CN101171360B - 具有金属纳米粒子涂层的微孔制品 - Google Patents
具有金属纳米粒子涂层的微孔制品 Download PDFInfo
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- CN101171360B CN101171360B CN200680015413.0A CN200680015413A CN101171360B CN 101171360 B CN101171360 B CN 101171360B CN 200680015413 A CN200680015413 A CN 200680015413A CN 101171360 B CN101171360 B CN 101171360B
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Abstract
本发明描述了涂覆金属纳米粒子的微孔衬底及其制备方法和用途。
Description
技术领域
本发明涉及涂覆金属纳米粒子的材料及其使用和制备方法。
背景技术
直径约1-100纳米(nm)的金属纳米粒子是用于诸如半导体技术、磁储存、电子产品制造以及催化作用这类的应用中的重要材料。金属纳米粒子已经通过下述方法制造:气体蒸发法、流动气流中的蒸发法、机械研磨法、溅射法、电子束蒸发法、化学还原法、热蒸发法、二元金属叠氮化物的电子束诱导雾化法、超声自由射流中的金属蒸汽的膨胀法、逆胶束法、激光烧蚀法、有机金属化合物的激光诱导击穿法、有机金属化合物的裂解法、有机金属化合物的微波等离子体分解法和其它的方法。
已知金属纳米粒子具有独特的光学性能。具体地说,金属纳米粒子具有突出的光学共振性。这种所谓的等离子体共振是由于在从金属球到入射电磁场的传导电子的并合耦合。这种共振可由吸收或散射决定,该吸收或散射随着涉及入射电磁辐射的波长的纳米粒子的半径的不同而不同。与这种等离子体共振有关的是金属纳米粒子内部强局部场的增强。可以制造各种可能有用的装置,以利用这些特定的光学性能。例如,已经制造了基于表面增强拉曼散射(SERS)的滤光器或化学传感器。
发明概述
本发明提供了一种制品,该制品包含其上具有金属纳米粒子涂层的微孔材料。 “金属”是指单质金属及其化合物。微孔材料可以是薄膜、片材或纤维的形式,但是优选是薄膜或片材的形式。涂层制品提供了一种便捷的存储纳米粒子和将该纳米粒子转移到另一种衬底例如玻璃、塑料和金属中的方式。这些涂层衬底可用于多种依靠金属纳米粒子的光学性能、化学性能或磁性的装置和技术中,这些装置包括光学装置,如透镜、片材、纤维、棱镜、滤光器和化学传感器。
本发明通过提供用于存储和转移纳米粒子的稳定制品来克服现有技术的局限。迄今为止,通过物理蒸气沉积技术或通过将纳米粒子的分散体/悬浮液涂覆到衬底上,纳米粒子被直接沉积到衬底的表面上。物理蒸气沉积设备不适于连续涂覆法。由于纳米粒子易于聚集和从溶液中沉淀出来,因此纳米粒子分散体通常是不稳定的。使用分散体也包括使用溶剂和还原剂,并将分散体暴露于其中,这可能会污染纳米粒子。
有利的是,本方法也允许在从涂层微孔膜中转移纳米粒子时,控制衬底上的纳米粒子的涂层密度(纳米粒子数/平方厘米)。
本发明的制品可用于制备涂覆纳米粒子的衬底,其用于多种应用,例如光交换装置、光通信系统、红外探测器、红外掩蔽装置、化学传感器、被动式太阳辐射收集或偏转装置等。
在一种实施方案中,本发明提供了一种制备涂覆纳米粒子的微孔膜的方法,该方法包括如下步骤:提供微孔材料、通过物理蒸气沉积法将不连续的金属纳米粒子涂层沉积到微孔材料的表面上。该方法还可包括在沉积前或沉积后对涂覆纳米粒子的制品进行拉伸的步骤。
在另一种实施方案中,本发明提供了一种在衬底上的纳米粒子涂层,包括:提供衬底和涂覆纳米粒子的微孔膜,使所述衬底和所述涂覆纳米粒子的制品在足够的压力的条件下接触,以将至少一部分所述纳米粒子从所述涂覆纳米粒子的制品中转移至所述衬底的表面上。
如本文所使用的,术语“微孔性的”指整个材料中在微观尺寸(即,在显微镜下是可见的,但使用肉眼无法观察到)的、连通或相互连接的孔或空隙中具有稀释剂相和/或气体,例如空气。
如本文所使用的,术语“热塑性聚合物”仅指常规的结晶和非结晶聚合物,该聚合物在通常的熔融加工条件下是可熔融加工的。
如本文所使用的,热塑性聚合物中所使用的术语“结晶”包括至少部分结晶的聚合物。在熔融加工的热塑性聚合物中的结晶聚合物的结构是熟知的。
如本文所使用的,热塑性聚合物中所使用的术语“无定形”包括没有实质晶序的聚合物,例如聚甲基丙烯酸甲酯、聚砜和无规立构聚苯乙烯。
如本文所使用的,术语“熔解温度”指这样的温度,在该温度下,以热塑性聚合物和相容性液体共混物的形式存在的热塑性聚合物熔化。
如本文所使用的,术语“结晶温度”指这样的温度,在该温度下,以热塑性聚合物和相容性液体熔融共混物的形式存在的热塑性聚合物结晶。
如本文所使用的,热塑性聚合物中所使用的术语“平衡熔点”指在出版的文献中找到的普遍认同的热塑性聚合物熔点温度。
从下面的发明详述和权利要求书中将明白本发明的各种特征、实施方案和优点。本发明的以上概述不是用来描述本公开的每个被说明的实施方案或每种实施方式。随后的详细说明将利用本文中所公开的原理更具体地例示了某些优选实施方案。
附图说明
图1是实施例2的吸收光谱。
图2是实施例3的吸收光谱。
发明详述
本发明部分地涉及其上含有不连续的金属纳米粒子涂层的微孔膜。纳米粒子涂层是通过物理蒸气沉积法沉积不连续的金属纳米粒子层而形成的。如本文所使用的, “不连续的”指纳米粒子涂层被设置为被未涂覆的区域所包围的纳米粒子的岛或聚集体。大部分金属纳米粒子通常是单质金属纳米粒子,尽管也预料到其它金属性纳米粒子,例如金属氧化物纳米粒子。
本发明提高了在微孔材料上的金属纳米粒子涂层,纳米粒子的平均数均粒径在1至100纳米的范围内,最优选在1至50纳米的范围内。涂层的平均厚度通常小于100纳米,优选小于10纳米。纳米粒子可基本上是球形的,但是在一些情况下是细长的,长宽比(长度与直径之比)大于1.5∶1(即基本上是椭圆形的)。任选地,微孔膜在沉积前或沉积后被拉伸(取向)。
受到金属纳米粒子涂覆的微孔材料的特征可以是这样的热塑性聚合物结构,该结构具有多个互连通道,以提供连通各孔的网络。在微孔片材中,典型的孔或空隙的尺寸在100埃至4微米的范围内。
通常,微孔热塑性聚合物材料可通过下述步骤制备:
a)将热塑性聚合物与增溶量的相容性液体(稀释剂)在足够高的温度下熔融共混,以形成均匀的溶液;
b)由所述溶液形成制品;
c)将所述成形制品在一定速率下冷却至足够的温度,以引发热力学、非平衡相分离;
d)进一步冷却所述制品,以固化所述热塑性聚合物;以及
e)任选地除去至少大部分所述相容性液体。
任选地在热塑性聚合物的固化(步骤d)后或除去相容性液体(步骤e)后对微孔膜进行取向。所述热力学、非平衡相分离可以是液液相分离或液固相分离。
当发生液液相分离时,网格(cells)包含被纤维状、带状或半连续的聚合物边界所包围的空隙体积。在定向时,网格在定向方向上被拉伸。定向制品的网格通常是椭圆形的,主轴与短轴的长宽比大于1.0,并且主轴通常位于平行于制品表面的平面内。当发生液固相分离时,材料内部结构的特征为热塑性聚合物的多个间隔的、任意设置的、非均匀形状的、等轴的热塑性聚合物粒子,在整个所述材料中相邻粒子彼此分离以给材料提供由互连微孔构成的网络,并通过多个构成热塑性聚合物的原纤维彼此连接。在定向时原纤维的拉伸提供热塑性聚合物粒子间的更大的间隔,增大了孔隙率。
有用的热塑性聚合物包括诸如聚酰胺、聚酰亚胺、聚氨酯、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯、聚酮、聚脲、聚丙烯酸酯和聚甲基丙烯酸酯之类的烯烃类聚合物、缩聚物和氧化聚合物。代表性的烯烃类聚合物包括高密度和低密度聚乙烯、聚丙烯、含聚乙烯基的聚合物、含丁二烯的聚合物、含丙烯酸酯的聚合物(例如聚甲基丙烯酸甲酯)和含氟聚合物(聚偏二氟乙烯)。缩聚物包括聚酯(例如聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯)、聚酰胺(例如尼龙6、尼龙11、尼龙13和尼龙66)、聚碳酸酯和聚砜。聚苯醚是可使用的氧化聚合物的代表。也可以使用热塑性聚合物的共混物。
合适的可结晶的聚合物的包括加聚物(例如聚烯烃)和缩聚物(例如聚酯和聚酰胺)。有用的聚烯烃优选包括乙烯和丙烯的聚合物,但是也可以包括甲基戊烯、丁烯、1-辛烯和苯乙烯等的聚合物,以及两种或多种这样的烯烃的共聚物,该烯烃可以聚合以获得结晶和无定形链段以及这种聚合物的立体定向修饰物的混合物,所述混合物例如,等规聚丙烯和无规立构聚丙烯的混合物、等规聚苯乙烯和无规立构聚丙烯的混合物。有用的聚酯包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚己二酸己二醇酯、聚丁二酸己二酯和聚酯共聚物。有用的聚酰胺包括聚己二酰己二胺、聚癸二酰己二胺和聚己内酰胺。这些聚合物被描述在例如美国专利No.4,247,498、4,539,256、4,726,989、4,867,881和4,849,311中。
相容性液体(通常称为稀释剂)是这样的材料:该材料在被加热至聚合物的熔解温度以上的温度时,能够与热塑性聚合物形成溶液,并且在冷却时,该材料从聚合物中相分离。液体和聚合物的相容性可以通过将聚合物和液体加热至形成透明、均匀的溶液来测定。如果在任何液体浓度下都不能形成聚合物和液体的溶液,那么该液体不适合与该聚合物一起使用。实际中,所使用的液体可包括在室温下是固体、但是在聚合物的熔解温度下是液体的化合物。总的来说,对于非极性聚合物而言,具有类似的室温溶解度参数的非极性有机液体在溶液温度下通常是有用的。类似地,极性有机液体通常和极性聚合物一起使用。当使用聚合物的共混物时,有用的液体是对所使用的每一种聚合物而言都是相容性液体的那些液体。当聚合物是嵌段共聚物时,例如苯乙烯-丁二烯共聚物,所选择的液体必须是与每一种聚合物嵌段都相容的。只要所选择的液体在聚合物的熔解温度下,在液体共混物中是可溶的,并且所形成的溶液在冷却时相分离,那么两种或多种液体的共混物就可以用作相容性液体。
现已发现可用作相容性液体的各种有机化合物包括:脂肪酸类和芳香酸类;脂肪醇类、芳香醇类和环醇类;醛类;伯胺类和仲胺类;芳香胺类和乙氧基化胺类;二胺类;酰胺类;酯类和二酯类;醚类;酮类以及各种烃类和杂环类。当所选择的聚合物是聚丙烯时,例如矿物油的脂肪烃类、例如邻苯二甲酸二丁酯的酯类、例如二苄醚的醚类可用作相容性液体。当聚合物是高密度聚乙烯时,例如矿物油的脂肪烃类或例如甲壬酮的脂肪酮类或例如邻苯二甲酸二辛酯的酯类可用作相容性液体。和低密度聚乙烯一起使用的相容性液体包括例如癸酸和油酸的脂肪酸类或例如癸醇的伯醇类。当聚合物是聚偏二氟乙烯时,例如邻苯二甲酸二丁酯的酯类可用作相容性液体。当所选择的聚合物是尼龙11时,例如碳酸丙二酯、碳酸乙二酯的酯类或环丁砜可用作相容性液体。当所选择的聚合物是聚甲基丙烯酸甲酯时,有用的相容性液体包括1,4-丁二醇和月桂酸。和聚合物聚苯醚一起使用的相容性液体为例如牛油胺。
用于所使用的稀释剂-聚合物系统的选自预定的浓度范围的实际的聚合物的浓度由功能考虑所限定。聚合物的浓度和分子量应当足够以提供这样的微孔结构,该结构在冷却时形成,具有足够的强度以用于进一步加工步骤中的处理。聚合物的浓度应当使得液体-聚合物熔融溶液的粘度适合于用于制品成形的设备。通常,相对于相容性液体的浓度为20至90wt%,相容性液体中的聚合物的浓度为约10至80wt%。热塑性聚合物和相容性液体的相对量随着每个系统的不同而不同。可用于给定的系统的聚合物的浓度可以通过参照用于聚合物-液体系统的温度-组成图来测定,如Smolders、van Aartsen和Steenbergen,Kolloid-Z.u.Z.在polymere,243,14-20(1971)中所阐述的。
微孔膜可以在至少一个方向上被取向,即被拉伸超出其弹性极限,以引入持久的设置或伸长,并且确保持久地开发或形成微孔。拉伸步骤通常包括双轴拉伸成型品。拉伸步骤在成形品中提供超出该成型品初始面积约10%至大于1200%的面积增长。取向可以在除去相容性液体前或后进行。这种结构的定向有助于在不改变粒子均匀度和在聚合物相中的聚集度的情况下,控制孔径并提高材料的孔隙率和机械性能。以可以另外进行拉伸,以提高膜的强度和特性。这可以导致具有改善的抗撕裂性的膜。
本发明的膜的取向处理可用作一种可变化地控制厚度的方法,并且可以制造相对薄的微孔膜。取向处理能够没有多少困难地制造薄膜。取向处理也增强了在许多微孔膜应用中都是有益的膜的机械强度。随着取向的增加,膜的厚度和抗流动性相称地降低,机械强度和孔隙率相称地提高,并且随着对孔径控制的增强,孔径范围也变大,使得通过选择微孔膜经历的定向的量,可以获得所需性能的优良的平衡。在拉伸时,聚合物制品被拉开,持久地细化连接区域中的聚合物,进而在涂覆的粒子间形成原纤维和孔,并且产生互相连接的微孔的网络。这种持久的细化也使制品持久地不透明。
如果稀释剂没有被除去,那么稀释剂保持涂覆在所得多孔聚合物相的表面上,或者至少包围在该表面周围,并且具有基于稀释剂和聚合物20至90wt%的浓度。
至少可以部分地除去稀释剂,以获得所需的孔隙率并减少稀释剂和纳米粒子一起转移至衬底中的稀释剂的量。除去处理可以通过已知的方法完成,例如洗涤法、溶剂提取法、取代法、蒸发法或任何其它方便的方法。如果在拉伸前或在拉伸时进行除去处理,所得膜是不透明的。如果在拉伸前或拉伸后进行稀释剂除去处理,所得膜保持为不透明的,并且较仅仅被拉伸处理的膜具有更多的孔。稀释剂除去处理发生在纳米粒子沉积之前,否则金属纳米粒子在稀释剂除去过程中也被除去了。尽管在稀释剂除去后,微孔膜包含至少5wt%的稀释剂,但是在进行稀释剂除去时,微孔膜可能包含至少20wt%或小于10wt%的稀释剂。
微孔片材可以被层叠、粘结或固定到各种其它材料(例如织造、编织或非织造织物、聚合物膜)或者类似或其它的微孔片材的一个或多个附加层上,以获得例如所需的厚度、空隙梯度、加工性能和机械性能。附加层可以在沉积前或沉积后被固定。附加层被固定到相对于涂覆纳米粒子的表面的主要表面、即非涂覆的表面上。层叠可以使用常规的方法进行,这些方法例如粘合剂粘结法、点焊法或其它不会对纳米粒子涂层产生不良影响的方法。
有用的制备微孔膜的方法可以在下列参考资料中找到。
美国专利No.4,247,498(Castro)公开了这种微孔聚合物,其特征在于相对均匀、三维的网状结构,该结构具有通过更小尺寸的孔连接的网格。微孔聚合物由热塑性聚合物通过下述步骤制备:加热聚合物和相容性液体的共混物,以形成均匀的溶液;在非平衡热力学条件下冷却溶液,以开始液液相分离;以及继续冷却,直到共混物获得充足的加工强度为止。
美国专利No.4,539,256(Shipman)公开了这样一种微孔片材,其特征在于多种热塑性聚合物的任意间隔、分散、等轴、非均匀的颗粒,相邻的热塑性粒子通过多个热塑性聚合物的原纤维彼此连接。所述片材通过下述步骤制备:将可结晶的热塑性聚合物和这样一种化合物熔融共混,该化合物在聚合物的熔解温度下与热塑性聚合物是可混溶的,但在或小于聚合物的结晶温度下冷却时相分离;形成熔融共混物的成形品;将成形品冷却至这样的温度,在该温度下所述聚合物结晶,以引起热塑性聚合物和化合物之间发生相分离。
美国专利No.4,726,989(Mrozinski)公开了加入成核剂的微孔材料,该微孔材料通过下述步骤制备:将可结晶的热塑性聚合物和能够诱导热塑性聚合物随后进行结晶的成核剂以及这样一种化合物熔融共混,该化合物在聚合物的熔解温度下与热塑性聚合物是可混溶的,但在或小于聚合物的结晶温度下冷却时相分离;形成熔融共混物的成形品;将成形品冷却至这样的温度,在该温度下成核剂诱导热塑性聚合物结晶,以便引起热塑性聚合物和化合物之间发生相分离。
美国专利No.4,867,881(Kinzer等人)描述了这样一种微孔制品,该微孔制品包括通过液液相分离而形成的热塑性聚合物结构,所述结构具有多个网格,所述网格与相邻网格通过通道互连,以提供连通各孔的网络,所述网格具有多个被纤维状、带状或半连续的边界所包围的空隙体积,并且是椭圆形的,所述结构至少在一个方向上被取向。
纳米粒子涂层通过产生纳米粒子的物理蒸气沉积法制备。金属在减压下被加热,直到发生蒸发为止。任选地,金属在存在气流的情况下进行蒸发,其中尽管可以使用任何不与金属发生反应的气体,但是气体优选是惰性的(非反应性的)。纳米粒子被转移或指引到微孔材料上(任选地通过气流),通过将金属蒸汽碰撞到微孔材料上而被沉积,其中发生成核和纳米粒子的生长。通常在没有气流的情况下,物理蒸气沉积法产生金属蒸汽,该蒸汽直接在微孔材料的表面上成核。在存在气体的情况下,金属蒸汽在气流中经历一定程度地均匀成核,以产生沉积到微孔材料的表面上的纳米粒子。
涂层可以通过这样的方法制备,该方法包括以下步骤:
a)任选地在存在非反应性气流的情况下蒸发金属,以提供金属蒸汽;
b)任选地提供能够与所述金属蒸汽(或在所述金属蒸汽中形成的金属纳米粒子)反应的第二反应性气体,并且使所述反应性气体与所述金属蒸汽(或金属纳米粒子)反应,以将所述金属蒸汽(或金属纳米粒子)转化为金属氧化物纳米粒子,以及
c)将所述金属蒸汽碰撞到所述微孔材料上,其中发生纳米粒子的成核和生长,以在所述微孔材料上提供纳米粒子涂层。
可以使用本领域普通技术人员已知的多种物理蒸气沉积法中的一种方法获得将金属纳米粒子沉积到微孔材料的表面上。这种方法包括蒸汽沉积法、阴极溅射法、热解法、离子镀法、电子束沉积法等。考虑到可获得的结构和厚度的均匀性,通常优选蒸汽沉积法和阴极溅射法。参照Vacuum Deposition of Thin Films,L.Holland,1970,Chapmanand Hall,London,英格兰,其中涉及许多可利用的提供金属蒸汽和蒸汽涂覆技术的方法。如果需要,纳米粒子层可以通过掩模被图案涂覆(pattern coated),使得金属纳米粒子的表面可以是图案化的。
纳米粒子涂层的平均厚度可以在沉积过程中使用市售的石英晶体微量天平来测定。在沉积后,许多化学测定结果可用于表征任何的特定区域中的金属的量。粒径(通过纳米粒子的聚集而形成)通常使用现有技术中已知的光散射法来测定。一次颗粒的直径通常使用透射电子显微镜或原子力显微镜来测定。
物理蒸气沉积(PVD)法包括通常通过在真空条件下蒸发或溅射来沉积原子。PVD法可通过下述步骤来表征:(1)使用电阻加热法、感应加热法、电子束加热法、激光束烧蚀法、直流等离子体产生法、射频等离子体产生法、分子束外延法或类似的方法产生金属蒸汽;(2)通过分子流、粘性流、等离子体气体传输等方式将金属蒸汽从原料输送到衬底上;以及(3)在热塑性聚合物膜上进行纳米粒子的生长,其中发生纳米粒子的成核和生长。使用PVD法尽管通常热塑性聚合物膜的温度低于聚合物的变形温度,但是可以用各种衬底温度来控制沉积的材料的结晶和生长方式。
为了避免薄膜衬底在沉积过程中变形或熔融,微孔材料通常被维持在等于或低于聚合物的热变形温度的温度下。微孔材料的完整性通过下述步骤来维持:控制沉积速率,使得纳米粒子的温度,或者纳米粒子在沉积时释放的热量(冷凝热)不导致薄膜热变形。通常,微孔材料的温度维持在沉积室的环境条件下,不需要对薄膜进行特别的冷却。
在优选实施方案中,纳米粒子涂料通过电子束蒸发法被施加到微孔材料上。该方法基于高能电子束轰击到待沉积的金属上所产生的热量。电子束通过电子枪产生,所述电子枪使用通过白热灯丝(阴极)所产生的电子的热电离子发射。发射的电子通过高电压差(数千伏)向阳极加速。坩锅(包含源金属)本身或邻近的穿孔盘可以用作阳极。经常施加磁场,以弯曲电子轨迹,使电子枪置于蒸发线以下。由于电子可以被聚集,因此可能在金属材料上获得非常局部的加热,以进行具有高密度的蒸发能力(数千瓦)的蒸发。该方法允许将蒸发速率控制在较低的值到非常高的值。冷却坩锅避免了来自加热和脱气中的污染问题。
当使用电场驱动的气体离子轰击目标(通常是阴极)时,通过溅射的物理蒸气沉积到部分真空(对于二极管系统而言,介于13.3至1.33Pa之间,对于磁控管系统而言,介于1.3至0.13Pa之间)的条件下完成。溅射气体通常是稀有气体例如氩气,但是溅射气体可以包括可以引入沉积的薄膜中的反应性元素,例如沉积氮化物、氧化物和碳化物。当溅射气体是离子化时,产生辉光放电或等离子体。离子气体通过电场或电磁场向目标加速。通过动量传递,目标中的原子被发射出来,并穿过真空室被沉积到衬底(热塑性聚合物膜)上。
在另一种实施方案中,纳米粒子涂料通过溅射镀法被施加到微孔材料上。溅射装置通常由三源磁控管溅射系统组成,这些系统排列在含有直径为38厘米(15英寸)的旋转鼓的圆柱形室的外圆周上。衬底装在转鼓上,并以1至8rpm的速度顺序地旋转通过溅射源前面的位置。溅射源被适当遮蔽起来,这样样品不会在同一时间被任两个溅射流所涂覆。材料沉积的速率和衬底在目标前旋转的速度决定了包含最终催化剂颗粒的各单层厚度。任何能抽足够真空的真空泵均可采用。一种这样的真空泵是Varian AV8低温泵(Varian Associates,Lexington,Mass),它可以和Alactel 2012A回转叶片式初级泵(Alactel VaccumProducts,Hingham,Mass)结合使用。低温泵可以通过碟形阀与溅射室部分隔离。在沉积期间,压力维持在0.28帕(2.1毫托),溅射气流速度由MKS流量控制器(MKS Instruments Inc.,Andover,Mass)控制。任何惰性或反应性的溅射气体均可采用。优选使用氩气或氩气和氧气的混合气体。通过改变氩气/氧气流量比就可以控制氧的化学计量。任何合适的目标和功率源均可采用。在一种实施方案中,AdvancedEnergy MDX 500电源(Advanced Engergy Industries,Inc.,Fort Collins,Colo)以电源的恒功率的模式使用。
可用于物理蒸气沉积步骤中的有用的金属包括例如Li、Na、K、Rb、Cs、Fr、Be、Mg、Ca、Sr、Ba、Ra、Y、La、Ac、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、In、Tl、Sn、Pb、 混合物、氧化物以及这些金属的合金甚至镧系元素和锕系元素。如果需要,金属可以顺序地或同时地被沉积。
特别有用的金属是金、铝、铜、铁、铂、钯、铱、铑、锇、钌、钛、钴、钒、镁、银、锌和镉、铟、镧、铟锡氧化物(ITO)和锑锡氧化(ATO)、锑铟锡氧化物(AITO)、锡、硼、六硼化镧、稀土金属及其混合物与合金、以及这些金属的混合物与合金。最优选的是贵金属。其它的金属对本领域技术人员来说是显而易见的。
本方法可以包括正如金或银一样的单质金属本身的蒸发,或者可以包括前体形式的蒸发,在与聚合物膜接触之前,在转移阶段中产生实际的单质金属。一个例子是使用氩气作为非反应性气体蒸发金属银,随后将银纳米粒子暴露于反应性氧气环境中,进而在与聚合物膜接触之前形成涂覆超细氧化银的纳米粒子(粒子核心是银)。由于反应性气体是在形成纳米粒子后引入到距离蒸发源较远的位点上,因此,最终的纳米粒子由中心的芯和外面的壳构成,其中中心的芯可以是金属,并且其中外面的壳可以包含通过反应性气体和金属纳米粒子反应而形成的层。
在使用的场合下,惰性气体通常选自He、Ne、Ar、Xe和N2。也可以使用两种或多种非反应性气体的混合物。当需要对金属进行改性时,反应性气体通过入气口引入,所述入气口位于这样的位置,使得反应性气体在坩锅中与体材料的反应最小化,并使反应性气体和夹带在气流中的粒子充分混合,进而发生与粒子的反应。反应性和非反应性气体通常都处于室温下,但是根据需要,温度可以升高或降低。术语“反应性”包括1)使用O2、NO、NO2、CO2、CO、AsH3、H2S、H2Se、NH3、三甲基氯硅烷、甲胺、环氧乙烷、水、HF、HCl或SO2或其组合直接与粒子反应,例如在粒子为金属的情况下反应,以形成相应的氧化物或其它化合物;或2)吸附,其中在与分散介质接触之前,将挥发性物质加入气体中,但是该物质在常规条件(标准大气压和25℃)下不是液体,并且该物质与分散介质不相溶,否则该物质发挥作用,使纳米粒子的表面免于与分散介质或分散介质中的添加剂接触。通常可以被吸附的物质包括聚合物,例如聚(甲基丙烯酸甲酯)和聚苯乙烯。
一种有用的涂覆纳米粒子的装置,该装置包括:
a)连接收集容器的炉,所述炉包括加热构件(例如电阻加热构件、感应加热构件、电子束加热构件、红外加热构件、激光加热构件和等离子流加热构件),并适于包括至少第一和可任选的第二入气管,所述第二入气管位于所述第一入气管的下游;以及用于抽空所述炉的构件(例如,诸如旋转式油泵、油扩散泵、活塞泵、RootsTM鼓风机、涡轮分子泵之类的泵)和收集容器,所述收集容器包含分散介质;
b)用于将金属加入所述炉及其抽出物中的构件(例如陶瓷或金属坩锅或厚板,其可以预载金属,或者在操作装置过程中连续或分批加料、或者电极可以是所述构件);
c)任选地通过所述第一入气管将第一、非反应性气体流加入所述炉中的构件(例如,微计量阀、电子流量控制器或气体分流管);
d)用于将所述金属纳米粒子蒸发到所述第一气流中的构件(例如通过电子束法、红外法、激光法、感应法、电阻法或等离子流法输入能量);
e)使所述蒸发的金属纳米粒子在所述第一气流中冷凝(例如降低温度、提高压力、改变所述非反应性气体的化学性质、控制所述转移管的长度、控制气流速率或其组合),以在所述第一气流中产生分散的纳米粒子的构件;
f)任选地,通过所述第二入气管将第二反应性气流加入所述炉中,以允许与所述金属纳米粒子发生反应的构件(例如微计量阀、电子流量控制器或气体分流管);
g)用于将所述纳米粒子碰撞到所述热塑性微孔材料的表面上的构件。
其它可以预料到的提供本发明的分散体的反应器的设计,包括旋转式金属原子反应器,例如在Metal Vapour Synthesis in OrganometallicChemistry,J.R.Blackborow和D.Young,Springer-Verlag(纽约),1979中所述的;和旋转盘组件,例如在Jpn.J.Appl.Phys.,13,749(1974)中所述的。两种类型的反应器都可以用于产生有机颜料的分散体。除了电阻加热以外,其它加热颜料或颜料前体的方式也是可以预料的。这些方式包括激光加热、感应加热、等离子体流加热、等离子体弧放电加热和其它本领域技术人员所知的方式。
热塑性微孔材料可以在金属纳米粒子的沉积前或沉积后被拉伸,但优选在沉积前被拉伸。选择拉伸条件,使得膜和纳米粒子涂层的完整性得以维持。因此,当在加工方向和/或转移方向上进行拉伸时,选择温度使得基本上避免膜的撕裂、畸变和碎裂。如果温度太低或者拉伸比过高,膜可能易于撕裂或甚至灾难性的破坏。优选拉伸温度高于聚合物的玻璃化转变温度。这种温度条件使膜在不损害膜的完整性的条件下在X和Y方向上进行拉伸。
聚合物膜可沿着一个主轴(单轴的)被拉伸,还可以沿着两个主轴(双轴的)被拉伸。拉伸可以依次进行或同时进行。拉伸的程度通常由拉伸比,即最终面积与初始面积的比例,来限定。延伸可通过联合使用本发明的技术来实现,包括压延步骤和长度拉伸步骤。通常,总拉伸比为至少1.1X,优选至少5X。
当拉伸时,也可以允许芯聚合物体通过交叉拉伸方向的自然缩减(等于拉伸比的平方根)以交叉拉伸(cross-stretch)方向在尺寸上松弛,或者也可以限制芯聚合物体(即在交叉拉伸尺寸上基本无变化)。将微孔膜在加工方向,如采用长度取向器,和在宽度方向使用拉幅机,或在对角线角下拉伸。
如果需要,可以对微孔膜进行退火,优选在拉伸后在足够高的温度下进行,以减轻压力,但是不要时间过长或者在过高的温度下以致于产生膜或涂层产物的降解。合适的退火温度随着所使用的聚合物的类型不同而不同。优选在退火步骤中不对膜施加压力。通常待退火的膜被置于非粘性的支持体上,在支持体周围流通热空气,或在支持体上放置辐射加热器。
如果需要,涂覆纳米粒子的制品还可包含保护层,以将纳米粒子从环境效应和机械应力中隔离。所需的是保护层可释放地固定到微孔材料的涂覆表面上,使得其可以被除去,并且纳米粒子转移到衬底表面上。附加层可以与金属纳米粒子层和热塑性膜层的暴露的表面(即未涂覆的区域)接触。该层保护纳米粒子层免于磨损或氧化,以及赋予耐化学性。
另外,涂层微孔膜的未涂覆表面可以具有粘结、层叠、固定或另外粘附到微孔膜的未涂覆的主要表面上的支持层。可以在沉积之前将支持层共挤出到微孔层的表面上,或者可以使用合适的压敏或非压敏粘合剂将支持层涂覆、粘结或层叠到微孔层的未涂覆的表面上。支持层优选由热塑性聚合物制成,所述热塑性聚合物可以与构建热塑性聚合物膜层中使用的热塑性聚合物相同或不同。其它合适的涂层包括但不限于硬涂层、粘合剂层、抗静电层、粘合促进底漆、UV稳定涂层、减磨层等。
在将不连续的纳米粒子涂层沉积后,大部分金属纳米粒子部分固定在微孔膜的主要表面上,并且当垂直于主要表面观察时暴露出来。由于物理蒸气沉积法是“视线”法,可以在主要表面下的微孔内发现少量(小于50%)的纳米粒子,但是立即与气氛连通。不希望束缚于理论,据信金属纳米粒子通过涂覆表面的剩余稀释剂固定到微孔聚合物上。但是一些纳米粒子可以通过潜在的沉积热引起的聚合物原纤维的部分熔融而直接固定聚合物表面上。不管采取什么方式将纳米粒子固定到微孔膜上,连接要足够弱,以允许压力转移到衬底上。
本发明也提供了一种制品和一种通过下述步骤将纳米粒子涂层沉积到衬底上的方法:使涂覆纳米粒子的微孔表面与合适的衬底在足够高的压力的条件下接触,以以至少部分的转移实现转移。为了实现转移,,仅仅轻微的压力(<1磅/平方英寸)就足够了,尽管可以使用更高的压力。“部分转移”指至少10%的纳米粒子从微孔膜转移至所希望的衬底中。优选转移至少50%的纳米粒子。不希望束缚于理论,据信残余稀释剂通过提供液体载体来帮助纳米粒子的转移。当施加压力时,推动一些稀释剂(具有分散在其中的纳米粒子)从微孔膜到达衬底的表面上。
转移可通过手或手指加压来完成,但是也可以使用工具,例如滚筒、触针、印模或压机。如果需要,纳米粒子可以以预选图案转移,由此使设置为所需图案的样板、掩模或印模与涂覆纳米粒子的制品或衬底接触,并施加压力。转移可以通过瞬间施压实现,或者持续施压(如使用压机)数分钟来实现。尽管不需要加热,但是在一些应用中,可以在加压的同时加热以实现转移。
衬底可由任何合适的材料制成,并且根据具体的最终用途,可以选自各种薄膜、片材、晶片和其它表面。有用的衬底包括无机衬底,例如金属、玻璃、陶瓷、硅和ITO;和有机衬底,包括热塑性和热固性聚合物,例如聚烯烃、聚醚砜、聚碳酸酯、聚酯、聚芳酯、聚酰亚胺和聚合物多层膜;以及有机/无机复合多层膜。还可以使用挠性玻璃卷或玻璃片。对于多种光学应用而言,衬底材料需要是透明的,或也可以对可见是光不透明的,例如为不锈钢、单晶硅、多晶硅等。衬底任选地使用底漆(例如硅烷偶联剂)进行预处理,以增强纳米粒子的粘附。
抗菌制品可通过将银、氧化银(或其它含银化合物)纳米粒子转移到织造或非织造织物或聚合物织物或聚合物薄膜衬底上来制备。在一些应用中,可能需要将抗菌纳米粒子直接转移到皮肤上,例如伤口或切口位置处。
有利的是,本方法也允许在从涂覆的微孔膜中转移纳米粒子时,控制衬底上纳米粒子的涂层密度。根据需要,微孔制品可以被拉伸(通过取向)或被收缩(通过对取向的微孔制品施加热)。当制品被收缩时,粒子间的距离缩小,因此赋予转移后的衬底更大的涂层密度。相反,当涂覆的微孔膜被拉伸时,粒子间的距离增大,并赋予了降低的涂层密度。
本发明提供了一种生产光学元件的方法,该方法包括:将涂覆纳米粒子的微孔膜在一定的压力下与合适的衬底接触足够的时间,以将一部分纳米粒子从所述微孔膜转移到所述衬底。
这种光学元件优选显示表面等离子体共振(SPR),所述表面等离子体共振是在金属纳米粒子和电介质的界面处振荡自由电荷的共振激发。当产生并收集SPR谱时,这些SPR谱可用于测定涉及两种或多种分子间的相互作用的特异性、动力学、亲和势和浓度,其中一种分子贴合在固态敏感表面上。反应动力学对应于与分析物和所连接的探测分子相互作用的缔合速率和解离速率。亲和势指分析物连接到探测分子的强度。特异性指分子连接到探测分子上以排除其它分子的倾向。SPR谱已被用于包括多种类型的分子的研究中,所述多种类型的分子包括蛋白质、多肽、核酸、碳水化合物、脂类以及低分子量物质(例如激素和药物)。
尽管转移的金属纳米粒子通常是不导电的,但是本发明也可用于产生导电线路,例如在电子电路中。该方法包括将预选图案形式的纳米粒子转移至可收缩的聚合物膜的表面上。然后将具有金属纳米粒子图案化涂层的可收缩的膜加热至实现膜的收缩,使得粒子间的距离缩短,涂层变成导电的。合适的可收缩的膜和产生收缩的方式的参考资料可以在受让人的共同待决申请U.S.S.N.10/739,8071中找到。
实施例
这些例子仅仅为说明性的目的,不意味着限制所附权利要求的范围。实施例中和说明书其余部分的所有的份数、百分比、比值等除非另外注明,都基于重量。除非另作说明,使用的溶剂及其他试剂得自Aldrich Chemical Company,Milwaukee,WI。
缩写表
缩写或商品名 | 说明 |
微孔膜 | 33微米的聚丙烯微孔膜,其孔隙率为70%,如U.S.5,238,623(Mrozinski等人)中的实施例2所述制备。 |
载玻片 | 厚度为0.2毫米的载玻片,购自VWR Scientific,West Chester,PA。 |
ITO载玻片 | 涂覆ITO(铟锡氧化物)的载玻片,厚度(包括ITO涂层)为1.6毫米。 |
PTFE 5490胶带 | 购自3M Compony,St.Paul,MN。 |
聚乙烯膜 | 透明的、单轴取向的聚乙烯,厚度为25微米,购自ChanghouPlastics, Guanming, China。 |
PET膜 | 聚对苯二甲酸乙二醇酯膜,厚度为51微米,购自ChanghouPlastics, Guanming, China。 |
MMOP膜 | 微图案化单轴取向的聚乙烯膜,其通过在室温下在手压机中将膜压制到不锈钢微复制工具上而图案化(Carver Hand Press Model C由Fred Carver Inc.,Wabash,IN制备)。 |
TEMOP膜 | 热压印单轴取向的聚乙烯膜,其通过在191℃(375)下在砑光辊上进行热压印而图案化。 |
MOP膜 | 透明的单轴取向的聚乙烯膜,其厚度为25微米,购自ChanghouPlastics,Guanming,China。 |
实施例1:
将银纳米粒子电子束蒸发到微孔膜上,以产生40埃的涂层。由于多孔结构引起的光散射,因此微孔膜具有白色、不透明的外观,但是所得涂层膜具有银胶态纳米粒子的微黄色特征。使用胶纸带将涂覆银的、双轴取向的膜连接到金属板上,然后以3.0米/分钟(10英尺/分钟)的速度穿过UV辐射源(装有H灯的Fusion UV Processor型DRS-120,得自Fusion UV Systems Inc.;Gaithersburg,MD)。由于吸收能量,这种暴露引起孔倒塌,并且在暴露中膜变为半透明的橙色。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析膜。数据通过845XUV-Vis System I软件(Hewlett Packard)处理。半透明的区域表现出最大值在425nm处的吸收。
实施例2:
如实施例1中所述,制备涂覆银的微孔膜的样品。使用带有约13×13厘米(5×5英寸)压盘的手压机将银纳米粒子转移至载玻片(CarverHand Press Model C,由Fred Carver Inc.;Wabash,IN制造)上。在膜的上部使用厚度为51微米的Teflon片材,以避免载玻片的破损。接触面约3平方英寸,压机上记录的压力为15,000 psi。在转移后玻璃上出现微黄色的色彩,表明已经发生纳米粒子的转移。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析涂覆纳米粒子的载玻片。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。如图1所示等离子峰集中在约450nm处。制备一系列涂覆纳米粒子的载玻片。将这些载玻片层叠,并使用上述UV-Vis分光光度计分析。随着在叠层中载玻片数目的增多,等离子峰的强度以加合的方式增加,但是峰的位置没有发生移动。
实施例3:
使用ITO载玻片,按照实施例2中所述进行类似的转移处理。使用UV-Vis分光光度计,在波程长度范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,程长为1厘米的条件下,分析涂覆纳米粒子的载玻片。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。首先表明,等离子峰被导电表面掩盖,但是在除去ITO表面的背景后,如图2所示在452nm处观察到等离子峰。
实施例4:
使用实施例2和3中类似的方法,将银纳米粒子转移到挠性聚合物材料上。按照实施例1中所述,制备涂覆银的微孔膜的样品。将一条PTFE 5490胶带粘合剂侧朝下放置在涂覆银的微孔膜上。当剥离胶带时,一些银纳米粒子转移到胶带的粘合剂层上。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析涂覆纳米粒子的胶带表面。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。在除去PTFE表面的背景时,在452nm处观察到等离子峰。胶带样品在两个方向上变形使等离子体共振峰最大值移动到520nm处。
实施例5:
使用实施例4中类似的方法,将银纳米粒子转移到挠性聚合物材料上。按照实施例1中所述,制备涂覆银的微孔膜的样品。如实施例4中所述,将银纳米粒子转移到聚乙烯膜上。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析涂覆纳米粒子的膜表面。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。在440nm处观察到等离子峰。
实施例6:
按照实施例1中所述,制备涂覆银的微孔膜的样品。如实施例4中所述,将银纳米粒子转移到PET膜上。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析涂覆纳米粒子的膜表面。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。在450nm处观察到等离子峰。
实施例7-9:
按照实施例1中所述,制备涂覆银的微孔膜的样品。如实施例4中所述,将银纳米粒子转移到MMOP膜上(实施例7)、TEMOP膜上(实施例8)或MOP膜上(实施例9)。使用UV-Vis分光光度计,在波长范围190至820纳米处,取样间隔为2纳米,积分时间为0.5秒,波程长度为1厘米的条件下,分析涂覆纳米粒子的膜表面。数据通过845X UV-Vis System I软件(Hewlett Packard)处理。对于实施例7(MMOP膜),在445nm处观察到主等离子峰。但是在较短的波长254和295nm处,清晰地观察到其它最大值。对于实施例8(TEMOP膜),在445nm处观察到主等离子峰,在254nm处观察到较小的次级最大峰。对于实施例9(MOP膜),在437nm处观察到主等离子峰,低波长峰被掩盖为肩峰。
Claims (10)
1.一种具有金属纳米粒子涂层的微孔制品,所述微孔制品包含微孔膜和在所述微孔膜上的不连续的金属纳米粒子涂层,其中所述金属纳米粒子包含平均主要尺寸小于100nm的单独粒子或粒子聚集体。
2.权利要求1的微孔制品,其中所述微孔膜包含热塑性聚合物结构,该热塑性聚合物结构具有多个互连的通道以提供连通孔的网络。
3.权利要求1的微孔制品,其中所述纳米粒子具有大于1.5∶1的长宽比。
4.一种制备权利要求1至3中任一项的具有金属纳米粒子涂层的微孔制品的方法,包括:
a)提供微孔膜,以及
b)通过物理蒸气沉积法将不连续的金属纳米粒子涂层沉积到所述膜的表面上。
5.权利要求4的方法,其中所述纳米粒子涂层的最大平均厚度小于100nm。
6.权利要求4的方法,其中所述金属纳米粒子以预选图案被沉积。
7.一种在衬底上提供纳米粒子涂层的方法,包括:
a)提供衬底和权利要求1至3中任一项的具有金属纳米粒子涂层的微孔制品,
b)使所述衬底和所述具有金属纳米粒子涂层的微孔制品在足够的压力下接触,以将至少一部分所述纳米粒子从所述具有金属纳米粒子涂层的微孔制品转移到所述衬底的表面。
8.权利要求7的方法,其中所述纳米粒子以预选图案被转移。
9.权利要求7的方法,其中所述衬底在沉积后具有表面等离子体共振。
10.权利要求7的方法,其中所述衬底是可收缩的热塑性膜衬底,还包括收缩所述可收缩的热塑性膜衬底以提供导电纳米粒子涂层的步骤。
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-
2005
- 2005-05-04 US US11/121,479 patent/US7666494B2/en not_active Expired - Fee Related
-
2006
- 2006-04-26 WO PCT/US2006/015808 patent/WO2006118903A2/en active Application Filing
- 2006-04-26 EP EP06751487A patent/EP1885905A2/en not_active Withdrawn
- 2006-04-26 JP JP2008510053A patent/JP2008540167A/ja active Pending
- 2006-04-26 CN CN200680015413.0A patent/CN101171360B/zh not_active Expired - Fee Related
-
2010
- 2010-01-11 US US12/685,008 patent/US8834686B2/en not_active Expired - Fee Related
- 2010-01-11 US US12/685,011 patent/US8062701B2/en not_active Expired - Fee Related
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US7666494B2 (en) | 2010-02-23 |
WO2006118903A2 (en) | 2006-11-09 |
US8834686B2 (en) | 2014-09-16 |
US8062701B2 (en) | 2011-11-22 |
WO2006118903A3 (en) | 2007-01-04 |
EP1885905A2 (en) | 2008-02-13 |
CN101171360A (zh) | 2008-04-30 |
US20100108494A1 (en) | 2010-05-06 |
US20060251874A1 (en) | 2006-11-09 |
US20100112199A1 (en) | 2010-05-06 |
JP2008540167A (ja) | 2008-11-20 |
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