一个实施方案的一种包含经排列的纳米颗粒的示例性材料。
图2示意性地表示了根据本公开的一个实施方案的一种包含经排列的纳米颗粒的示例性材料。
图3示意性地表示了在根据本公开的一个实施方案的示例性方法之前随机排列的纳米颗粒。
图4示意性地表示了根据本公开的一个实施方案的示例性方法，沿随机排列的纳米颗粒布置的一个带正电的探头和一个带负电的探头。
图5示意性地表示了根据本公开的一个实施方案的示例性方法，通过施加磁场定向的纳米颗粒排列。
图6示意性地表示了根据本公开的一个实施方案的示例性方法，通过施加磁场定位的纳米颗粒排列。
图7示意性地表示了根据本公开的一个实施方案的示例性方法，通过在第二位置施加磁场定位的纳米颗粒排列。
图8示意性地表示了根据本公开的一个实施方案的示例性方法，定位为预定图案的纳米颗粒排列。
图9示意性地表示了根据本公开的一个实施方案的示例性方法，定位为预定图案之前的纳米颗粒排列。
图10示意性地表示了根据本公开的一个实施方案的示例性方法，定位为预定图案的纳米颗粒排列。
相同的参考数字可用于整个附图中任何可能的位置以代表相同的部件。
发明详述
本发明提供一种包含排列成预定图案的纳米颗粒的材料以及一种将纳米颗粒排列成预定图案的方法。本公开的实施方案能使纳米颗粒排列成复杂的预定图案以提供新的性能，由于纳米颗粒的施放(apply)和排列中具有一致性和控制力而能减少或消除纳米颗粒碎片的数量，能将较宽尺寸范围的纳米颗粒用于特定图案如线性图案，能减少或消除基体中的空穴，能减少或消除分层，能减少或消除纳米颗粒不期望的移动，能仅通过使用纳米颗粒带来独特的性能，及能有上述优点的组合。
在本公开的实施方案中，材料是涂层或复合材料的一部分或者形成涂层(例如在陶瓷基SiC纤维晶须、有机基碳晶须、有机基玻璃晶须和/或其他形式的芳族聚酰胺纤维上)或复合材料(例如陶瓷基体复合材料、有机基体复合材料和/或热塑性的和/或热固性的聚合物)。
参考图1-2，在一个示例性实施方案中，将包含多个纳米颗粒104的材料100排列并布置在基体材料108上以形成预定图案102。本文中使用的术语“纳米颗粒”涉及具有纳米级(10-9米)尺寸的任何结构。作为个体，纳米颗粒104是视觉上不可见的。例如，在本公开的实施方案中，纳米颗粒104具有小于约1500nm的直径，约10nm到约1500nm之间的直径范围，约10nm到约1000nm之间的直径范围，约20nm到约500nm之间的直径范围，约50nm到约500nm之间的直径范围，约100nm到约500nm之间的直径范围，约20nm到约400nm之间的直径范围，或者约40nm到约200nm之间的直径范围，通过纳米颗粒104的中央的20％、50％、80％或其全部来测量其直径，例如通过电子显微镜结合图像分析工具来测量。另外地或备选地，在本公开的实施方案中，纳米颗粒104具有在最大方差范围内小于20％的方差、小于5％的方差或小于1％的方差。
在本公开的实施方案中，纳米颗粒104是纳米尺度的石墨烯片、纳米管、纳米纤维、纳米粘土片(clayplatelet)、纳米棒、纳米尺度的增强物、其他合适的纳米结构或其组合。在一个实施方案中，纳米颗粒104是纳米填料。合适的纳米填料包括，例如纳米尺度的石墨烯片、纳米纤维和纳米管。
基体材料108是有机物、金属、陶瓷、玻璃、碳基、聚合物或其组合。本文使用的术语“聚合物”及其语法变化涉及但并不限于均聚物、共聚物(例如嵌段、接枝、无规和交替共聚物)、三元共聚物及其混合物。在一个实施方案中，基体材料108是包含聚交酯、聚乳酸、聚烯烃、聚丙烯腈、聚氨酯、聚碳酸酯、聚己内酯、聚乙烯醇、纤维素、壳聚糖尼龙、聚苯乙烯、蛋白质及其组合的聚合物。在一个实施方案中，基体材料108是包含聚(二烯丙基二甲基氯化铵)、聚丙烯酸、聚(硫酸氢丙烯胺)(poly(allylaminehydrosulfate))、聚(4-苯乙烯磺酸)、聚乙烯基硫酸钾盐，4-苯乙烯磺酸钠盐水合物、聚磺苯乙烯、聚乙烯亚胺、其他合适的聚合物或其组合的聚合物。
在一个实施方案中，基体材料108是仅由直链聚乙烯亚胺主链组成的聚合物、包含直链聚乙烯亚胺主链的嵌段、水溶性聚合物嵌段(例如聚乙二醇、聚丙酰乙烯亚胺和/或聚丙烯酰胺)、疏水性聚合物嵌段(例如聚苯乙烯或包含聚苯基噁唑啉、聚辛基噁唑啉、聚十二烷基噁唑啉的聚噁唑啉)的嵌段共聚物或聚丙烯酸酯(例如聚甲基丙烯酸甲酯和聚甲基丙烯酸丁酯)。
将多个纳米颗粒104的方向排列为预定图案102。将纳米颗粒104按经排列的方向施放到基体材料108中，和/或将其与基体材料108混合之后排列形成预定图案102。本文中使用的术语“预定图案”涉及设计好的排列。设计好的排列通过有意的纳米颗粒104的定位和定向而形成。设计好的排列由任何合适的方法形成，包含但不限于利用计算机辅助设计(CAD)程序。术语“预定图案”包含特意形成的图案，而不包含不均匀的随机的排列、不一致地形成的排列或不可预见的排列。
参考图1，在一个实施方案中，预定图案102包含基本上排列成平行方向的多个纳米颗粒104。参考图2，在一个实施方案中，预定图案102包含如此排列的多个纳米颗粒104，多个纳米颗粒104的一部分排列成基本直线方向，同时多个纳米颗粒104的一部分排列成曲线方向。在一个实施方案中，预定图案102是复杂的预定图案(例如回路图案、非线性图案、曲线图案或几何图案如正方形、矩形、圆形、椭圆形或其他合适的形状)。
在一个实施方案中，通过施加磁力来排列纳米颗粒104。在该实施方案中，纳米颗粒104是有磁性的或被磁化的。在该实施方案中，产生磁场，通过施加磁场来排列纳米颗粒104，并将基体材料108固化以固定纳米颗粒104的位置。在另一个实施方案中，在预定温度之上施加热量以去除纳米颗粒104的磁性。在一个备选的实施方案中，不在预定温度之上施加热量而保留纳米颗粒104的磁性。在一个实施方案中，将纳米颗粒104与基体材料108混合然后进行排列。在该实施方案中，向混合物施加磁场从而按预定图案102排列纳米颗粒104。与在混合物之外排列纳米颗粒104相比，在混合物中排列纳米颗粒104时包含更强的磁场。在一个实施方案中，磁场强度对应于混合物的粘度(例如对更高粘度的混合物施加更强的磁场)。
参考图1-2，在一个实施方案中，在基体材料108中按经排列的方向施放纳米颗粒104。例如，在该实施方案中，将纳米颗粒104排列在施放器106中。施放器106基于磁场使纳米颗粒104定向并按一致且可控的方向施放纳米颗粒104。在该实施方案中，由于可以按一致且可控的方向施放，可以使用其他方法难以排列的非常小的纳米颗粒104。
磁场是任何合适的磁场。在一个实施方案中，磁场是一个磁场。在该实施方案中，纳米颗粒104是有磁性的或被磁化的。磁场以推动、吸引、排斥、旋转或其他方式调整在磁场内的纳米颗粒104的方向。在一个实施方案中，将磁场施加一段预定的时间和/或直到将纳米颗粒104排列为预定图案102。在一个实施方案中，利用多个磁场将纳米颗粒104排列为复杂的预定图案。在一个实施方案中，施加具有第一强度的第一磁场和具有第二强度的第二磁场，第一强度与第二强度不同。在其他实施方案中，将其他的场(例如离子场或电场)用于调谐(tune)至极化场线的调谐的纳米颗粒。
图3-8显示了将纳米颗粒104排列为预定图案102的示例性方法的步骤。在一个实施方案中，该示例性方法包括将纳米颗粒104排列在基体材料108中。在另一个实施方案中，该示例性方法包括在向基体材料108施放纳米颗粒104之前，将纳米颗粒104在施放器106内排列。
参考图3，在第一步中，以接近预定路径302的随机排列方式提供纳米颗粒104。虽然预定路径302显示为一条曲线，但是也可以是预定图案102任何合适的前体。参考图4，在第二步中，沿预定路径302放入一个带正电的探头402和一个带负电的探头404。参考图5，在第三步中，启动带正电的探头402和带负电的探头404从而生成场(例如磁场、离子场、电场或其组合)并调整纳米颗粒104的部分504的方向(例如，在一个实施方案中，方向的调整包括对被对齐(aligned)的纳米颗粒104的部分504进行排列成行)。参考图6，在第四步中，调整纳米颗粒104的该部分504的位置(例如，在一个实施方案中，该部分504的位置大致沿着预定路径302)。参考图7，在任选的第五步中，沿接近纳米颗粒104第二部分702的预定路径302放置带正电的探头402和带负电的探头404。图8显示了根据该示例性方法以预定图案102排列的纳米颗粒104。
参考图9-10，在一个实施方案中，将纳米颗粒104放置并排列在部件902(例如纤维复合材料中的一个孔或结)的周围。图9显示了施加场之前，纳米颗粒104从部件902中延伸穿过。图10显示了放入并启动带正电的探头402和带负电的探头404以形成纳米颗粒104的预定图案102。在该实施方案中，预定图案102类似于硬木夹板产品。在其他的实施方案中，预定图案102类似于任何合适的木纹图案、任何合适的大理石花纹、任何其他的天然图案、任何合适的非天然的图案、美学设计或任何其他合适的图案。
虽然参考优选的实施方案对本发明进行了描述，本领域的技术人员应当理解，在未脱离本发明范围的条件下可以对要素作出各种的改变以及等价替换。此外，在不脱离其实质范围的情况下，为适用于特定的情况或材料，可以对本发明的教导作出多种修正。因此，本发明的目的不限于预期作为用于实施本发明的最佳方式公开的特定的实施方案，而将包含落入所附权利要求范围内的所有实施方案。

Claims (17)

1.一种形成具有纳米颗粒的材料的方法，该方法包括：
提供多个纳米颗粒(104)和基体材料(108)；
通过施加磁场在基体材料(108)中将多个纳米颗粒(104)排列成预定图案(302)；
固化基体材料(108)从而固定多个纳米颗粒(104)中至少一部分的位置，
其中将磁场施加于施放器(106)，从而在施放器(106)内将该多个纳米颗粒(104)中的至少一部分定位，施放器(106)将多个纳米颗粒(104)排列在基体材料(108)中。
2.根据权利要求1所述的方法，其进一步包括将具有预定图案(302)的基体材料(108)用作涂层。
3.根据权利要求2所述的方法，其中将涂层用于芳族聚酰胺纤维。
4.根据权利要求1所述的方法，其中基体材料(108)选自陶瓷基体复合材料、有机基体复合材料、热塑性聚合物、热固性聚合物及其组合物。
5.根据权利要求1所述的方法，其中多个纳米颗粒(104)中至少一部分是有磁性的。
6.根据权利要求1所述的方法，其中多个纳米颗粒(104)中至少一部分是被磁化的。
7.根据权利要求1所述的方法，其中将磁场施加至基体材料(108)的混合物。
8.根据权利要求1所述的方法，其中预定图案(302)包含的纳米颗粒(104)中的至少一部分为平行。
9.根据权利要求1所述的方法，其中预定图案(302)包含的纳米颗粒(104)中的至少一部分排成直线。
10.根据权利要求1所述的方法，其中预定图案(302)包含的纳米颗粒(104)中的至少一部分为非线性。
11.根据权利要求1所述的方法，其中预定图案(302)包含的纳米颗粒(104)中的至少一部分形成曲线的一部分。
12.根据权利要求1所述的方法，其中预定图案(302)包含的纳米颗粒(104)中的至少一部分形成复杂预定图案的一部分。
13.根据权利要求1所述的方法，其中通过施加第一磁场和第二磁场来排列纳米颗粒(104)。
14.由一种形成具有纳米颗粒的材料的方法形成的产品，该方法向包含多个纳米颗粒(104)的基体材料(108)施加磁场，从而排列该多个纳米颗粒(104)以形成预定图案(302)；固化基体材料(108)从而固定多个纳米颗粒(104)中至少一部分的位置，
其中将磁场施加于施放器(106)，从而在施放器(106)内将该多个纳米颗粒(104)中的至少一部分定位，施放器(106)将多个纳米颗粒(104)排列在基体材料(108)中。
15.一种具有纳米颗粒的材料，其包含：
基体材料(108)；以及
基体材料(108)中的预定图案(302)，预定图案(302)包含多个纳米颗粒(104)，
其中基体材料(108)选自陶瓷基体复合材料、有机基体复合材料、热塑性热固性聚合物、芳族聚酰胺纤维上的涂层及其组合，
固化基体材料(108)从而固定多个纳米颗粒(104)中至少一部分的位置，其中将磁场施加于施放器(106)，从而在施放器(106)内将该多个纳米颗粒(104)中的至少一部分定位，施放器(106)将多个纳米颗粒(104)排列在基体材料(108)中。
16.根据权利要求15所述的具有纳米颗粒的材料，其中多个纳米颗粒(104)中至少一部分是有磁性的。
17.根据权利要求15所述的具有纳米颗粒的材料，其中预定图案(302)包含形成复杂预定图案的一部分的多个纳米颗粒(104)。
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