CN115151417A - 功能化纺织品组合物和制品 - Google Patents
功能化纺织品组合物和制品 Download PDFInfo
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- CN115151417A CN115151417A CN202080096048.0A CN202080096048A CN115151417A CN 115151417 A CN115151417 A CN 115151417A CN 202080096048 A CN202080096048 A CN 202080096048A CN 115151417 A CN115151417 A CN 115151417A
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- ceramic material
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- hydroxides
- ceramic
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- 239000000203 mixture Substances 0.000 title claims description 110
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- 239000000758 substrate Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
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- 150000004679 hydroxides Chemical class 0.000 claims description 28
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
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Abstract
提供了功能化纺织品材料。纺织品表面的至少一部分包括陶瓷材料,诸如无粘合剂多孔结构化陶瓷,并且任选地,施加了一个或多个功能层,得到具有一种或多种期望的功能特性的纺织品材料,所述功能特性诸如亲水性、疏水性、阻燃性、光催化性、防污性和/或除臭性。
Description
相关申请的交叉引用
本申请要求2019年12月12日提交的PCT申请号PCT/US2019/065978的优先权,并且要求2020年3月13日提交的美国临时申请号62/989,092、2020年3月13日提交的美国临时申请号62/989,150、2020年6月12日提交的美国临时申请号63/038,642、2020年6月12日提交的美国临时申请号63/038,693以及2020年6月16日提交的美国临时申请号63/039,965的权益,所有这些申请以引用的方式整体并入本文。
技术领域
本发明涉及纺织品,其包括在纺织品表面上的陶瓷材料,特别是无粘合剂陶瓷,诸如金属氧化物和/或金属氢氧化物陶瓷。纺织品经过改性以包括一种或多种在使用应用或环境中提供增强的特性的功能。
背景技术
对纺织品表面的功能化在纺织品性能方面提供了所需益处。为了制造耐多种环境条件并且提供显著的性能增强的纺织品材料,必须开发新的纺织品组合物。期望的性能特征可以通过对纺织品表面的功能化来提供。
发明内容
本文提供了组合物,其包括在多孔基材上的功能化陶瓷材料。
在一个方面,提供了组合物,其包括在多孔基材上的无粘合剂陶瓷材料,诸如纺织品或过滤材料。在一个实施方案中,基材包括平均孔直径小于约250μm的孔,并且基材上的陶瓷材料不实质地改变基材的平均孔直径。在另一个实施方案中,基材包括平均孔直径小于约250μm的孔,并且基材上的陶瓷材料部分地或完全地填充基材的孔,从而分别减小平均孔直径或消除基材的孔。在一些实施方案中,在将陶瓷材料沉积在基材上之前,根据ASTMD737,基材具有约0.1立方英尺每分钟(CFM)至约100CFM的空气渗透率。
在一些实施方案中,陶瓷材料主要是结晶的。在一些实施方案中,陶瓷材料包括金属氧化物、金属氧化物的水合物、金属氢氧化物和/或金属氢氧化物的水合物。在一些实施方案中,陶瓷材料包括金属氢氧化物,并且金属氢氧化物的至少一部分包括层状双氢氧化物。在一些实施方案中,陶瓷材料是结构化陶瓷材料,诸如纳米结构化陶瓷材料。
在一些实施方案中,陶瓷材料包含过渡金属、II族元素、稀土元素、铝、锡或铅。例如,陶瓷材料可以包含锌、铝、锰、镁、铈、铜、钆、钨、锡、锌、铅和钴中的一种或多种。在某些实施方案中,陶瓷材料包括:锌和铝氧化物和/或氢氧化物的混合物;锰和镁氧化物和/或氢氧化物的混合物;锰氧化物和/或氢氧化物;铝氧化物和/或氢氧化物;混合金属锰氧化物和/或氢氧化物;镁和铝氧化物和/或氢氧化物的混合物;镁氧化物和/或氢氧化物;镁、铈和铝氧化物和/或氢氧化物的混合物;锌、镨和铝氧化物和/或氢氧化物的混合物;钴和铝氧化物和/或氢氧化物的混合物;锰和铝氧化物和/或氢氧化物的混合物;铈和铝氧化物和/或氢氧化物的混合物;铜和铝氧化物和/或氢氧化物的混合物;锌和铝氧化物和/或氢氧化物的混合物;Zn-铝酸盐的混合物;包含一种或多种包含Zn、Al和氧的相的混合物;锌氧化物和/或氢氧化物;或上述化合物或其混合物中任一种的水合物。
在一些实施方案中,陶瓷材料包括高达约25μm的厚度,诸如约0.2μm至约25μm的厚度。
在一些实施方案中,陶瓷材料包括约5%至约80%,诸如大于约10%,或约30%至约95%的孔隙率。
在一些实施方案中,多孔基材包括织造材料、针织材料、非织造织物或纺织品或纸或者由其组成。多孔基材可包括例如聚酰胺、聚酯、棉、羊毛、聚乙烯、聚丙烯、纤维素材料、芳族聚酰胺、聚氨酯、活性炭、玻璃纤维、钢合金、黄铜合金、铝合金、铝或铜或者由其组成。在各种实施方案中,多孔基材可以是纺织品材料,其包括天然纤维、合成纤维、金属网、或金属布或其组合或者由其组成。在一些实施方案中,例如,在将陶瓷材料沉积在基材上之前,纺织品表面已被氧化、灰化或活化。在一个实施方案中,基材是金属化纺织品,其在纺织品表面上包括一种或多种金属,诸如但不限于铝、铁、镍、钛、不锈钢合金或铜。
在一些实施方案中,陶瓷材料和/或任选的顶涂层(功能层)材料赋予组合物一种或多种功能特性,诸如但不限于亲水性、疏水性、阻燃性、光催化性、防污性、除臭性、微生物生长抑制、冰或冷凝物管理、防冰、防霜、超疏水性、超亲水性、耐腐蚀性、电磁调制、热调制、透气性、动态抗风和/或颜色。在某些实施方案中,将两种或更多种此类功能特性赋予至组合物的单层(例如,纺织品、织物或过滤材料的单层)。
在一些实施方案中,陶瓷材料由功能层进一步改性。在一些实施方案中,功能层(例如,顶涂层)材料赋予一种或多种功能特性,其量值比由直接沉积在不包括陶瓷材料的相同纺织品表面上的相同顶涂层材料赋予的相同功能特性大。例如,陶瓷材料和功能层材料可以协同地赋予一种或多种功能特性,其量值比由独立地沉积在相同纺织品表面上的陶瓷材料或功能层材料赋予的相同功能特性大。
在一些实施方案中,功能层赋予疏水性。例如,赋予组合物疏水性的功能层可以包括含氟聚合物、弹性体、塑料或具有头基和尾基的分子,例如,其中头基包括硅烷基、膦酸酯基、膦酸基、羧酸基、乙烯基、醇基、氢氧基(hydroxide group)、硫醇盐基(thiolate group)和/或硫醇基,并且其中尾基包括烃基、碳氟基、乙烯基、苯基、环氧基、丙烯酸基、丙烯酸酯基、羟基、羧酸基、硫醇基和/或季铵基。
在一些实施方案中,基材上的陶瓷材料是部分填充的多孔结构。例如,孔可以部分地填充有第二陶瓷材料或具有头基和尾基的分子。
在一些实施方案中,组合物表现出对小分子的粘附性高于对生物分子或来自皮脂的组分(诸如但不限于甘油三酯、蜡酯、角鲨烯和/或游离脂肪酸)的粘附性。
在一些实施方案中,组合物具有光催化性,并且粘附至表面的材料在暴露于光时被光催化降解。
在一些实施方案中,与不包括陶瓷材料的相同基材相比,组合物表现出对耐久型防泼水物质的粘附性更高。
在另一方面,提供了制品,其包括本文所述的任何组合物(包括在多孔基材上的官能化陶瓷材料的组合物)。在某些非限制性实施方案中,制品包括过滤器、膜、衣服、外套、野营装备、管道绝热物、地毯、汽车座椅、家具装饰材料(upholstery)、床上用品、建筑表面(例如,墙包板(sheathing)、地面包板或壁板)和窗饰(window covering)。
在一些实施方案中,如本文所述的组合物或制品能够承受大于约1kPa的静水压力。
在一些实施方案中,如本文所述的组合物或制品包括大于未用陶瓷材料(和在一些实施方案中任选的功能层)改性的相同基材的蒸气透过率的约80%的湿气透过率。
在一些实施方案中,如本文所述的组合物或制品包括大于约150度的座滴法水接触角(sessile drop water contact angle)。
在一些实施方案中,如本文所述的组合物或制品包括锰氧化物陶瓷和烷基硅烷或烷基膦酸酯功能层。
具体实施方式
本文提供了组合物,其包括在多孔基材(诸如纺织品)上的陶瓷材料(诸如无粘合剂陶瓷材料)。在一些实施方案中,基材包括平均孔直径小于约250μm的孔,并且陶瓷不实质地改变基材的平均孔直径。在其他实施方案中,基材包括平均孔直径小于约250μm的孔,并且陶瓷部分地或完全地填充孔,从而分别减小平均孔直径或消除基材的孔。
提供了技术纺织品,其包括由纺织品表面上的如本文所述的组合物赋予的期望的功能特性,诸如但不限于亲水性、疏水性、阻燃性、光催化性、防污性、除臭性、微生物生长抑制、冰或冷凝物管理、防冰、防霜、超疏水性、超亲水性、耐腐蚀性、电磁调制、热调制、透气性、动态抗风和/或颜色。在一些实施方案中,纺织品的单层包括两种或更多种由纺织品表面上的如本文所述的组合物(陶瓷材料)赋予的此类功能特性。
陶瓷(例如多孔陶瓷(例如,金属氧化物和/或金属氢氧化物))表面改性组合物沉积在纺织品表面上。在一些实施方案中,陶瓷(例如结构化陶瓷)沉积至基材表面上,并且提供一种或多种功能特性的功能层(例如顶涂层)沉积或施加在陶瓷材料上。
组合物作为在基材(诸如纺织品)表面上的无粘合剂表面改性材料(例如表面固定陶瓷材料)提供。在一些实施方案中,陶瓷材料包括金属氧化物和/或氢氧化物陶瓷,例如,单一金属或混合金属氧化物和/或氢氧化物陶瓷。在一些实施方案中,陶瓷材料包括金属氢氧化物和/或氢氧化物陶瓷,例如,单一金属或混合金属氧化物和/或氢氧化物陶瓷。在一些实施方案中,陶瓷材料包括金属氧化物和金属氢氧化物陶瓷,其中金属氧化物和金属氢氧化物包含相同或不同的单一金属或混合金属。在一些实施方案中,陶瓷材料包括金属氧化物和/或金属氢氧化物陶瓷,其中基材被水或其他化合物水合,导致表面能发生变化且可能导致陶瓷的金属氧化物与金属氢氧化物组成的比率发生变化。在一些实施方案中,陶瓷材料包括金属氢氧化物,其中至少一部分的金属氢氧化物呈层状双氢氧化物的形式,例如,至少约5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%的金属氢氧化物是层状双氢氧化物。
在本文所述的组合物的一些实施方案中,“金属氧化物”或“金属氢氧化物”可以分别呈金属氧化物或金属氢氧化物的水合物的形式,或者一部分的金属氧化物或金属氢氧化物可以分别呈金属氧化物或金属氢氧化物的水合物的形式。
混合金属氧化物或混合金属氢氧化物可分别包括例如多于一种金属的氧化物或氢氧化物,金属诸如但不限于铁、钴、镍、铜、锰、铬、钛、钒、锆、钼、钽、锌、铅、锡、钨、铈、镨、钐、钆、镧、镁、铝或钙。
本文所述的表面改性材料(例如,无粘合剂多孔陶瓷材料)在没有粘合剂的情况下沉积至基材上(例如,通过与基材表面上的金属反应所产生)。在一些实施方案中,如本文所述的表面改性材料被固定在基材上。
在一些实施方案中,陶瓷材料是结构化(诸如纳米结构化)陶瓷材料。
PCT申请号PCT/US19/65978中提供了无粘合剂陶瓷表面改性材料的非限制性实例,其以引用的方式整体并入本文。
定义
本文提供的数值范围包括限定范围的数值。
除非上下文另外明确指出,否则“一个”、“一种”和“所述”包括复数指称。
如本文在说明书和权利要求书中所使用,短语“和/或”应当理解为意指所结合的元素中的“任一者或两者”,即,在一些情况下结合存在并且在其他情况下分开存在的元素。除非有明确相反的说明,否则无论与明确标识的那些元素相关还是无关,除由“和/或”分句明确标识的元素以外的其他元素可任选地存在。因此,作为非限制性实例,当与诸如“包含”的开放式语言结合使用时,对“A和/或B”的提及在一个实施方案中可以指代在没有B的情况下的A(任选地包括除B以外的元素);在另一个实施方案中可以指代在没有A的情况下的B(任选地包括除A以外的元素);在又一实施方案中可以指代A和B两者(任选地包括其他元素);等。
“粘合剂(binder)”或粘合剂(binding agent)是以机械方式、以化学方式、通过粘附力或通过内聚力将其他材料保持或拉在一起以形成内聚的整体的任何材料或物质。
“无粘合剂”是指不存在被明确地添加以维持所考虑的材料的结构完整性的粘合剂,特别是关于有机粘合剂或树脂(例如,聚合物、胶水、粘附剂、沥青)或无机粘合剂(例如,石灰、水泥、玻璃、石膏等)。
“封端剂”是指减缓晶体生长并允许对纳米表面形貌的调节的化合物或剂。
“陶瓷”是指包含金属、非金属或离子键和共价键的无机化合物的固体材料。
“织物”是指可以由纤维构造并通过化学、机械、热和/或溶剂处理来粘合在一起的非织造材料。织物可以包括例如毡以及既不是织造也不是针织的其他材料。
“纤维”是指可以形成纺织品的线或丝。
“亲水”是指对水具有高亲和力的表面。接触角可能非常低和/或不可测量。
“层状双氢氧化物”是指一类离子固体,其特征在于具有通用序列[AcB Z AcB]n的层状结构,其中c代表金属阳离子层,A和B是氢氧根阴离子层,并且Z是其他阴离子和/或中性分子(诸如水)层。层状双氢氧化物还描述于PCT申请号PCT/US2017/052120中,其以引用的方式并入本文。
“纳米结构化”组合物在本文中是指具有在至少一个维度上小于100纳米的特征部的组合物。
流体力学中的“渗透率”是多孔材料允许流体通过它的能力的量度。介质的渗透率与孔隙率有关,还与介质中孔的形状及其连通性水平有关。
“孔径分布”是指如通过压汞法(mercury intrusion porosimetry,MIP)和Washburn方程所确定的每个孔直径或孔直径范围的相对丰度。
“孔隙率”是材料中空隙(即“空的”)空间的量度,并且是空隙体积占总体积的分数,介于0与1之间,或为介于0%与100%之间的百分比。孔隙率可以通过压汞法测量。
“多孔”是指固体材料内的空间、孔洞或空隙。
“超疏水”是指极难用水润湿的表面。水滴在超疏水材料(此处是超疏水表面)上的接触角是指>150°的接触角。高度疏水的接触角>120°。
“每平方米投影基材面积的表面积”是指实际测量的表面积(通常以平方米测量)除以基材的表面积(如果它是原子级光滑的(无表面粗糙度),也通常以平方米测量)。
“协同”或“协同的”是指两种或更多种物质、材料或剂之间的与它们分开的、单独的效应的总和相比产生更大(正协同)或更小(负协同)的联合效应的相互作用或协作。
“纺织品”是指由天然或人造纤维网格组成的柔性材料。例如,纺织品材料可以通过针织、编织、毡制、簇绒或粘合以连接纤维或纤维组来产生,其中纤维包括所有长度的天然和合成形式,包括金属纤维。纺织品还包括粗绳(rope)和细绳(cord)。
“厚度”是指基材表面与表面改性(例如陶瓷)材料顶部之间的长度。
“可调”是指材料的功能、特征或品质被改变或修改的能力。
“蒸气透过率”是指每单位面积每单位时间在与层的平面正交的方向上穿过层的蒸气质量。
“水柱突破压力(water column breakthrough pressure)”是指水柱底部的层承受的静水压力克服层支持水柱的能力,使得水流过层时的垂直水柱的具体高度。
基材
多孔材料(诸如纺织品材料或织物)充当用于沉积如本文所述的陶瓷材料的基材。例如,基材可以由织造材料、针织材料、非织造织物或纺织品或纸构成。基材可以包括天然纤维、合成纤维、金属网、或金属布或其组合。在某些非限制性实施方案中,基材包括聚合物(例如,聚酰胺(例如,尼龙)、聚酯、聚乙烯、聚丙烯、聚氨酯)、纤维素材料(例如,人造丝)、棉、羊毛、芳族聚酰胺、活性炭、玻璃纤维、合金(例如,钢、黄铜或铝合金)或金属(例如,铝、铜)或者由其组成。
在一些实施方案中,纺织品基材是金属化纺织品。金属化纺织品在纺织品表面上包括一种或多种金属,诸如但不限于铝、铁、镍、钛、或铜或其组合。在一个实施方案中,金属化纺织品用铝金属化。纺织品表面上的金属的厚度可为约25nm至约2000nm、约25nm至约100nm、约50nm至约250nm、约100nm至约500nm、约500nm至约1000nm、约1000nm至约2000nm、约750nm至约1500nm、约100nm至约2000nm或约500nm至约2000nm。
在一些实施方案中,在沉积互连的陶瓷材料之前,基材被氧化、活化或灰化。在一些实施方案中,此氧化步骤通过将基材浸没在氧化剂中进行。在一些实施方案中,氧化剂包括过硫酸盐、高锰酸盐、硝酸盐或过氧化物。在一些实施方案中,氧化剂浴被加热。在一些实施方案中,使用过硫酸钾、高锰酸钾或过氧化氢氧化表面。在一些实施方案中,使用UV/臭氧或等离子体将基材氧化、活化或灰化。在一些实施方案中,使用氧等离子体将表面氧化和/或活化。
在一些实施方案中,根据ASTM D737,基材的空气渗透率是约0.1立方英尺每分钟(CFM)至约100CFM。在其他实施方案中,空气渗透率是约0.5CFM、约1CFM、约2CFM、约5CFM、约10CFM、约20CFM、约30CFM、约40CFM、约50CFM、约60CFM、约70CFM、约80CFM、约90CFM或约100CFM。在其他实施方案中,空气渗透率是约1CFM至约5CFM、或约1CFM至约20CFM、约0.1CFM至约0.5CFM、约20CFM至约50CFM、或约50CFM至约100CFM。在一些实施方案中,陶瓷材料或功能化材料使空气渗透率改变不多于约20%。
功能化
如本文所述的多孔基材是包括一种或多种期望的功能特性的功能化产品组合物(例如,技术纺织品或过滤材料)。此类功能特性可以包括但不限于疏水性、微生物生长抑制或耐微生物生长、阻燃性、亲水性、耐腐蚀性(resistance to corrosion)、冰或冷凝物管理、防冰、防霜、超疏水性、超亲水性、耐腐蚀性、电磁调制、热调制、透气性、动态抗风和/或颜色或其组合。
在一些实施方案中,如本文所述的功能化基材(例如,纺织品)不包括碳氟化合物化学品。在一些实施方案中,如本文所述生产的功能化基材(例如,纺织品)包括在基材的单层中的多种期望的特性(功能)。在一些实施方案中,如本文所述生产的功能化基材(例如,纺织品)包括在包括天然或合成纤维的纺织品基材上的功能化结构化陶瓷。
在一些实施方案中,沉积在基材上的陶瓷可以被设计为具有所需的孔隙率或开口分数,其可用于赋予功能特征,以及为结构化陶瓷材料的沉积提供结合表面。
在一些实施方案中,将一个或多个功能层(诸如顶涂层材料)施加至结构化陶瓷材料,以赋予纺织品材料所需的功能特性。一种或多种功能特性可以由结构化陶瓷和/或施加的顶涂层材料赋予。通过本文所述的方法赋予至纺织品的功能的非限制性实例包括疏水性、微生物生长抑制、阻燃性、亲水性、耐腐蚀性、冰或冷凝物管理、防冰、防霜、超疏水性、超亲水性、微生物生长抑制、耐腐蚀性、电磁调制、热调制、透气性、动态抗风、抗臭性或臭味消除(例如,除臭性)和/或颜色及其组合。在一些实施方案中,将多种功能赋予至纺织品材料的单层(即,多功能单层纺织品)。
在一些实施方案中,由如本文所述施加或沉积在陶瓷上的顶涂层材料赋予的功能相对于施加或沉积在包括陶瓷的相同基材上的相同材料的功能增强。在一些实施方案中,陶瓷材料和顶涂层材料协同地赋予一种或多种功能特性,其量值比由独立地沉积在相同基材表面上的陶瓷材料或顶涂层材料赋予的相同功能特性大。
在一些实施方案中,疏水功能由脂肪酸或ScotchgardTM(3M)提供。在一些实施方案中,抗微生物功能由SmartShield Antimicrobial Protective Spray(Sylvane)提供。在一些实施方案中,阻燃功能由No Burn 1005Fabric Fire Protection(No-Burn,Inc.)或含哈龙(halon)化合物提供。在一些实施方案中,亲水功能由聚乙烯吡咯烷酮(PVP)、聚氨酯、聚丙烯酸(PAA)、聚环氧乙烷(PEO)或多糖材料提供。
在某些非限制性实施方案中,顶涂层可包括油漆、油漆粘合剂、疏水性材料、亲水性材料、金属或含金属化合物或抗微生物剂。
在一些实施方案中,陶瓷表面改性材料是部分填充的多孔结构。例如,孔可以部分地填充有第二陶瓷材料(例如,不同于无粘合剂多孔陶瓷材料的陶瓷材料)或具有头基和尾基的分子,例如,其中头基包括硅烷基、膦酸酯基、膦酸基、羧酸基、乙烯基、醇基、氢氧基、硫醇盐基、硫醇基和/或铵基(例如,季铵基),并且其中尾基包括烃基、碳氟基、乙烯基、苯基、环氧基、丙烯酸基、丙烯酸酯基、羟基、羧酸基、硫醇基和/或季铵基。
在一些实施方案中,顶涂层是表面改性顶涂层,其降低表面上的外部或内部流体的粘滞阻力。在一些实施方案中,涂层沉积到表面上,所述涂层包括纳米结构化涂层组合物和表面改性顶涂层,其减少外部或内部流体在表面上的粘滞阻力,并且还包括额外的益处,诸如耐腐蚀性、耐结垢性、自清洁、传热特征、光学特征、化学惰性、其他有用特性或特性的组合。
在一些实施方案中,顶涂层是或含有抗微生物剂。例如,抗微生物剂可以是电荷转移化合物或破坏离子穿过细胞膜的运动的剂,例如季胺。在一些实施方案中,抗微生物剂是β-内酰胺、氨基糖苷、四环素、氯霉素、大环内酯、林可酰胺、磺酰胺、喹诺酮、聚烯、唑或灰黄霉素。
在一些实施方案中,顶涂层是或含有油漆粘合剂。例如,油漆粘合剂可以是醇酸树脂、丙烯酸树脂、乙烯基丙烯酸树脂、乙酸乙烯酯/乙烯(VAE)、聚氨酯、聚酯、硅酮、多元醇、三聚氰胺树脂、蜡、环氧树脂、硅烷或油。
陶瓷材料
如本文所述的陶瓷材料(诸如结构化陶瓷材料)沉积在多孔基材表面的至少一部分上。在一些实施方案中,陶瓷材料是纳米结构化陶瓷材料。在一些实施方案中,陶瓷材料是多孔的。在一些实施方案中,陶瓷材料是无粘合剂陶瓷材料,诸如无粘合剂纳米结构化陶瓷材料。在一些实施方案中,陶瓷材料是无粘合剂多孔陶瓷材料,诸如无粘合剂多孔纳米结构化陶瓷材料。
在一些实施方案中,陶瓷材料包括:每平方米投影基材面积约1.5m2至100m2、约10m2至约1500m2或约70m2至约1000m2的表面积;每克陶瓷材料约15m2至约1500m2或约50m2至约700m2的表面积;约5nm至约200nm、约2nm至约20nm或约4nm至约11nm的平均孔直径;至多约100微米、至多约50微米、至多约25微米、至多约20微米或约0.2微米至约25微米的厚度;约5%至约95%、约10%至约90%、约30%至约70%、约30%至约95%或大于约10%的孔隙率;如通过压汞法测定的约100mm3/g至约7500mm3/g的空隙体积;或其任何组合。
在一些实施方案中,陶瓷材料(例如,金属氧化物、金属氢氧化物和/或其水合物)包含锌、铝、锰、镁、铈、铜、钆、钨、锡、铅、和钴中的一种或多种。在一些实施方案中,陶瓷材料包含过渡金属、II族元素、稀土元素(例如,镧、铈、钆、镨、钪、钇、钐或钕)、铝、锡、锌或铅。
在一些实施方案中,陶瓷表面改性材料包括约0.5或1至约100微米或约0.5至约20微米的厚度或至多约50微米或至多约25微米的厚度。在一些实施方案中,无粘合剂多孔陶瓷材料包括约0.2微米至约25微米的厚度。在一些实施方案中,厚度为至少约0.2、0.5、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24或25微米中的任一个。在一些实施方案中,厚度为约0.2至约0.5、约0.5至约1、约1至约5、约3至约7、约5至约10、约7至约15、约10至约15、约12至约18、约15至约20、约18至约25、约0.5至约15、约2至约10、约1至约10、约3至约13、约0.5至约15、约0.5至约5、约0.5至约10、或约5至约15微米中的任一个。
在一些实施方案中,陶瓷表面改性材料包括每平方米投影基材面积约1.1m2至约100m2的表面积。在一些实施方案中,无粘合剂多孔陶瓷材料包括每平方米投影基材面积约10m2至约1500m2的表面积。在一些实施方案中,每平方米投影基材面积的表面积是至少约10、50、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900、950、1000、1050、1100、1150、1200、1250、1300、1350、1400、1450或1500m2中的任一个。在一些实施方案中,每平方米投影基材面积的表面积是约10至约100、约50至约250、约150至约500、约250至约750、约500至约1000、约750至约1200、约1000至约1500、约70至约1000、约150至约800、约500至约900、或约500至约1000m2中的任一个。
在一些实施方案中,陶瓷材料包括每克陶瓷材料约15m2至约1500m2的表面积。在一些实施方案中,每克陶瓷材料的表面积是至少约15、50、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900、950、1000、1050、1100、1150、1200、1250、1300、1350、1400、1450或1500m2中的任一个。在一些实施方案中,每克陶瓷材料的表面积是约15至约100、约50至约250、约150至约500、约250至约750、约500至约1000、约750至约1200、约1000至约1500、约50至约700、约75至约600、约150至约650或约250至约700m2中的任一个。
在一些实施方案中,陶瓷表面改性材料是多孔的并且包括在约2nm至约50nm的范围内的中孔平均孔径。在其他实施方案中,平均孔径在约50nm至约1000nm的范围内。在一些实施方案中,无粘合剂多孔陶瓷材料包括约2nm至约20nm的平均孔直径。在一些实施方案中,平均孔直径是至少约2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20nm中的任一个。在一些实施方案中,平均孔直径是约2至约5、约4至约9、约5至约10、约7至约12、约9至约15、约12至约18、约15至约20、约4至约11、约5至约9、约4至约8或约7至约11nm中的任一个。
在一些实施方案中,陶瓷表面改性材料是多孔的,孔隙率为约5%至约95%。在一些实施方案中,孔隙率可以是至少约或大于约5%、10%、15%、20%、25%、30%、35%、40%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%中的任一个。在一些实施方案中,孔隙率为约10%至约90%、约30%至约90%、约40%至约80%或约50%至约70%。
在一些实施方案中,陶瓷表面改性材料是多孔的,渗透率为约1至10,000毫达西。在一些实施方案中,渗透率可以是至少约1、10、100、500、1000、5000或10,000毫达西中的任一个。在一些实施方案中,渗透率为约1至约100、约50至约250、约100至约500、约250至约750、约500至约1000、约750至约2000、约1000至约2500、约2000至约5000、约3000至约7500、约5000至约10,000、约1至约1000、约1000至约5000或约5000至约10,000毫达西。
在一些实施方案中,陶瓷材料是多孔的并且包括如通过压汞法测定的约100mm3/g至约7500mm3/g的空隙体积。在一些实施方案中,空隙体积是至少约100、200、300、400、500、600、700、800、900、1000、1500、2000、2500、3000、3500、4000、4500、5000、5500、6000、6500、7000或7500mm3/g中的任一个。在一些实施方案中,空隙体积是约100至约500、约200至约1000、约400至约800、约500至约1000、约800至约1500、约1000至约2000、约1500至约3000、约2000至约5000、约3000至约7500、约250至约5000、约350至约4000、约400至约3000、约250至约1000、约250至约2500、约2500至约5000或约500至约4000mm3/g中的任一个。
陶瓷沉积层可设计成赋予一种或多种功能特征以及为功能化层(诸如顶涂层材料)提供结合表面。
使用应用
如本文所述的改性基材(例如,纺织品)包括一种或多种增强系统或使用应用的性能的功能特性。
例如,改性基材可以表现出对小分子(例如,低分子量(例如,小于900Da和/或大小为1nm或更小)有机化合物,诸如药物或抗生素)的粘附性高于对生物分子或皮脂组分(例如,甘油三酯、蜡酯、角鲨烯和/或脂肪酸)的粘附性。这种组合物可以例如以预涂有药物或生物杀灭剂并且不累积来自体油(皮脂)的气味的绷带(例如,铸造衬垫(cast liner))的形式提供。
在另一个实例中,基材被功能化成具有光催化性,并且粘附至表面的材料当暴露于光时被光催化降解。例如,气味促进化合物(诸如皮脂组分)当暴露于光时可能被分解。
在另一个实例中,与未用如本文所述的陶瓷材料改性的相同基材相比,组合物表现出对耐久型防泼水物质的粘附性更高。与本文所述的组合物形成对比,若干种商业耐久型防泼水制剂基于含氟聚合物,并且可能需要频繁地重新施用以维持性能。其他材料包括全氟酸、全氟烷基和多氟烷基物质(PFAS)、全氟丁磺酸、全氟辛酸、Scotchgard和Quarpel。这些材料中有许多材料对健康和环境有不利影响。
提供了包括本文所述的组合物的制品。此类制品的非限制性实例包括过滤器、膜、衣服、外套、野营装备(例如,帐篷、睡袋)、管道绝热物、地毯、家具装饰材料、汽车座椅(例如,婴儿座椅)、床上用品(例如,防水透气床上用品,诸如床单)、建筑包板、鞋类和窗饰。
在一个实施方案中,组合物用作膜,诸如但不限于食品包装。例如,膜可充当某些化合物的屏障,但允许氧气和其他材料通过,或者可用于将水与空气分开(例如,防泼水或挡水),或者可将固体与液体分开并挡住固体(例如,粗棉布)。在其他实施方案中,膜可以允许水蒸气通过,但不允许液态水通过。
以下实施例旨在说明但不限制本发明。
实施例
实施例1
将防撕裂(rip-stop)尼龙用作用于生产防水透气纺织品材料的基材。织造防撕裂尼龙通过气相沉积用铝金属化,以生产铝厚度为25nm至2000nm,通常约300nm的镀铝尼龙。
然后用多孔基于镁氧化物的陶瓷涂覆镀铝样品,在25至75mM硝酸镁水溶液和类似量的六亚甲基四胺中,在约60℃至80℃的温度下持续约5至90分钟的时间,沉积得到所述陶瓷。然后将网在约100℃至250℃的温度下煅烧约1小时。对沉积结构进行成像以评估均匀性。
纺织品通过在十六烷基膦酸中分批浸没90分钟来功能化以赋予超疏水性,然后在105℃下干燥90分钟。根据AATCC 127和ASTM E96标准测试样品,并且观察到其具有优于现有防水透气商业产品的抗水性和水蒸气渗透率性能。
实施例2
不锈钢网层在酸蚀刻剂中产生凹坑,然后用无粘合剂结构化锰氧化物陶瓷表面改性剂涂覆,在25至75mM硝酸锰水溶液和类似量的六亚甲基四胺或尿素中,在约60℃至80℃的温度下持续约60至240分钟的时间,沉积得到所述表面改性剂。然后将网在约400℃至600℃的温度下煅烧约1小时,得到表面亲水性。通过座滴法测量水接触角小于5度。将网放入装有约1cm去离子水的杯子中。2分钟后,测定毛细升高为高于液位约3cm。如PCT申请号PCT/US19/65978(参见例如图1A至图1C)中所述测定毛细升高。测定蒸气透过率为130g/h/m2。测试水柱突破压力,并且所述层不能支持任何可测量的水柱高度。
实施例3
使用与实施例2中所述的方法相似的方法,用由锰氧化物构成的陶瓷材料涂覆不锈钢网层。然后使用十六烷基膦酸在异丙醇中的稀(约0.5%)溶液对表面进行功能化,从而得到表面疏水性。通过座滴法测量水接触角为151度。将所述层放入装有约1cm去离子水的杯子中。2分钟后,在高于液位的表面上,水没有明显的上升。测定蒸气透过率为145g/h/m2。测定水柱突破压力确定为25cm水头(water head)。
实施例4
测试没有任何表面预加工的不锈钢网层。通过座滴法测量水接触角为20度。将所述层放入装有约1cm去离子水的杯子中。2分钟后,在高于液位的表面上,水没有明显的上升。测定蒸气透过率为152g/h/m2。测试水柱突破压力,并且所述层不能支持任何可测量的水柱高度。
实施例5
用由镁氧化物构成的陶瓷材料涂覆铝网层,在25至75mM硝酸镁水溶液和类似量的六亚甲基四胺中,在约60℃至80℃的温度下持续约30至90分钟的时间,沉积出所述陶瓷材料。然后将网在约300℃至600℃的温度下煅烧约1小时,从而得到表面亲水性。通过座滴法测量水接触角小于5度。将所述层放入装有约1cm去离子水的杯子中。2分钟后,测定毛细升高为高于液位约5cm。测定蒸气透过率为约150g/h/m2。测试水柱突破压力,所述层不能支持任何可测量的水柱高度。
实施例6
使用与实施例5中所述的程序相似的程序,用由镁氧化物构成的陶瓷材料涂覆铝网(荷兰斜纹(Dutch twill))层。然后使用十六烷基膦酸在异丙醇中的稀溶液对表面进行功能化,从而得到表面疏水性。通过座滴法测量水接触角为160度。将所述层放入装有约1cm去离子水的杯子中。2分钟后,在高于液位的表面上,水没有明显的上升。测定蒸气透过率为150g/h/m2。测定水柱突破压力为约100cm水头。
实施例7
测试没有任何表面预加工的铝网层。通过座滴法测量水接触角为20度。将所述层放入装有约1cm去离子水的杯子中。2分钟后,在高于液位的表面上,水没有明显的上升。测定蒸气透过率为153g/h/m2。测试水柱突破压力,并且所述层不能支持任何可测量的水柱高度。
实施例8
使用与实施例1中所述的方法相似的方法,用由镁氧化物构成的陶瓷材料涂覆40d(40旦尼尔)织造聚酰胺纺织品层,从而得到表面亲水性。通过座滴法测量水接触角小于5度。测定蒸气透过率为175g/h/m2。测试水柱突破压力,并且所述层不能支持任何可测量的水柱高度。
实施例9
用由镁氧化物构成的陶瓷材料涂覆40d织造聚酰胺纺织品层。然后使用十六烷基膦酸在异丙醇中的稀溶液对表面进行功能化,从而得到表面疏水性。测定蒸气透过率为170g/h/m2。测定水柱突破压力为55cm水头。
实施例10
测试没有任何表面预加工的40d织造聚酰胺纺织品层。测定蒸气透过率为170g/h/m2。测试水柱突破压力,并且所述层不能支持任何可测量的水柱高度。
实施例11
将织造聚酯纺织品和织造尼龙纺织品溅射约250nm的铝。将纺织品切成小块并涂覆3种不同的陶瓷材料:a)基于镁氧化物/氢氧化物的陶瓷,b)和基于锰氧化物/氢氧化物的陶瓷,c)和基于锌氧化物/氢氧化物的陶瓷。所有三种陶瓷都含有大量的铝氧化物/氢氧化物。以类似于实施例1中所述方法的方法沉积陶瓷(使用陶瓷中发现的每种相应的阳离子的2+金属硝酸盐或金属硫酸盐)。测试样品的接触角,并且样品表现出小于15度的接触角。然后将陶瓷改性纺织品浸涂到十六烷基膦酸在异丙醇中或十六烷基三乙氧基硅烷在乙醇中的稀释浴(0.1%至1%)中。在硅烷的情况下,有时使用少量的乙酸催化剂。然后再次测量样品的接触角,并且样品表现出约150至160度的接触角。湿气透过率在未改性织物的测量误差内。
实施例12
通过在室温下,将纺织品在约200-500mM硫酸锌、约50-150mM过硫酸钾和约1.2至1.7摩尔氢氧化铵的批料中浸泡约5至60分钟,用基于锌氧化物的陶瓷涂覆织造聚酯纺织品、聚酰胺纺织品和Tencel纺织品。通过用硫酸镍代替硫酸锌同样在聚酯上形成镍氧化物沉积物。通过用硫酸锰代替硫酸锌并且用高锰酸盐代替过硫酸盐同样在聚酯上形成锰氧化物沉积物。然后将这些样品在约105℃至约140℃的温度下干燥约1至2小时的时间。测试样品的接触角,并且样品表现出小于15度的接触角。然后将陶瓷改性纺织品浸涂到十六烷基膦酸在异丙醇中或十六烷基三乙氧基硅烷在乙醇中的稀释浴(0.1%至1%)中。在硅烷的情况下,有时使用少量的乙酸催化剂。然后再次测量样品的接触角,并且样品表现出约150至160度的接触角。
实施例13
将织造聚酰胺和聚酯纺织品浸没在氧化剂浴中以活化表面。典型的氧化程序包括将纺织品浸没在浓度为约5mM至约200mM的过硫酸钾或高锰酸钾和浓度为约10mM至约400mM的氢氧化铵的水浴中。典型的浴具有约1:2的高锰酸钾或过硫酸钾与氢氧化铵的摩尔比。氧化温度的范围为约室温至约80℃。
实施例14
将织造聚酯和聚酰胺纺织品在UV/臭氧和/或氧等离子体中氧化,使得结构化陶瓷层的粘附力更好。
实施例15
在约室温至约80℃的温度下,将织造聚酰胺和聚酯纺织品浸没在约5至200mM高锰酸钾和约10至400mM氢氧化铵的水浴中约5分钟至约1小时。高锰酸盐与氢氧化铵的典型比率为约1比2。然后使基材干燥,然后通过在约60℃至80℃的温度下,将基材浸泡在25至150mM金属(Mn、Zn或Mg)硝酸盐水溶液和类似量的六亚甲基四胺中约5至90分钟的时间,使基材沉积有包含锰氧化物/氢氧化物、锌氧化物/氢氧化物或镁氧化物/氢氧化物的结构化陶瓷层。然后将网在约100℃至250℃的温度下干燥约1小时。测量样品的接触角,并测出其小于约15度。然后将陶瓷改性纺织品浸涂到十六烷基膦酸在异丙醇中或十六烷基三乙氧基硅烷在乙醇中的稀释浴(0.1%至1%)中。在硅烷的情况下,有时使用少量的乙酸催化剂。然后再次测量样品的接触角,并且样品表现出约150至160度的接触角。
虽然为达到清楚理解的目的,上述发明已通过图解和实施例的方式作了一些详细描述,但是对本领域的技术人员显而易见的是,在不脱离所附权利要求书中划定的本发明的精神和范围的情况下,可以进行某些改变和修改。因此,描述不应解释为限制本发明的范围。
本文中引用的所有公布、专利和专利申请出于所有目的均以引用的方式整体并入本文,并且其程度如同每个单独的公布、专利或专利申请明确地并单独地表明为以引用的方式并入本文一般。
Claims (43)
1.一种组合物,其包含在多孔基材上的无粘合剂陶瓷材料。
2.根据权利要求1所述的组合物,其中所述基材包括平均孔直径小于约250μm的孔,并且其中所述陶瓷材料不实质地改变所述平均孔直径。
3.根据权利要求1所述的组合物,其中所述基材包括平均孔直径小于约250μm的孔,并且其中所述陶瓷部分地或完全地填充所述孔,从而分别减小所述平均孔直径或消除所述孔。
4.根据权利要求1至3中任一项所述的组合物,其中根据ASTM D737,所述基材包括约0.1立方英尺每分钟(CFM)至约100CFM的空气渗透率。
5.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料主要是结晶的。
6.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包括金属氧化物、金属氧化物的水合物、金属氢氧化物和/或金属氢氧化物的水合物。
7.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包括金属氢氧化物,并且其中所述金属氢氧化物的至少一部分包括层状双氢氧化物。
8.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包括纳米结构化陶瓷材料。
9.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包含过渡金属、II族元素、稀土元素、铝、锡或铅。
10.根据权利要求9所述的组合物,其中所述陶瓷材料包含锌、铝、锰、镁、铈、铜、钆、钨、锡、锌、铅和钴中的一种或多种。
11.根据权利要求10所述的组合物,其中所述陶瓷材料包括:锌和铝氧化物和/或氢氧化物的混合物;锰和镁氧化物和/或氢氧化物的混合物;锰氧化物和/或氢氧化物;铝氧化物和/或氢氧化物;混合金属锰氧化物和/或氢氧化物;镁和铝氧化物和/或氢氧化物的混合物;镁氧化物和/或氢氧化物;镁、铈和铝氧化物和/或氢氧化物的混合物;锌、镨和铝氧化物和/或氢氧化物的混合物;钴和铝氧化物和/或氢氧化物的混合物;锰和铝氧化物和/或氢氧化物的混合物;铈和铝氧化物和/或氢氧化物的混合物;铜和铝氧化物和/或氢氧化物的混合物;锌和铝氧化物和/或氢氧化物的混合物;Zn-铝酸盐的混合物;包含一种或多种包含Zn、Al和氧的相的混合物;锌氧化物和/或氢氧化物;或上述化合物或其混合物中任一种的水合物。
12.根据权利要求11所述的组合物,其中所述陶瓷材料包括至多约25μm的厚度。
13.根据权利要求12所述的组合物,其中所述陶瓷材料包括约0.2μm至约25μm的厚度。
14.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包括约5%至约80%的孔隙率。
15.根据权利要求14所述的组合物,其中所述陶瓷材料包括大于约10%的孔隙率。
16.根据权利要求14所述的组合物,其中所述陶瓷材料包括约30%至约95%的孔隙率。
17.根据权利要求1至3中任一项所述的组合物,其中所述多孔基材包括织造材料、针织材料、非织造织物或纺织品或纸。
18.根据权利要求17所述的组合物,其中所述多孔基材包括聚酰胺、聚酯、棉、羊毛、聚乙烯、聚丙烯、纤维素材料、芳族聚酰胺、聚氨酯、活性炭、玻璃纤维、钢合金、黄铜合金、铝合金、铝或铜。
19.根据权利要求17所述的组合物,其中所述多孔基材是纺织品材料,其包括天然纤维、合成纤维、金属网、或金属布或其组合。
20.根据权利要求17至19中任一项所述的组合物,其中纺织品表面已被氧化、灰化或活化。
21.根据权利要求17所述的组合物,其中所述基材是在纺织品表面上包括一种或多种金属的金属化纺织品。
22.根据权利要求21所述的方法,其中纺织品表面上的所述金属包括铝、铁、镍、钛或铜。
23.根据权利要求1至3中任一项所述的组合物,其中所述无粘合剂陶瓷赋予所述组合物一种或多种功能特性。
24.根据权利要求23所述的组合物,其中所述一种或多种功能特性包括亲水性、疏水性、阻燃性、光催化性、防污性、除臭性、微生物生长抑制、冰或冷凝物管理、防冰、防霜、超疏水性、超亲水性、耐腐蚀性、电磁调制、热调制、透气性、动态抗风和/或颜色。
25.根据权利要求23所述的组合物,其中所述功能特性中的两种或更多种被赋予至所述组合物的单层。
26.根据权利要求1-3中任一项所述的组合物,其中所述陶瓷材料由功能层进一步改性。
27.根据权利要求26所述的组合物,其中所述功能层赋予一种或多种功能特性,其量值比由直接沉积在不包括所述陶瓷材料的相同纺织品表面上的相同功能层材料赋予的相同功能特性大。
28.根据权利要求26所述的组合物,其中所述陶瓷材料和所述功能层协同地赋予一种或多种功能特性,其量值比由独立地沉积在相同纺织品表面上的所述陶瓷材料或所述功能层材料赋予的相同功能特性大。
29.根据权利要求26所述的组合物,其中所述功能层赋予疏水性。
30.根据权利要求29所述的组合物,其中所述功能层包括含氟聚合物、弹性体或塑料。
31.根据权利要求29所述的组合物,其中所述功能层包括具有头基和尾基的分子,
其中所述头基包括硅烷基、膦酸酯基、膦酸基、羧酸基、乙烯基、醇基、氢氧基、硫醇盐基、硫醇基和/或铵基,并且
其中所述尾基包括烃基、碳氟基、乙烯基、苯基、环氧基、丙烯酸基、丙烯酸酯基、羟基、羧基、硫醇基和/或季铵基。
32.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料是部分填充的多孔结构。
33.根据权利要求32所述的组合物,其中所述孔部分地填充有第二陶瓷材料或具有头基和尾基的分子。
34.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料对小分子的粘附性高于对生物分子或来自皮脂的组分的粘附性。
35.根据权利要求34所述的组合物,其中所述来自皮脂的组分包括甘油三酯、蜡酯、角鲨烯和/或游离脂肪酸。
36.根据权利要求1至3中任一项所述的组合物,其中所述陶瓷材料包括光催化性,并且其中粘附至表面的材料在暴露于光时被光催化降解。
37.根据权利要求1至3中任一项所述的组合物,其中与不包括所述陶瓷材料的相同基材相比,所述组合物对耐久型防泼水物质的粘附性更强。
38.一种制品,其包括根据权利要求1至37中任一项所述的组合物。
39.根据权利要求38所述的制品,其选自过滤器、膜、衣服、外套、野营装备、管道绝热物、地毯、汽车座椅、家具装饰材料、床上用品、鞋类、建筑包板和窗饰。
40.根据权利要求1至39中任一项所述的组合物或制品,其中所述组合物或制品能承受大于约1kPa的静水压力。
41.根据权利要求1至39中任一项所述的组合物或制品,其中所述组合物或制品包括大于不包括所述陶瓷材料的相同基材的蒸气透过率的约80%的湿气透过率。
42.根据权利要求1至39中任一项所述的组合物或制品,其中所述组合物或制品包括大于约150度的座滴法水接触角。
43.根据权利要求1至39中任一项所述的组合物或制品,其中所述组合物或制品包括锰氧化物陶瓷和烷基硅烷或烷基膦酸酯功能层。
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