CN105102105A - 纳米多孔薄膜及其制造方法 - Google Patents
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Abstract
公开了一种制造纳米多孔薄膜的方法。该方法提供包括原子级薄材料层和聚合物层的复合膜,并接着以高能粒子撞击该复合膜,以形成至少穿过该原子级薄材料层的多个孔隙。纳米多孔薄膜还具有原子级薄材料层和相邻于该石墨烯层的一侧的聚合物膜层,该原子级薄材料层具有从中穿过的多个孔。聚合物膜层具有从中穿过的多个扩大的孔隙,该多个扩大的孔隙与多个孔对齐。所有扩大的孔隙可与所有孔同心对齐。在一个实施方式中,原子级薄材料层为石墨烯。
Description
相关申请的交叉引用
本申请要求于2013年3月13日提交的第61/779,098号临时申请的优先权,其内容通过引用被并入本文。
技术领域
一般而言,本发明设计纳米多孔薄膜及用于制造该薄膜的方法。更具体地,本发明涉及由原子级薄材料层和聚合物膜制成的纳米多孔薄膜,其中,纳米尺寸的孔设置在该原子级薄层中,并且同心纳米尺寸或微米尺寸的孔设置在该聚合物膜中。
背景技术
操纵用于纳米技术组件的单个原子的能力持续发展。这些发展的中的一些属于材料领域,且特别是原子级薄材料,其可使用单一分子组件或所选择的分子组件的组合。这种材料的一个示例是石墨烯,其为二维芳香族碳聚合物,二维芳香族碳聚合物具有众多的应用,范围从电子存储器、蓄电器、复合增强、薄膜等。其它的原子级薄材料被认为具有其自身的有益特性。
原子级薄材料的一个非限制性示例为石墨烯。石墨烯薄膜是单原子层厚度的碳原子层,结合在一起以限定片体。可称为层或片的单石墨烯薄膜的厚度约为0.2到0.3纳米(nm)厚,或在本文中有时称为“薄”。石墨烯层的碳原子限定由六个碳原子构成的六边形环状结构(苯环)的重复图案,其形成碳原子的蜂巢式晶格。间隙孔由片体中的每六个碳原子环状结构形成,并且该间隙孔宽度小于1纳米。事实上,本领域技术人员将理解的是,间隙孔被认为在其最长尺寸上宽约0.23纳米。因此,除非有穿孔,否则间隙孔的尺寸及配置以及石墨烯的电子性质排除了跨越石墨烯厚度的任何分子的运输。
最近的发展已聚焦在石墨烯薄膜上,该石墨烯薄膜用于用作诸如咸水脱盐的应用中的过滤薄膜。这种应用的一个示例公开于第8,361,321号美国专利中,其通过引用并入本文。由于石墨烯的这些各种使用以及其它原子级薄材料的发展,需要制造具有纳米或微米尺寸的孔或洞的材料和支撑衬底。
因为薄膜通常必须是非常薄的以允许在整个薄膜的厚度中保持这样小的孔隙尺寸,所以具有0.1到10nm孔隙尺寸的纳米多孔薄膜是难以制造的。因此,承担孔隙的薄膜必需支撑在较厚的多孔衬底上,以使最后的复合薄膜具有足够的机械强度。
制造这种复合薄膜的当前方法使用穿孔的石墨烯(厚度约1纳米)作为活性薄膜材料,并且使用多孔聚碳酸酯膜(厚度约5到10微米)作为支撑衬底。在这两层中的每一层上的孔已经被制造之后,这两层被匹配到另一个上。在两衬底中的孔没有彼此定位或对齐,因此通过复合膜的流动受到重叠的孔的统计量的限制。换言之,基于一致地对齐于多孔聚碳酸酯膜的孔的石墨烯薄膜材料中孔的随机排列,通过复合膜的流动受到限制。
匹配穿孔的原子级薄材料(例如,石墨烯)与多孔聚碳酸酯膜以产生用于纳米过滤的复合薄膜被认为提供了超越其它过滤型薄膜的改进。其它的纳米多孔薄膜由较厚的聚合物膜制成,该聚合物膜具有进行纳米尺度排除的曲折路径,但是由于其厚度,它们一般会具有极低的渗透性。因此,在本领域中需要提供具有对齐的同心孔的具有原子级薄材料层和聚合物层的纳米多孔薄膜。此外,在本领域中需要提供穿过原子级薄材料层和聚合物膜层的同心孔的纳米多孔薄膜,其中,穿过聚合物膜层的孔的直径实质上比穿过原子级薄材料层的孔的直径大。
发明内容
根据上述情况,本发明的第一方面提供纳米多孔薄膜及其制造方法。
本发明的另一方面提供用于制造纳米多孔膜的方法,其包括提供含有原子级薄材料层及聚合物膜的复合膜,以及以高能粒子撞击复合膜,以形成至少穿过原子级薄材料层的多个孔隙。
上述实施方式的另一方面提供选择高能粒子以形成穿过原子级薄材料层及聚合物膜的多个孔隙,以使得聚合物膜化学功能化。
上述实施方式的又一方面提供蚀刻聚合物膜,以在聚合物膜中形成多个扩大的孔隙。
上述实施方式的再一方面提供多个扩大的孔隙中的每个,以使得它们基本上与穿过原子级薄材料层的多个孔隙中的一个对齐。
上述实施方式的再一方面提供穿过原子级薄材料层的多个孔隙,其尺寸范围从0.5nm到约10nm,其中,多个扩大的孔隙的尺寸范围从10nm到1000nm,并且其中,多个扩大的孔隙以使得其具有大于多个孔隙的直径。方法还可包括控制撞击和蚀刻,以使得多个扩大的孔隙具有大于多个孔隙的直径。
上述实施方式的又一方面提供用于将所述原子级薄材料层设置为碳材料的单原子层,或将所述原子级薄材料层设置为碳材料的多原子层。方法还可包括从含有石墨烯、少层石墨烯、二硫化钼、氮化硼、六方晶氮化硼、二硒化铌、硅烯(silicene)和锗烯(germanene)的组中选择原子级薄材料。
方法的又一方面是利用聚碳酸酯作为聚合物膜。
方法的另一方面是提供多孔聚合物膜作为复合膜的一部分。
在该方法的另一模式中,高能粒子可被选择,以便为聚合物膜留下朝向孔隙扩大化学惰性。并且,方法可包括,在撞击期间,将原子级薄材料层化学结合至聚合物膜。或方法可撞击原子级薄材料层,以形成仅穿过原子级薄材料层的多个孔隙。
且方法可提供穿过原子级薄材料层的多个孔隙,该多个空隙的尺寸范围从约0.5nm到约10nm。
本发明的又一方面是提供一种纳米多孔薄膜,其包括原子级薄材料层,其具有从中穿过的多个孔,以及相邻于原子级薄材料层的一侧的聚合物膜层,聚合物膜层具有从中穿过的多个扩大的孔隙,其中多个扩大的孔隙与多个孔对齐。
在上述方面的一个变形中,薄膜可被建构为使得多个孔的直径范围可从0.5nm到10nm,并且其中,多个扩大的孔隙的直径范围从10nm到1000nm。
并且多个扩大的孔隙可具有大于多个孔的直径。
在上述方面的另一变形中,薄膜可被建构为使得多个扩大的孔隙可具有大于多个孔的直径。
在上述方面的又一变形中,薄膜可被建构为使得原子级薄材料层在多个孔的边缘化学结合至聚合物膜。
并且上述方面的又一变形是薄膜可被建构为使得基本上多个扩大的孔隙中的全部均与多个孔同心对齐。
上述方面的又一变形是原子级薄材料层可选自含有石墨烯、少层石墨烯、二硫化钼、氮化硼、六方晶氮化硼、二硒化铌、硅烯和锗烯的组。
附图说明
结合以下的说明、所附权利要求及附图,本发明的这些及其它特征与优点将变得更好理解。附图可以或可以不按比例绘制,并且某些零件的比例可出于说明方便而被放大。
图1是根据本发明的概念的用最初非多孔的聚合物膜来制造纳米多孔薄膜的过程的示意图;以及
图2是根据本发明的概念的用最初多孔的聚合物膜来制造纳米多孔薄膜的过程的示意图。
具体实施方式
现在参照图1,可看到形成纳米多孔薄膜的方法一般用数字10来表示。首先,提供复合膜12,其中膜12包括原子级薄材料,其以压到非多孔聚合物膜16的层14的形式存在。复合膜12可通过在热压制造操作中将原子级薄材料层14层压到聚合物膜16提供,其中膜12和层14被带到一起并升高到足够的温度,以使得至少提供膜12和层14之间的最小互连力。可使用其它方法来形成复合膜12。在以下呈现的实施方式中,原子级薄材料为石墨烯。可用于层14的其它原子级薄材料包括但不限于少层石墨烯、二硫化钼、氮化硼、六方晶氮化硼、二硒化铌、硅烯和锗烯。
在一个实施方式中,且如上所述,石墨烯层为单原子层厚度的碳原子层,结合在一起以限定片体。可称为层或片的单石墨烯薄膜的厚度约为0.2到0.3纳米(nm)。在一些实施方式中,可形成具有较大厚度和相应的较大强度的多石墨烯层。当薄膜生长或形成时,多石墨烯片体可设置为多层。或者,多石墨烯片体可通过将一层石墨烯层层叠或设置于另一石墨烯层的顶部实现。对本文中公开的所有实施方式,可使用单个石墨烯层或多石墨烯层(有时称为少层石墨烯)。测试显示多层石墨烯由于其自身的粘附性而维持它们的完整性及功能性。这改善了薄膜的强度和在某些情况下的流动性能。一旦穿孔,在将讨论的方法中,相对于聚亚酰胺或其它聚合物材料的过滤材料,石墨烯层提供显著改善过滤性能的高通量吞吐量材料。在多数实施方式中,石墨烯薄膜为0.5到2纳米厚。但可使用高达10纳米或更多的厚度。在任何情况下,除非存在穿孔,否则间隙孔的尺寸和配置和石墨烯的电子性质排除了跨越石墨烯的厚度的任何分子的运输。间隙孔尺寸非常小以至于不允许水或离子通过。
多数实施方式中的非多孔聚合物膜16为厚度范围从10微米到数千微米不限的聚碳酸酯膜。在多数实施方式中,聚合物膜16的厚度范围从25微米到250微米。诸如聚酯、聚亚酰胺、聚丙烯、聚偏二氟乙烯、或聚甲基丙烯酸甲酯等的其它材料可用于膜。
方法10中的下一个步骤是产生高能粒子18。该粒子可以以具有足够高能量以穿过聚合物复合膜的电子、离子、中子、离子簇等的形式存在,这些粒子的能量通常为>1MeV/具有介于106离子/cm2和1013离子/cm2之间通量的微米厚度,且这些粒子在一般由数字20表示的撞击操作中被导向朝向复合膜12。在一个实施方式中,高能粒子被导向朝向可为石墨烯或上述其它原子级薄材料的层14。然而,在其它实施方式中认为,高能粒子18可通过撞击导向朝向复合膜12的聚合物膜16侧。本领域技术人员将理解的是,术语撞击也可称为辐射。在任何情况下,粒子18穿过膜在聚合物膜材料的次纳米到纳米尺度上留下化学官能性“轨迹”。事实上,高能粒子18的撞击形成穿过膜12的轨迹孔隙22。轨迹孔隙22是统一尺寸的且范围可从直径0.5nm到直径10nm不限。孔隙的直径尺寸由撞击步骤20以及高能粒子18的特定类型的选择来确定。本领域技术人员将理解的是,在高能粒子和撞击步骤的选择上,可使用各种因素,以便直接影响直径尺寸。这些因素包括但不限于高能粒子撞击复合膜的停留时间、对高能粒子选择到粒子或材料的类型、以及诸如粒子通量的其它因素。需注意的是,选择用在撞击步骤中的高能粒子18沿聚合物膜16中的轨迹孔隙22的整个表面形成化学功能化24。本领域技术人员将理解的是,孔隙22的化学功能化24改变聚合物膜材料的化学性质。延伸穿过层14的孔隙的一部分可通过辐射被功能化,但官能性对于将描述的进一步的化学过程将是惰性的。
当撞击步骤20完成时,复合膜12经历刻蚀过程26。在此过程26中,整个膜12被浸入适当的流体或气体中。在聚碳酸酯的情况下,使用氢氧化钠溶液并持续预定的时间周期。依据被使用为聚合物膜16的聚合物,可使用其它类型的刻蚀流体或气体。刻蚀过程中的流体或气体侵蚀孔隙22中的聚合物材料的化学功能化24,以便有效地移除化学功能化区域并扩大或增加轨迹孔隙22的直径,以形成穿过聚合物膜16的扩大的孔隙28。本领域技术人员将理解的是,刻蚀步骤并未以任何显著方式改变关联于或延伸穿过层14的孔隙22。
在一个实施方式中,本领域技术人员将注意到的是,在石墨烯膜或层14中的任何缺陷可通过添加附加石墨烯层来缓解。因此,石墨烯层中的重叠缺陷的机率随各附加层显著降低。由于其原子尺度的厚度,附加石墨烯层应不改变高能粒子18通过复合膜12的穿透。在任何情况下,多个扩大的孔隙28设置在聚合物膜层16中。依据化学功能化24的数量和刻蚀过程26的参数,可控制孔隙的尺寸和直径。
在本实施方式中,孔隙28的直径范围可从10nm到1000nm,且为由这些参数确定的一致统一尺寸。作为刻蚀过程的结果,残余聚合物结构30设置用于支撑层14的相邻侧。在本实施方式中,刻蚀过程的最终结果提供具有多个石墨烯孔或孔隙32的层14,多个石墨烯孔或孔隙32可具有0.5到10nm的直径。此外,石墨烯孔32与扩大的孔隙28同心地对齐。因此,复合膜12设置有最大数量的同心对齐的石墨烯孔隙和聚合物膜孔隙,以便在活性薄膜(石墨烯)和衬底(聚合物)两者中提供一对一的孔映射。也可以说,通过刻蚀过程形成的石墨烯孔隙及聚合物膜孔隙彼此一致,其中石墨烯孔隙及聚合物膜孔隙彼此相邻。将上述公开的其它薄材料与聚合物膜和撞击过程一起使用将提供类似的纳米多孔薄膜。
现在参照图2,用于形成纳米多孔薄膜的替代方法一般由数字50来表示。该实施方式类似于图1中所示的方法,除了多孔薄膜首先被以在第一实施方式中所使用的方法层压到石墨烯薄膜上。具体地,方法50使用复合膜52,复合膜52使用与石墨烯层14基本相同的石墨烯层54。此外,石墨烯层14的所有特征均由石墨烯层54来提供。在该特定实施方式中,多孔聚合物层56可以由聚碳酸酯、聚酯、聚亚酰胺、聚丙烯、聚偏二氟乙烯、聚甲基丙烯酸甲酯,或者其它类似的材料来构成。聚合物层56设置有一般以标号58表示的扩大的孔隙。
在本实施方式中,复合膜52在过程59中被高能粒子60撞击。所选择的高能粒子类似于先前实施方式中的高能粒子;然而,选择它们以使得形成在聚合物层56中的任何孔隙不会通过撞击过程59产生化学功能化。
在本实施方式中,多孔聚合物层56设置有扩大的孔隙58,其具有10到1000nm的直径。本领域技术人员将理解的是,扩大的孔隙58的直径甚至可大于1000nm。在任何情况下,高能粒子60的撞击被导向朝向石墨烯层54,但应理解的是,撞击可通过在多孔聚合物层56中投射粒子60而发生。在本实施方式中,可选择高能粒子以使得留下聚合物层或膜朝向孔隙扩大的化学惰性。
作为撞击过程59的结果,延伸穿过石墨烯层54的多个孔隙62被产生。孔隙62与扩大的孔隙58对齐,并且可以与其同心或可以不与其同心。撞击还导致孔隙66的形成,孔隙66延伸穿过石墨烯并且仅部分地进入聚合物膜56,以形成腔室67。并且,在一些情况下,粒子60产生完全延伸穿过石墨烯层54和聚合物层56两者的孔隙68。还将理解的是,在石墨烯层14和聚合物层56之间可形成化学结合70,以进一步将聚合物层56固定到石墨烯层54。因此,公开的实施方式提供具有直径范围从0.5nm到10nm的孔隙62的对齐,其中底层的孔隙58具有可与之同心的扩大的直径。此外,在本实施方式中,多于一个孔或孔隙可在石墨烯层54中产生,聚碳酸酯或聚合物膜层56中的每个孔隙导致更高的渗透性。作为撞击过程的结果,应被理解的是,多个孔隙58与多个孔隙62对齐。因此,孔隙58和孔隙62将彼此相邻,以允许流体从中流过。换言之,对齐的孔隙58和孔隙62可不必具有相同的相对中心点。然而,在撞击过程后,显著数量的孔隙58和孔隙62将被同心地彼此对齐。其它实施方式可使用上述公开的其它薄材料和其它聚合物材料。
基于前述,本发明的优点已经显而易见。通过在能量粒子撞击前以未穿孔的薄材料层覆盖非多孔聚合物膜,任何后来形成的薄材料穿孔都与聚合物膜中的轨迹一致。如在第一实施方式中所公开的,轨迹的后续刻蚀留下在直径方面未受影响的石墨烯孔隙,但在聚合物膜中产生与石墨烯孔隙同心的更大的孔隙,以允许更高的复合膜整体渗透性。因此,在石墨烯薄膜和聚合物膜两者中的一对一孔映射允许在石墨烯和支撑薄膜中同时形成孔。公开的制造纳米多孔薄膜的方法在薄膜性能和制造性两方面是有利的。通过在石墨烯穿孔和支撑膜中的孔隙之间具有精确的重合,复合薄膜的渗透性比具有随机孔对准的复合膜高很多。此外,从制造的角度来看,同时处理活性层和支撑膜可能是更为容易的且更具可扩展性。在穿孔前结合额外的石墨烯层来排除缺陷也允许有意的穿孔持续通过所有的石墨烯层。若石墨烯层被个别穿孔,重叠穿孔仅会随机发生,从而降低薄膜渗透性。
在提供粒子撞击前的多孔聚合物膜的使用的实施方式中,可通过粒子的选择实现优点,该粒子可与在聚碳酸酯膜中产生轨迹所需的类型不同。换言之,多孔聚合物膜的使用可允许制造过程中形成复合膜中的弹性。此外,多孔聚合物膜的使用可允许在复合膜的使用中的优势。这样的构造可允许复合膜的额外弹性。还将理解的是,所公开的实施方式可同时形成孔隙并将石墨烯膜化学结合到支撑膜,以便进一步地强化复合材料。
因此,可以看出,本发明的目的已通过使用上文呈现的结构和其方法而被满足。虽然根据专利法规,仅已呈现并详细描述了最佳模式和优选的实施方式,但是应当理解的是,本发明不局限于此。因此,为了理解本发明的真正范围和广度,应参照以下权利要求。
Claims (22)
1.一种制造纳米多孔薄膜的方法,包括:
提供包括原子级薄材料层和聚合物膜的复合膜,以及
以高能粒子撞击所述复合膜,以形成至少穿过所述原子级薄材料层的多个孔隙。
2.根据权利要求1所述的方法,还包括:
选择高能粒子以形成穿过所述原子级薄材料层及所述聚合物膜的所述多个孔隙,使得所述聚合物膜化学功能化。
3.根据权利要求2所述的方法,还包括:蚀刻所述聚合物膜,以在所述聚合物膜中形成多个扩大的孔隙。
4.根据权利要求3所述的方法,其中,所述多个扩大的孔隙中的每个与穿过所述原子级薄材料层的所述多个孔隙中的一个基本对齐。
5.根据权利要求4所述的方法,其中,穿过所述原子级薄材料层的所述多个孔隙的尺寸范围从0.5nm到约10nm,其中,所述多个扩大的孔隙的尺寸范围从10nm到1000nm,并且其中,所述多个扩大的孔隙具有大于所述多个孔隙的直径。
6.根据权利要求4所述的方法,还包括:
控制所述撞击和蚀刻,以使得所述多个扩大的孔隙具有大于所述多个孔隙的直径。
7.根据权利要求1所述的方法,还包括:
将所述原子级薄材料层设置为碳材料的单原子层。
8.根据权利要求1所述的方法,还包括:
将所述原子级薄材料层设置为碳材料的多原子层。
9.根据权利要求1所述的方法,还包括:
使用聚碳酸酯作为所述聚合物膜。
10.根据权利要求1所述的方法,还包括:
提供多孔聚合物膜作为所述复合膜的一部分。
11.根据权利要求10所述的方法,还包括:
选择高能粒子,所述高能粒子使所述聚合物膜朝向孔隙扩大在化学上呈惰性。
12.根据权利要求11所述的方法,还包括:
在撞击期间,将所述原子级薄材料层化学结合至所述聚合物膜。
13.根据权利要求11所述的方法,还包括:
撞击所述原子级薄材料层,以形成仅穿过所述原子级薄材料层的所述多个孔隙。
14.根据权利要求13所述的方法,其中,穿过所述原子级薄材料层的所述多个孔隙的尺寸范围从约0.5nm到约10nm。
15.根据权利要求1所述的方法,还包括:
从含有石墨烯、少层石墨烯、二硫化钼、氮化硼、六方晶氮化硼、二硒化铌、硅烯和锗烯的组中选择所述原子级薄材料。
16.一种纳米多孔薄膜,包括:
原子级薄材料层,具有从中穿过的多个孔;以及
聚合物膜层,相邻于所述原子级薄材料层的一侧,所述聚合物膜层具有从中穿过的多个扩大的孔隙,其中所述多个扩大的孔隙与所述多个孔对齐。
17.根据权利要求16所述的薄膜,其中,所述多个孔的直径范围能够从0.5nm到10nm,并且其中,所述多个扩大的孔隙的直径范围从10nm到1000nm。
18.根据权利要求16所述的薄膜,其中,所述多个扩大的孔隙具有大于所述多个孔的直径。
19.根据权利要求16所述的薄膜,其中,所述多个扩大的孔隙具有大于所述多个孔的直径。
20.根据权利要求16所述的薄膜,其中,所述原子级薄材料层在所述多个孔的边缘化学结合至所述聚合物膜。
21.根据权利要求16所述的薄膜,其中,基本上所述多个扩大的孔隙中的全部均与所述多个孔同心对齐。
22.根据权利要求16所述的薄膜,其中,所述原子级薄材料层选自含有石墨烯、少层石墨烯、二硫化钼、氮化硼、六方晶氮化硼、二硒化铌、硅烯和锗烯的组。
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EP (1) | EP2969153A1 (zh) |
CN (1) | CN105102105A (zh) |
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WO (1) | WO2014159043A1 (zh) |
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US20140272286A1 (en) | 2014-09-18 |
TW201505957A (zh) | 2015-02-16 |
WO2014159043A1 (en) | 2014-10-02 |
EP2969153A1 (en) | 2016-01-20 |
US20170043300A1 (en) | 2017-02-16 |
US9505192B2 (en) | 2016-11-29 |
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