TW202136179A - 功能化織物材料之總成及其使用方法 - Google Patents
功能化織物材料之總成及其使用方法 Download PDFInfo
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Abstract
本發明描述材料之堆疊層之總成。該等總成包括功能及結構層。功能層包括天然、合成或金屬材料之編織或非編織基板上之無膠結陶瓷材料。功能及結構材料之層可經組態以將水分或熱量自內表面輸送至曝露於周圍環境之外表面。
Description
本發明係關於用陶瓷表面修飾材料(特定言之,無膠結陶瓷(諸如金屬氧化物及/或金屬氫氧化物陶瓷)或轉化塗層於織物表面上)及此等材料之層之總成使該織物表面功能化以相較於個別或非功能化層提供功能益處。
相對於非功能化織物層,織物表面之功能化提供關於織物性能之所需益處。當相較於個別功能層或非功能化層之總成時,可向單一系統或製品提供多種有利性質之層之總成係期望的且可提供額外益處。此外,期望之性能特性可通過個別功能層之積體以形成總成來增強。
本文提供材料之功能及結構層及/或具有其他有利性質之層之總成。功能層可包括陶瓷材料於基板(諸如織物基板)上。
在一項態樣中,提供包括頂表面及底表面之材料之總成,其中該總成包括:(a)包含一或多種功能性質之材料之x At
層,其中該等At
層包含包括頂表面之最上層;(b)包含一或多種功能性質之材料之y Ab
層,其中該等Ab
層包含包括底表面之最底層;及(c) 介於x At
層與y Ab
層之間之絕緣、結構或另外功能有利之材料之z B層,其中x、y及z係相同或不同的層數,其中該等At
層及/或該等Ab
層可各包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上,且其中各At
層及/或各Ab
層上之陶瓷材料係相同或不同的。在一項實施例中,至少一個At
層包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在另一實施例中,至少一個Ab
層包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在另一實施例中,至少一個At
層及至少一個Ab
層各包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在一些實施例中,該頂表面及/或該底表面包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料。在一些實施例中,Ab
層及/或At
層包括多種功能(例如,與美學及/或性能相關)性質。
在另一態樣中,本文提供包括頂表面及底表面之材料之總成,其中該總成包括:(a)包含一或多種功能性質之材料之x A層,其中該等A層包含包括頂表面之最上層,其中該等A層各包含陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上;及(b)絕緣、結構或另外功能有利之材料之z B層,其中該等B層包含包括底表面之最底層,且其中x及z係相同或不同的層數。在一些實施例中,該總成不包括Ab
層。
在另一態樣中,本文提供包括頂表面及底表面之材料之總成,其中該總成包括:(a)包含一或多種功能性質之材料之x At
層,其中該等At
層包含包括頂表面之最上層;及(b)包含一或多種功能性質之材料之y Ab
層,其中該等Ab
層包含包括底表面之最底層,其中該等At
層及該等Ab
層各包含陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上,其中該等At
層上之陶瓷材料不同於該等Ab
層上之陶瓷材料,且其中x及y係相同或不同的。在一些實施例中,該總成不包括B層。在一項實施例中,至少一個At
層包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在另一實施例中,至少一個Ab
層包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在另一實施例中,至少一個At
層及至少一個Ab
層各包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料於基板上。在一些實施例中,該頂表面及/或該底表面包括陶瓷材料諸如無膠結陶瓷例如無膠結多孔陶瓷材料。在一些實施例中,Ab
層及/或At
層包括多種功能(例如,與美學及/或性能相關)性質。
在一些實施例中,陶瓷材料主要係結晶質。在一些實施例中,該陶瓷材料包括金屬氧化物、金屬氧化物之水合物、金屬氫氧化物及/或金屬氫氧化物之水合物。在一些實施例中,該陶瓷材料包括金屬氫氧化物,及該金屬氫氧化物中之至少一部分包括層狀雙氫氧化物。在一些實施例中,該陶瓷係結構化陶瓷,諸如奈米結構化陶瓷。
在一些實施例中,陶瓷材料包括混合金屬氧化物、混合金屬氧化物之水合物、混合金屬氫氧化物及/或混合金屬氫氧化物之水合物。在一些實施例中,該陶瓷材料包括混合金屬氫氧化物,及該金屬氫氧化物中之至少一部分包括層狀雙氫氧化物。
在一些實施例中,陶瓷材料包括混合金屬氧化物、混合金屬氧化物之水合物、混合金屬氫氧化物及/或混合金屬氫氧化物之水合物之化學轉化。在一些實施例中,該陶瓷材料包括混合金屬氫氧化物,及該金屬氫氧化物中之至少一部分包括其中嵌入離子已經交換之層狀雙氫氧化物(例如,如最初產生之層狀雙氫氧化物中之嵌入金屬離子已交換為不同嵌入離子)。
在一些實施例中,至少一個At
及/或至少Ab
層之基板包括為編織、非編織或針織物之合成或天然織物,或金屬網、金屬篩或金屬布。在一些實施例中,至少一個At
及/或至少一個Ab
層之基板包括合成或天然材料膜或聚合物。
在一些實施例中,各At
及/或Ab
層包括選自以下之一或多種功能性質:冰或冷凝物操作、防冰、防霜凍、超疏水性、超親水性、抑制或抵抗微生物生長、耐腐蝕性、電磁調製、熱調製、阻燃性、透氣性、動態抗風性、顏色、吸收性、阻隔性、維護性質(例如,色牢度、抗降解性,例如,在清洗期間,易於清潔,抗皺性、抗異味性)、美學性質(例如,顏色反射率、光潔度(例如,啞光、乳白色)、色彩深度(例如,作為觀察角度函數之顏色變化))、氣味控制、耐磨性、機械性質(例如,剛度、抗拉強度(例如,抗撕裂性)、抗衝擊性)、表面摩擦、手感、耐久性或其組合。
在一些實施例中,x及/或y大於1,及各At
及/或Ab
層包括至少一個與其他At
及/或Ab
層不同之功能性質。在一些實施例中,各At
層包括至少一個與其他At
層不同之功能性質。在其他實施例中,各Ab
層包括至少一個與其他Ab
層不同之功能性質。在其他實施例中,At
層包括與Ab
層不同之功能性質。
在一些實施例中,包括頂表面之最上層(最上At
層)及包括底表面之最底層(最底Ab
層)具有相同功能性質。在一些實施例中,包括該頂表面之最上層(最上At
層)及包含該底表面之最底層(最底Ab
層)具有不同功能性質。
在一些實施例中,各B層包括選自以下之一或多種結構性質:熱阻、電阻、結構支撐、機械墊充、美學、舒適性、保護性、耐久性、維護性質(例如,快乾、易於折疊、色牢度、抗降解性,例如,在清洗期間,易於清潔,抗皺性)、流體輸送特性或其組合。在一些實施例中,一或多個B層包括(例如)選自玻璃纖維、鬆散陶瓷及其他無機材料之陶瓷材料。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
及/或Ab
層)包括施加至或沈積於賦予或增強一或多種功能性質之陶瓷材料上之功能材料(例如,表面功能性表塗層材料)。在一些實施例中,由此等功能材料賦予之至少一種功能性質具有比由直接沈積於不包含陶瓷材料之相同基板上之相同表面功能性表塗層材料賦予之相同功能性質更大之量級。在本文總成之一些實施例中,至少一個A層(例如,至少一個At
及/或Ab
層)包括功能材料(例如,表面功能性表塗層材料),且該陶瓷材料及該功能材料協同賦予之一或多種功能性質具有比由獨立沈積於相同織物表面上之陶瓷材料或表塗層材料賦予之相同功能性質更大之量級。
在一些實施例中,功能層賦予疏水性質。例如,賦予組合物疏水性質之功能層可包括含氟聚合物、彈性體、塑膠或具有頭部基團及尾部基團之分子,例如,其中該頭部基團包括矽烷基、膦酸酯基、膦酸基、羧酸基、乙烯基、醇基、氫氧化物基、硫醇酯基、硫醇基及/或銨基(例如,第四銨基),且其中該尾部基團包括烴基、氟碳基、乙烯基、苯基、環氧基、丙烯酸基、丙烯酸酯基、羥基、羧酸基、硫醇基及/或第四銨基。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
及/或至少一個Ab
層)上之無膠結陶瓷材料係部分填充之多孔結構。例如,該陶瓷材料之孔可用第二陶瓷材料或用具有頭部基團及尾部基團之分子填充。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
層及/或至少一個Ab
層)可承受大於約1 kPa之靜水壓。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
層及/或至少一個Ab
層)包括大於未經陶瓷材料(及在一些實施例中,可選功能層)修飾之相同基板之蒸氣透過率之約80%之濕氣透過率。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
層及/或至少一個Ab
層)包括大於約150度之不濡液滴水接觸角。
在本文總成之一些實施例中,至少一個A層(例如,至少一個At
及/或Ab
層)改善美學、穿戴者舒適性、耐久性或所需性質之維持。(參見,例如,Venkatraman, P.,「Fabric Properties and Their Characteristics, in Materials and Technology for Sportswear and Performance Apparel」,2015, CRC Press, ISBN 9781482220513)。
在一些實施例中,將總成併入高性能外衣、醫用繃帶、醫用石膏、手術服、過濾或分離介質、包裝材料、醫院床上用品、吸收性織物、防護面具、防護外衣、建築織物或土工織物內。
在一些實施例中,提供包括如本文描述之總成之管道絕緣或管道保護材料,其中一或多個At
層包括疏水或超疏水功能性質,其中一或多個B層包括熱絕緣、保護性(例如,在操作條件下或在使用環境中,防止管道腐蝕及/或磨損,及/或防止對接近該管道之個體造成損害)或結構性質,且其中一或多個Ab
層包括親水或超親水功能性質。例如,該管道絕緣或管道保護材料可圍繞管道,其中該最底Ab
層係與該管道接觸,且其中該最上At
層係與周圍環境接觸。一或多個At
及/或Ab
層可包括陶瓷塗層編織材料。例如,該編織材料可選自不銹鋼合金編織材料、碳鋼合金編織材料、鋁合金編織材料及織物。在一些實施例中,至少一個B層可包括選自玻璃纖維、碳化矽 (例如,金剛砂)、陶瓷纖維絕緣、聚矽氧或聚矽氧發泡體、礦棉、玄武岩、氣泡玻璃、聚醯亞胺、矽酸鈣或二氧化矽之材料。本文亦提供經如本文描述之絕緣、保護性或性能材料圍繞之管道、管段或反應器段(諸如生物反應器、吸附床、催化反應器或蒸餾塔)。
在一些實施例中,提供包括如本文描述之總成之織物材料,其中一或多個At
層包括疏水或超疏水功能性質,其中一或多個B層包括熱絕緣、保護或結構性質,且其中一或多個Ab
層包括親水或超親水功能性質。在一些實施例中,一或多個At
及/或Ab
層之基板包括編織材料。例如,該編織材料可選自織物、聚醯胺、聚酯、纖維素材料、棉、羊毛、聚合物膜、不銹鋼合金編織材料及鋁合金編織材料。在一些實施例中,一或多個At
及/或Ab
層之基板包括耐綸或聚對酞酸乙二酯(PET)。在一些實施例中,一或多個B層包括選自聚酯、毛片、羊毛、羽毛、絨毛及其他主要有機材料之材料。
相關申請案之交叉參考
本申請案主張2019年12月12日申請之PCT申請案第PCT/US2019/065978號之優先權,且主張2020年3月13日申請之美國臨時申請案第62/989,092號、2020年3月13日申請之62/989,150、2020年6月12日申請之63/038,642、2020年6月12日申請之63/038,693及2020年6月16日申請之63/039,965之權益,其等中之所有均以全文引用之方式併入本文中。
本文描述材料之堆疊層之總成,且其使用方法及應用。本文描述之總成包括一或多種功能(「A」)層,及視需要,一或多種結構或整體性質(「B」)層。該等功能層包括結構化陶瓷於基板材料上以為使用之特定應用提供所需性質,結構陶瓷可提供所需功能性質及/或其可藉由施加或沈積額外之表面化學表塗層材料進一步功能化。基板表面中之至少一部分經歷化學轉化以提供結構化(例如,奈米結構化)陶瓷材料,及可選後續過程提供陶瓷之額外功能化。層可經佈置以定向方式賦予功能性質,諸如蒸氣或熱能在朝向曝露於周圍環境之表面之方向上移動。層可經佈置以組合方式賦予功能性質,諸如耐磨層及絕緣層以提供機械及熱保護。
A層包括結構陶瓷於基板表面上,及視需要,表面功能表塗層,以向該基板提供一或多種功能性質。陶瓷,例如,多孔陶瓷(例如,金屬氧化物及/或金屬氫氧化物)表面修飾組合物係沈積於織物或織品基板表面上。該等組合物係作為無膠結表面修飾材料提供於該基板之表面上,例如,表面固定之陶瓷材料。在一些實施例中,該陶瓷材料包括金屬氧化物及/或氫氧化物陶瓷,例如,單一金屬或混合金屬氧化物及/或氫氧化物陶瓷。在一些實施例中,該陶瓷材料包括金屬氧化物及金屬氫氧化物陶瓷,其中該金屬氧化物及該金屬氫氧化物包括相同或不同之單一金屬或混合金屬。在一些實施例中,該陶瓷材料包括金屬氧化物及/或金屬氫氧化物陶瓷,其中該基板係由水或其他化合物水合導致改變表面能及可能該陶瓷之金屬氧化物與金屬氫氧化物組成之比率。在一些實施例中,該陶瓷材料包括金屬氫氧化物,其中該金屬氫氧化物中之至少一部分係呈層狀雙氫氧化物之形式,例如,該金屬氫氧化物之至少約5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%係層狀雙氫氧化物。在一些實施例中,該層狀雙氫氧化物之嵌入離子可經交換以賦予額外益處。在本文描述之組合物之一些實施例中,「金屬氧化物」或「金屬氫氧化物」可分別呈金屬氧化物之水合物或金屬氫氧化物之形式,或該金屬氧化物或金屬氫氧化物之一部分可分別呈金屬氧化物之水合物或金屬氫氧化物之形式。
混合金屬氧化物或混合金屬氫氧化物可分別包括(例如)多於一種金屬之氧化物或氫氧化物,該諸如(但不限於)鐵、鈷、鎳、銅、錳、鉻、鈦、釩、鋯、鉬、鉭、鋅、鉛、錫、鎢、鈰、鐠、釤、釓、鑭、鎂、鋁或鈣。
本文之表面修飾材料(例如,無膠結多孔陶瓷材料)係在無黏合劑之情況下沈積於基板(例如,藉由在該基板表面上與金屬反應產生)上。在一些實施例中,將如本文描述之表面修飾材料固定化於該基板上。
在一些實施例中,結構化陶瓷材料係奈米結構化陶瓷材料。
在一些實施例中,結構化陶瓷材料經受導致經修飾之結構化(例如,奈米結構化)陶瓷材料之額外化學轉化過程。
無膠結陶瓷表面修飾材料之非限制性實例提供於PCT申請案第PCT/US19/65978號中,其係以全文引用之方式併入本文中。
定義
本文提供之數值範圍包括定義該範圍之數字。
除非內文另有明確規定,否則「一」、「一個」及「該」包括複數個參考物。
如本文用於說明書及申請專利範圍中之片語「及/或」應瞭解為意謂如此結合之元素中之「一者或兩者」,即,在一些情況下結合存在及在其他情況下析取存在之元素。除非另有明確相反指示,否則除由「及/或」字句明確識別之元素外,無論與經明確識別之彼等元素相關或無關,其他元素均可視需要存在。因此,作為一非限制性實例,對「A及/或B」之參考在結合諸如「包含」之開放式語言一起使用時在一項實施例中可係指A無B (視需要包括除B外之元素);在另一實施例中,係指B無A (視需要包括除A外之元素);在又另一實施例中,係指A及B (視需要包括其他元素);等」。
「黏合劑」或結合劑係將其他材料保持或吸引在一起以藉由黏附或內聚機械、化學地形成內聚整體之任何材料或物質。
「無黏合劑」係指缺乏黏合劑,尤其關於有機黏合劑或樹脂(例如,聚合物、膠黏劑、黏合劑、瀝青)或無機黏合劑(例如,石灰水泥、水泥玻璃、石膏等)。
「封端劑」係指減緩晶體生長且允許調節奈米表面之形態學之化合物或藥劑。
「陶瓷」係指包含金屬、非金屬或離子鍵及共價鍵之無機化合物之固體材料。
「轉化塗層」係指其中反應物與待處理之表面化學反應以將基板轉化為不同化合物之表面層。此過程通常非加性或沈積。
「織品」係指可自纖維構成並藉由化學、機械、熱量及/或溶劑處理結合在一起之非編織材料。織品可包括(例如)毛氈,及既非編織亦非針織之其他材料。
「纖維」係指形成織物之線或細絲。
「親水」係指對水具有高親和力之表面。接觸角可非常低及/或不可估量。
「層」係指材料之片材、量或厚度,通常數個、覆蓋表面或主體或獨立式(例如,由一或多個支撐結構支撐)中之一者。
「層狀雙氫氧化物」係指一類離子固體,其等特徵在於具有通用序列[AcB Z AcB]n
之層狀結構,其中c表示金屬陽離子之層,A及B係氫氧化物陰離子之層,及Z係其他陰離子及/或中性分子(諸如水)之層。層狀雙氫氧化物亦描述於PCT申請案第PCT/US2017/052120號中,其係以引用之方式併入本文中。
「奈米結構」組合物在本文中係指在至少一個維度上具有小於100奈米之特徵之組合物。
流體力學中之「滲透性」係多孔材料容許流體通過其之能力之量度。介質之滲透性係與孔隙率相關,但亦與該介質中該等孔之形狀及其等連通性水平相關。
「孔徑分佈」係指如藉由壓汞法(MIP)及沃什伯恩方程確定之各孔直徑或範圍或孔直徑之相對豐度。
「孔隙率」係材料中空隙(即,「空」)空間之量度,及係空隙之體積佔總體積之分數(0至1),或作為介於0%與100%之間之百分比。孔隙率可藉由壓汞法量測。
「多孔」係指固體材料內之空間、孔或空隙。
「超親水」係指表面具有過量親水性,或對水具有吸引力。水在超親水材料上之接觸角等於零度。
「超疏水」係指極難潤濕之表面。水滴在超疏水材料(本文係超疏水表面)上之接觸角係指> 150°之接觸角。高度疏水接觸角係>120o
。
「每平方米預計基板面積之表面積」係指實際量測之表面積(通常以平方米量測)除以若基板係原子上光滑(無表面粗糙度)時之表面積(通常亦以平方米量測)。
「協同」或「協同作用」係指兩種或更多種物質、材料或藥劑間相互作用或協作以產生比其等單獨、個別效應之總和更大(正協同)或更小(負協同)之組合效應。
「織物」係指由天然或人造纖維之網路構成之可撓性材料。例如,織物材料可藉由通過針織、編織、氈合、簇絨或結合連接纖維或纖維之群組產生,其中纖維包含所有長度之天然及合成形式,包括金屬纖維。織物亦包括繩索及粗線。
「厚度」係指基板之表面與表面修飾(例如,陶瓷)材料之頂部間之長度。
「表塗層」係指材料或化學處理,其中表面及化學物質通過表面能、抗微生物性、顏色、熱性質、電性質或反應性之變化相互作用、結合或分散以形成經修飾之表面。性質變化可在原子、分子、特徵或整體零件長度尺度上實現。
「可調」係指材料之功能、特性或品質待改變或修飾之能力。
「蒸氣透過率」係指每單位面積每單位時間在與層平面正交之方向上通過該層之蒸氣之質量。
「水柱突破壓力」係指垂直水柱之特定高度,在該高度下,水柱底部由層經受之靜水壓克服該層支撐該水柱之能力,導致水流過該層。
材料之總成
本文揭示材料之層之總成。該等層一般組態成堆疊,該堆疊之頂部具有頂表面及該堆疊之底部具有底表面。該頂表面係一般與該總成位於或使用之周圍環境(例如,空氣)接觸。該底表面可與使用該總成之裝置、表面或個體接觸或接近,例如,待保護之裝置或表面,或針對個體在使用之特定周圍環境中之舒適性。
層之堆疊包括材料,該等材料包括位於基板(本文中稱為「A」層)上之陶瓷(例如,無膠結陶瓷,諸如無膠結多孔陶瓷材料)。A層賦予總成所需功能性質。例如,該陶瓷材料可賦予選自以下之一或多種性質:疏水性、抑制微生物生長、阻燃性、親水性、耐腐蝕性、冰或冷凝物操作、防冰、防霜凍、超疏水性、超親水性、抑制微生物生長、耐腐蝕性、電磁調製、熱調製、透氣性、動態抗風性及/或顏色或其組合。本文總成之一些實施例包括頂部A層及底部A層,頂部A層包括該總成之頂表面(面向周圍環境),底部A層包括該總成之底表面(面向使用該總成之裝置、表面或個體)。如本文描述之無膠結多孔陶瓷材料係位於頂表面及底表面中之各者上。各A層上之無膠結多孔陶瓷材料可與該總成中之各其他A層相同或不同。
層之一些堆疊包括一或多個包括結構及/或絕緣材料之「B」層,其介於該堆疊之頂部之一或多個A層(「At
」層)與在該堆疊之底部之一或多個A層(「Ab
」層)之間。在一些實施例中,該總成包括具有結構及/或絕緣材料之一個B層。在其他實施例中,該總成包括具有結構及/或絕緣材料之兩個或更多個B層,且各B層可由與該總成中之各其他B層相同或不同之材料或組合物構成。
在一些實施例中,總成包括一個At
層及一個Ab
層,且該At
層可由與該Ab
層相同或不同之材料或組合物(例如,相同或不同之基板及/或陶瓷組合物)構成。在一些實施例中,該總成包括兩個或更多個At
層(即,複數個At
層)及/或兩個或更多個Ab
層(即,複數個Ab
層),且各At
層及/或各Ab
層可由與各其他A層(即,各其他At
及/或Ab
層)相同或不同之材料或組合物(例如,相同或不同之基板及/或陶瓷組合物)構成。
在一些實施例中,總成之至少一個A層(例如,至少一個At
及/或Ab
層)賦予該總成一或多種功能性質,例如,選自冰或冷凝物操作(抵抗結冰或引導或放置引導冰或冷凝物以所需方式形成、收集及輸送之材料)、防冰性能或防霜凍性質、超疏水性(例如,預防滲水造成之結垢)、超親水性(例如,將水自表面吸除以最小化時間或濕度及/或防止與水分相關之損害)、抗微生物調節(抑制、消除或防止微生物生長)、耐腐蝕性或預防、電磁調製(電磁性質之變化,例如,漫反射或鏡面發射、漫反射或鏡面反射、吸附、透射)、熱調製、阻燃性、透氣性(容許水蒸氣通過材料輸送)、動態抗風性(蒸氣透射對施加之風速之非線性影響)、機械保護(磨損或抗衝擊性)及顏色及/或其他美學性質或其組合。
在一些實施例中,包括總成之頂表面之At
層及包括總成之底表面之Ab
層賦予不同之功能性質。在一項實施例中,包括總成之頂表面之At
層係疏水或超疏水的及包括總成之底表面之Ab
層係親水或超親水的。在另一實施例中,包括總成之頂表面之At
層係疏水或超疏水的及包括總成之底表面之Ab
層係抗微生物的。在另一實施例中,包括總成之頂表面之At
層係疏水或超疏水的,包括總成之底表面之Ab
層係抗微生物的,及在包括總成之底表面之Ab
層上之Ab
層係疏水或超疏水的。
在某些實施例中,將表塗層材料沈積或施加至陶瓷材料上,藉此賦予及/或增強總成之A層之一或多種如本文描述之功能性質。在一些實施例中,由施加或沈積於如本文描述之陶瓷上之表塗層材料賦予之功能性相對於施加或沈積於不包括陶瓷之相同基板上之相同之材料之功能性係經增強。在一些實施例中,陶瓷材料及表塗層材料協同賦予之一或多種功能性質具有比由獨立沈積於相同基板表面上之陶瓷材料或表塗層材料賦予之相同功能性質更大之量級。
在一些實施例中,疏水功能性係由脂肪酸諸如硬脂酸或ScotchgardTM
(3M)提供。在一些實施例中,抗微生物功能性係由SmartShield抗微生物防護噴霧劑(Sylvane)提供。在一些實施例中,阻燃性功能性係由No Burn 1005織品防火(No-Burn, Inc.)或含有哈龍之化合物提供。在一些實施例中,親水功能性係由聚乙烯吡咯啶酮(PVP)、聚胺基甲酸酯、聚丙烯酸(PAA)、聚環氧乙烷(PEO)或多醣材料提供。
在某些非限制性實施例中,表塗層可包括塗料、塗料黏合劑、疏水材料、親水材料、金屬或含有金屬之化合物、顏料及/或著色劑或抗微生物劑。
在一些實施例中,表塗層係表面修飾之表塗層,其減小該表面上外部或內部流體之黏性阻力。在一些實施例中,將塗層沈積於包括奈米結構化塗料組合物及表面修飾之表塗層之表面上,其減小該表面上外部或內部流體之黏性阻力且進一步包括額外益處,諸如耐腐蝕性、耐結垢性、自清潔、傳熱特性、光學特性、化學惰性、其他有用性質或性質之組合。
在一些實施例中,表塗層係或含有抗微生物劑。例如,抗微生物劑可為電荷轉移化合物或破壞粒子跨細胞膜移動之藥劑(例如,第四胺)。在一些實施例中,該抗微生物劑係β-內醯胺、胺基糖苷、四環素、氯黴素、大環內酯、林可醯胺、磺醯胺、喹諾酮、多烯、唑或灰黃黴素。
在一些實施例中,表塗層係或含有塗料黏合劑。例如,該塗料黏合劑可為醇酸樹脂、丙烯酸樹脂、乙烯基-丙烯酸樹脂、乙酸乙烯酯/乙烯(VAE)、聚胺基甲酸酯、聚酯、三聚氰胺樹脂、環氧樹脂、矽烷或油。
在一些實施例中,陶瓷表面修飾材料係部分填充之多孔結構。例如,該等孔可用第二陶瓷材料(例如,不同於基板表面上之陶瓷材料之陶瓷材料)或用具有頭部基團及尾部基團之分子部分填充,例如,其中該頭部基團包括矽烷基、膦酸酯基、膦酸基、羧酸基、乙烯基、醇基、氫氧化物基、硫醇酯基、硫醇基及/或銨基(例如,第四銨基),且其中該尾部基團包括烴基、氟碳基、乙烯基、苯基、環氧基、丙烯酸基、丙烯酸酯基、羥基、羧酸基、硫醇基及/或第四銨基。
在一些實施例中,總成之至少一個B層賦予選自熱阻、電阻、結構支撐、機械墊充及流體轉移或其組合之一或多種結構及/或絕緣性質。在一些實施例中,總成之至少一個B層包括陶瓷材料,諸如玻璃纖維、鬆散陶瓷或其他無機材料。
無膠結陶瓷
如本文描述之層狀總成中之「A」層包括無膠結多孔陶瓷材料於基板上。此等陶瓷材料之非限制性實例係描述於PCT/US19/65978中,其係以全文引用之方式併入本文中。
本文描述之材料之層之總成(堆疊)之A層之基板係通常適用於用於該總成之應用之可撓性材料。在一些實施例中,該基板係編織材料,諸如(但不限於)不銹鋼合金、碳鋼合金或鋁合金編織材料。在一些實施例中,該基板係織物、聚合物(例如,聚醯胺、聚酯)、纖維素材料、天然材料(例如,棉、羊毛)或合成材料(例如,耐綸、PET)。在一些實施例中,該基板包括合成或天然纖維織物,其係編織、非編織或針織物。在一些實施例中,該基板包括金屬網、金屬篩或金屬布。在一些實施例中,該基板包括天然或合成聚合物膜或基板(例如,不一定編織成織物之薄(膜)或較厚(基板)聚合物(例如,塑膠)材料之塗層)。
在一些實施例中,無膠結陶瓷材料包括:每平方米預計基板面積約1.5 m2
至100 m2
、約10 m2
至約1500 m2
或約70 m2
至約1000 m2
之表面積;每公克陶瓷材料約15 m2
至約1500 m2
、或約50 m2
至約700 m2
之表面積;約5 nm至約200 nm、約2 nm至約20 nm或約4 nm至約11 nm之平均孔徑;高達約100微米、高達約50微米、高達約25微米、高達約20微米或約0.2微米至約25微米之厚度;約5%至約95%、約10%至約90%、約30%至約70%、約30%至約95%或大於約10%之孔隙率;如藉由壓汞法測定之約100 mm3
/g至約7500 mm3
/g之空隙體積;或其任何組合。
在一些實施例中,陶瓷材料(例如,其金屬氧化物、金屬氫氧化物及/或水合物)包括鋅、鋁、錳、鎂、鈰、銅、釓、鎢、錫、鉛及鈷中之一或多者。在一些實施例中,該陶瓷材料包括過渡金屬、II族元素、稀土元素(例如,鑭、鈰、釓、鐠、鈧、釔、釤或釹)、鋁、錫、鋅或鉛。
在一些實施例中,無膠結陶瓷表面修飾材料包括約0.5或1至約100微米、或約0.5微米至約20微米之厚度,或高達約50微米、或高達約25微米之厚度。在一些實施例中,該無膠結多孔陶瓷材料包括約0.2微米至約25微米之厚度。在一些實施例中,該厚度係至少約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微米中之任何一者。在一些實施例中,該厚度係約0.2至約0.5、約0.5至約1、約1至約5、約3至約7、約5至約10、約7至約15、約10至約15、約12至約18、約15至約20、約18至約25、約0.5至約15、約2至約10、 約1至約10、約3至約13、約0.5至約15、約0.5至約5、約0.5至約10或約5至約15微米中之任何一者。
在一些實施例中,無膠結陶瓷表面修飾材料包括每平方米預計基板面積約1.1 m2
至約100 m2
之表面積。在一些實施例中,該無膠結多孔陶瓷材料包括每平方米預計基板面積約10 m2
至約1500 m2
之表面積。在一些實施例中,該表面積係每平方米預計基板面積至少約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1500 m2
中之任何一者。在一些實施例中,該表面積係每平方米預計基板面積約10至約100、約50至約250、約150至約500、約250至約750、約500至約1000、約750至約1200、約1000至約1500、約70至約1000、約150至約800、約500至約900或約500至約1000 m2
中之任何一者。
在一些實施例中,無膠結陶瓷材料包括每公克陶瓷材料約15 m2
至約1500 m2
之表面積。在一些實施例中,該表面積係每公克陶瓷材料至少約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1500 m2
中之任何一者。在一些實施例中,該表面積係每公克陶瓷材料約15至約100、約50至約250、約150至約500、約250至約750、約500至約1000、約750至約1200、約1000至約1500、約50至約700、約75至約600、約150至約650或約250至約700 m2
中之任何一者。
在一些實施例中,無膠結陶瓷表面修飾材料係多孔的且包括在約2 nm至約50 nm之範圍內之中孔平均孔徑。在其他實施例中,該等平均孔徑在約50 nm至約1000 nm之範圍內。在一些實施例中,該無膠結多孔陶瓷材料包括約2 nm至約20 nm之平均孔徑。在一些實施例中,該平均孔徑係至少約2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20 nm中之任何一者。在一些實施例中,該平均孔徑係約2至約5、約4至約9、約5至約10、約7至約12、約9至約15、約12至約18、約15至約20、約4至約11、約5至約9、約4至約8或約7至約11 nm中之任何一者。
在一些實施例中,無膠結陶瓷表面修飾材料係多孔的,具有約5%至約95%之孔隙率。在一些實施例中,該孔隙率可為至少約或大於約5%、10%、15%、20%、25%、30%、35%、40%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%中之任何一者。在一些實施例中,該孔隙率係約10%至約90%、約30%至約90%、約40%至約80%或約50%至約70%。
在一些實施例中,無膠結多孔表面修飾材料係多孔的,具有約1至10,000毫達西之滲透性。在一些實施例中,該滲透性可為至少約1、10、100、500、1000、5000或10,000毫達西中之任何一者。在一些實施例中,該滲透性係約1至約100、約50至約250、約100至約500、約250至約750、約500至約1000、約750至約2000、約1000至約2500、約2000至約5000、約3000至約7500、約5000至約10,000、約1至約1000、約1000至約5000或約5000至約10,000毫達西。
在一些實施例中,無膠結陶瓷材料係多孔的且如藉由壓汞法測定,包括約100 mm3
/g至約7500 mm3
/g之空隙體積。在一些實施例中,該空隙體積係至少約100、200、300、400、500、600、700、800、900、1000、1500、2000、2500、3000、3500、4000、4500、5000、5500、6000、6500、7000或7500 mm3
/g中之任何一者。在一些實施例中,該空隙體積係約100至約500、約200至約1000、約400至約800、約500至約1000、約800至約1500、約1000至約2000、約1500至約3000、約2000至約5000、約3000至約7500、約250至約5000、約350至約4000、約400至約3000、約250至約1000、約250至約2500、約2500至約5000或約500至約4000 mm3
/g中之任何一者。
陶瓷沈積層係經設計以賦予如本文描述之材料之總成之層一或多種功能特性及/或可經設計以為功能化表塗層提供結合表面。
製造陶瓷材料之方法
如本文描述之陶瓷表面修飾材料諸如無膠結陶瓷多孔表面修飾材料可藉由一種方法產生,該方法包括使清潔基板(例如,織物基板)以具有一或多種金屬鹽之水溶液浸漬或以其他方式接觸一定時間以在該基板上達成多孔塗料組合物之所需厚度。該溶液亦可含有螯合劑或錯合物形成劑。pH、溫度及沈積時間(例如,約5分鐘至約300分鐘)適用於待產生之表面修飾材料之所需厚度、形態學及表面孔隙率。該溶液之pH可在1至12之範圍內調整以藉由添加酸性或鹼性材料調整表面修飾之特性(例如,所需晶體結構及/或表面孔隙率)。金屬鹽可包括(例如)鎂、鋁、鈰、鐵、鈷、釓、錳、鎢、鋅、釩、鈦及/或錫之鹽。該等鹽可為具有以下之陰離子之金屬陽離子鹽,例如,硫酸根、硝酸根、氯化物或乙酸根。在其他實施例中,鈉陽離子鹽係與金屬陰離子(諸如,例如,錫酸鈉)一起使用。在一些實施例中,金屬鹽濃度係於水溶液中約1 mM至約5 M。在一些實施例中,在約1 mM至約5 M之濃度下包括約1 mM至約5 M濃度之螯合劑或錯合物形成劑,諸如,例如,檸檬酸、尿素、二胺、三胺或四胺、硫甘油、油酸或其他脂肪酸、多元醇、吐溫80或其他表面活性劑。可視需要包括pH控制化學物質及緩衝劑。
在一些實施例中,基板係藉由清洗及沖洗及各種金屬清潔溶液或針對特定基板概述之清潔溶液進行清潔以移除鬆散且輕微黏附之碎屑。針對成功移除鬆散且輕微黏附之碎屑可接受各種處理條件。
在一些實施例中,基板係使用基於鹼性之清潔溶液處理以皂化並自該基板移除脂肪及油。一項實例係使用pH約11或更大之於水溶液中之燒鹼。其他實施例可使用脫脂之替代方式,諸如基於蒸氣或溶劑之方法或專有清潔劑。針對成功移除表面脂肪及油可接受各種處理條件。
在一些實施例中,基板係經進一步製備以使用已知方法均質化表面用於通過基板材料之鹼性蝕刻處理該表面。此處理產生表面氧化物及表面氫氧化物、反應產物及金屬間材料,其等中之一些不溶於蝕刻溶液中且必須藉由沖洗、機械方式或藉由在工業中稱為除汙之方法自該基板移除。除汙或脫氧溶液通常包括酸溶液,諸如鉻酸、硫酸、硝酸或磷酸或其中之組合。可採用硫酸鐵溶液。除汙溶液藉由增溶或機械移除(例如,含有矽之顆粒)移除反應產物、氧化物、氫氧化物及金屬間材料。許多專有表面製備材料可購買獲得。可成功採用他表面製備選擇諸如酸蝕刻、電拋光、超聲處理或移除基板氧化物、氫氧化物、反應產物及金屬間化合物之其他表面整理處理預備方法。針對成功表面製備基板並移除汙漬可接受各種處理條件。
在其他實施例中,用於後續處理之替代表面製備包括曝露於強氧化劑(諸如過硫酸鹽、次氯酸鹽、高錳酸鹽、氧化酸、UV/臭氧或氧電漿)以活化該基板。
在一些實施例中,基板係使用一或多個處理步驟處理,其中該基板與沖洗液反應以形成奈米結構化材料。本文描述之溶液係水基溶液且於該水溶液中包括約1 mM至約5 M之金屬鹽及/或包括約1 mM至約5 M之濃度之螯合劑或錯合物形成劑諸如多元醇、聚醚、尿素、二級或更高級胺、二胺、三胺或四胺。不包括不同水槽深度之靜水壓之處理條件介於65至200 kPa之範圍內,且取決於濃度及組成,此等溶液之跨液相平衡之溫度介於-20℃至190℃之範圍內。
在一些實施例中,自溶液移除基板並在約100℃至約1000℃之溫度下加熱約0小時至約5小時之週期。在一些實施例中,自該溶液移除該基板並在約100℃至約1000℃之溫度下加熱約0小時至約24小時之週期以自該基板及金屬氧化物表面修飾移除大體上所有水。可使用受控常壓爐處理以進一步修飾表面條件。
視需要,將基板浸漬於功能分子與適當溶劑之稀釋溶液(例如,小於約2%或約0.001%至約2%)內,該稀釋溶液可化學結合至陶瓷表面使得孔經功能化但保持打開。
在一些實施例中,該方法包括用一、二或更多種材料部分填充孔。例如,該方法包括(a)取出具有表面固定之多孔陶瓷表面之基板,浸漬於可化學結合至陶瓷表面使得孔經功能化但保持打開之功能分子之稀釋溶液內,及/或(b)將該基板浸漬於另一溶液內以於孔內及在如上文描述之表面上沈積更多陶瓷,並如之前加熱以驅除水;及視需要重複(a)或(b)或(a)及(b)以於各種功能分子及/或金屬氧化物之孔內堆疊多個層。可採用引入第一或第二材料之其他非限制性方法,諸如噴塗、傾倒、滴落或氣相沈積。
在一些實施例中,該方法包括用一或多種材料完全填充孔。例如,該方法包括取出具有表面固定之多孔陶瓷表面之基板,並將其浸漬於可化學結合至陶瓷表面之功能分子之更濃縮溶液(例如,約1%至約20%)內,使得該等孔經物質填充;及/或將該基板浸漬於如上文描述之另一金屬鹽溶液內並驅除如上文描述之水以完全填充該等孔。可採用引入孔填充材料之其他非限制性方法,諸如噴塗、傾倒、滴落、霧化或氣相沈積。
例示性實施例
下文提供如本文描述之材料之總成之例示性實施例。材料之組合及及用途之應用係作為實例提供且無意限制。醫用繃帶
如本文描述之總成可經組態用於醫用繃帶中。該繃帶係經設計以維持清潔並避免外部水分通過具有超疏水性質之外層,吸附層自傷口移除水分,墊充層以為傷口提供保護,及有助於保持傷口乾燥之親水內層。該等層中之各者可用抗微生物性質或癒合劑、軟膏或其他材料進一步功能化。
如圖1中顯示,此總成之實例包含包括超疏水陶瓷於合成基板材料(例如,耐綸或PET)上之At
層及包含包括超親水陶瓷於天然基板材料(棉)上之Ab
層。介於At
與Ab
層之間之B層提供吸收性、結構及墊充性質。 高性能外衣
如本文描述之總成可經組態用於外衣(諸如高性能外衣)中。可提供內層,該內層橫向芯吸水分並通過該層至周圍頂層、絕緣層及具有高水蒸氣輸送率及亦排斥水及油(例如)以促進清潔之外層。
如圖2中顯示,此總成之實例包含包括超疏水陶瓷於合成基板(例如,耐綸或PET)上之At
層及包含包括超疏水陶瓷於合成基板(例如,耐綸或PET)上之Ab
層。介於At
與Ab
層之間之B層提供熱絕緣性質。管道絕緣
如本文描述之總成可經組態以用作管道絕緣或管道保護。該總成係經設計為高溫熱絕緣外套,具有疏水「周圍環境側」襯墊及親水「熱側」襯墊,該襯墊圍繞並與該管道接觸。例如,該周圍環境側襯墊可由具有陶瓷(例如,奈米結構化)表面及疏水功能性之金屬網(例如,不銹鋼網)構成,其藉由防止水分進入絕緣內維持絕緣性能。該熱側襯墊可由具有顯示芯吸水分並促進蒸發之毛細管作用之陶瓷(例如,奈米結構化)表面之金屬網構成。此系統之技術及商業優勢藉由組合金屬網層與阻隔性層以較小之成本提供與現存絕緣外套材料相同之優勢。與金屬箔相反,該系統亦可比現存基於特氟龍之解決方案具有更高溫度操作,且該系統係外部防水但蒸氣仍可透過。
如圖3中顯示,此總成之實例包含包括超疏水陶瓷於金屬網基板上之At
層及包含包括超親水陶瓷於金屬網基板上之Ab
層。介於At
與Ab
層之間之B層提供熱絕緣性質。醫用石膏
作為上文描述之醫用繃帶應用之拓展,如本文描述之總成可經組態以用作醫用石膏。可向層之堆疊之底部提供額外抗微生物層,以防止感染及/或以防止與難以清潔相關聯之氣味,導致微生物入侵。亦可添加額外層。
如圖4中顯示,此總成之實例包含包括超疏水陶瓷於合成基板材料(例如,耐綸或PET)上之At
層及包括總成之底表面及包括抗微生物陶瓷於合成基板材料(例如,耐綸或PET)上之Ab
層。包括總成之底表面之Ab
層上之Ab
層包括超親水陶瓷於合成基板材料(例如,耐綸或PET)上。介於At
與Ab
層之間之B層提供結構及墊充性質。醫療 / 手術服
如本文描述之總成可經組態用於醫療/手術裝置或服裝中。該總成係經設計以透氣(高水分輸送率)並抗微生物且耐飛濺(拒水劑),提供阻隔性性質而不犧牲舒適性。
如圖5中顯示,此總成之實例包含包括超疏水陶瓷於合成基板材料(例如,耐綸或PET)上之At
層及包括抗微生物陶瓷於合成(例如,耐綸或PET)或天然(例如,棉)基板材料上之Ab
層。用途之其他應用
其中可採用如本文描述之材料之總成之應用之額外非限制性實例包括(其中層自該總成之底表面層至頂表面層(周圍環境曝露)列舉):
過濾/分離:粒徑排阻(保留) (A) -結構完整性(B) -抗微生物(A)
包裝材料:水分輸送(A) -結構完整性(B) -墊充(B) -拒水劑(A)
醫院床上用品:墊充(B) -水分輸送(A) -透氣性(A) -吸濕性(A) -抗微生物(A) -
防護面具:水分輸送(A) -透氣性(A) -抗微生物(A) -耐化學性(A) -拒水劑(A)
防護外衣:水分輸送(A) -透氣性(A) -耐化學性(A) -拒水劑(A) -熱絕緣(B) -結構(B) -阻燃劑
建築織物:水分輸送(A) -透氣性(A) -耐化學性(A) -拒水劑(A) -熱絕緣(B) -阻燃劑(A) -顏色(A) - UV穩定性(A)
土工織物:水分輸送(A) -透氣性(A) -耐化學性(A) -拒水劑(A) -熱絕緣(B) -結構(B) -環境穩定性(A)
上文描述之製品及用途之應用中層之順序可與彼等例示者不同,及在一些實施例中,如本文描述之多種功能性可組合至單一層內。
下列實例意欲闡述而非限制本發明。
實例實例 1 :測試層狀堆疊性能之方法
採用下列方法以表徵如本文描述之材料之總成。
層之接觸角係使用不濡液滴方法藉由將10微升液滴分配至表面上測定。使用位於與該表面相同高度之照相機以捕獲液滴頭之影像。該接觸角係藉由量測該表面與接觸表面之液體-蒸氣界面之間之角度測定。此過程重複三次及記錄之接觸角係三次獨立量測之平均值。
層之堆疊之蒸氣透過率係如下測定。將各層切割成相同尺寸並聚集。將裝滿已知質量之乾燥劑之容器密封至該堆疊之底層之底側。對於由多個層構成之堆疊,該等層沿其等邊緣密封在一起,因此蒸氣進入該堆疊之唯一方法係通過該堆疊之頂層。將該堆疊及乾燥劑放置於具有受控溫度及濕度之室內。每30分鐘,將樣品聚集以測定來自該室之水蒸氣已通過該等層並吸附至該乾燥劑上之量。倘若該乾燥劑之質量增加10%,則停止該測試並測定每單位面積每單位時間內蒸氣傳輸通過各堆疊之速率。
水柱突破壓力係如下測定。將內徑為12.7 mm之垂直管密封至堆疊之頂層。對於由多個層構成之堆疊,該等層沿其等邊緣密封在一起,使得水可僅藉由分別流動通過頂層及底層進入或離開該堆疊。管係藉由向該管之側面向下分配水進行填充,以免將水直接衝擊在該堆疊之頂層上。增量式分配水使得水柱之高度每次增加1 cm,接著5秒週期,在此期間不分配水。管柱係以此方式填充直至該水柱之高度開始下降,指示該管柱中之水穿透該材料堆疊。記錄各樣品之最大填充高度。實例 2
如下製備如下文實例中描述之功能化網材料。首先將網基板浸入丙酮浴中及然後浸入IPA浴中以移除任何殘餘之油。然後容許將零件空氣乾燥15分鐘。接著將該等網基板放置於含有20至250 mM金屬硝酸鹽或硫酸鹽或混合金屬硝酸鹽或硫酸鹽及相似莫耳量之二胺、三胺或四胺之生產浴中,其等容許在50至85℃之反應溫度下反應並沈降。將該等總成維持在該浴中歷時在約5分鐘至約3小時之範圍內之時間。將該等總成移除並排乾及放置於烘箱內以在50至600℃熱處理下乾燥及/或煆燒數分鐘至數小時。視需要,此沈積及煆燒步驟可視需要重複。冷卻後,該等零件係如下文實例中描述進一步處理及/或測試。實例 3
用包含氧化錳之陶瓷材料塗覆不銹鋼網層,藉此產生表面親水性質。水接觸角經由不濡液滴方法量測為小於5度。將該層放置於具有約1 cm去離子水之杯中並使層狀樣品之部分與該去離子水接觸。2分鐘後,如由可見濕線觀察到之毛細管上升經測定為該樣品在液位上方約3 cm。毛細管上升係如PCT申請案第PCT/US19/65978號(參見,例如,圖1A至1C)中描述測定。蒸氣透過率係經測定為130 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 4
用包含氧化錳之陶瓷材料塗覆不銹鋼網層。然後使用十六烷基膦酸於異丙醇中之稀釋溶液將表面功能化,藉此產生表面疏水性質。水接觸角係經由不濡液滴方法量測為151度。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,液位上方之表面無明顯水上升。蒸氣透過率係經測定為145 g/hr/m2
。水柱突破壓力係經測定為25 cm水頭。實例 5
測試無任何表面製備之不銹鋼網層。水接觸角係經由不濡液滴方法量測為20度。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,液位上方之表面無明顯水上升。蒸氣透過率係經測定為152 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 6
測試厚度為5.08 cm及熱絕緣值為R-6.7之玻璃纖維絕緣層。蒸氣透過率係經測定為48 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 7
測試兩個層之堆疊。如實例3中描述,頂層係疏水不銹鋼網。如實例5中描述,底層係玻璃纖維絕緣。該等兩個層係藉由使用卡普頓(Kapton)膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為43 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為23 cm水頭。實例 8
測試兩個層之堆疊。如實例4中描述,頂層係無任何表面製備之不銹鋼網。如實例5中描述,底層係玻璃纖維絕緣。該等兩個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為49 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 9
測試三個層之堆疊。如實例3中描述,頂層係疏水不銹鋼網。如實例5中描述,中間層係玻璃纖維絕緣。如實例2中描述,底層係親水不銹鋼網。該等三個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為53 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為22 cm水頭。實例 10
測試三個層之堆疊。如實例4中描述,頂層係無任何表面改變之不銹鋼網。如實例5中描述,中間層係玻璃纖維絕緣。如實例4中描述,底層係無任何表面改變之不銹鋼網。整個堆疊之蒸氣透過率係經測定為55 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 11
用包含氧化鎂之陶瓷材料塗覆鋁網層,藉此產生表面親水性質。水接觸角係經由不濡液滴方法量測為小於5度。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,毛細管上升係經測定為液位上方約5 cm。蒸氣透過率係經測定為150 g/hr/m2
。水柱突破壓力係經測試,該層無法支撐水柱之任何可量測高度。實例 12
用包含氧化鎂之陶瓷材料塗覆鋁網層。然後使用十六烷基膦酸於異丙醇中之稀釋溶液將表面功能化,藉此產生表面疏水性質。水接觸角係經由不濡液滴方法量測為160度。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,液位上方之表面無明顯水上升。蒸氣透過率係經測定為150 g/hr/m2
。水柱突破壓力係經測定為100 cm水頭。實例 13
測試無任何表面製備之鋁網層。水接觸角係經由不濡液滴方法量測為20度。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,液位上方之表面無明顯水上升。蒸氣透過率係經測定為153 g/hr/m2
。水柱突破壓力係經測試,且該層無法支撐水柱之任何可量測高度。實例 14
測試兩個層之堆疊。如實例11中描述,頂層係疏水鋁網。如實例5中描述,中間層係玻璃纖維絕緣。該等兩個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為48 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為62 cm水頭。實例 15
測試兩個層之堆疊。如實例12中描述,頂層係無任何表面製備之鋁網。如實例5中描述,中間層係玻璃纖維絕緣。該等兩個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為48 g/hr/m2
。水柱突破壓力係經測試,且該層無法支撐水柱之任何可量測高度。實例 16
測試三個層之堆疊。如實例11中描述,頂層係疏水鋁網。如實例5中描述,中間層係玻璃纖維絕緣。如實例10中描述,底層係親水鋁網。該等三個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為48 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為62 cm水頭。實例 17
測試三個層之堆疊。如實例12中描述,頂層係無任何表面改變之鋁網。如實例5中描述,中間層係玻璃纖維絕緣。如實例12中描述,底層係無任何表面改變之鋁網。該等三個層係藉由使用卡普頓膠帶以不壓縮該絕緣層之方式密封邊緣連接在一起。整個堆疊之蒸氣透過率係經測定為47 g/hr/m2
。水柱突破壓力係經測試,且該層無法支撐水柱之任何可量測高度。實例 18
測試厚度為0.005 cm之聚酯膜之水分阻隔性層。蒸氣透過率係經測定為1 g/hr/m2
。水柱突破壓力係經測定為大於200 cm水頭。實例 19
測試兩個層之堆疊。如實例16中描述,頂層係聚酯膜。如實例4中描述,底層係玻璃纖維絕緣。蒸氣透過率係經測定為1 g/hr/m2
。水柱突破壓力係經測定為大於200 cm水頭。實例 20
用包含氧化鎂之陶瓷材料塗覆40 d (40丹尼)編織聚醯胺織物層,藉此產生表面親水性質。水接觸角係經由不濡液滴方法量測為小於5度。蒸氣透過率係經測定為175 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 21
用包含氧化鎂之陶瓷材料塗覆40d編織聚醯胺織物層。然後使用十六烷基膦酸於異丙醇中之稀釋溶液將表面功能化,藉此產生表面疏水性質。蒸氣透過率係經測定為170 g/hr/m2
。水柱突破壓力係經測定為55 cm水頭。實例 22
測試無任何表面製備之40d編織聚醯胺織物層。蒸氣透過率係經測定為170 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 23
測試厚度為1.1 cm及熱絕緣值為R-1.6之新雪麗(Thinsulate) G80層。蒸氣透過率係經測定為100 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 24
測試兩個層之堆疊。如實例19中描述,頂層係疏水40d編織聚醯胺織物。如實例21中描述,底層係新雪麗G80。整個堆疊之蒸氣透過率係經測定為100 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為55 cm水頭。實例 25
測試兩個層之堆疊。如實例20中描述,頂層係無任何表面製備之40d編織聚醯胺織物。如實例21中描述,底層係新雪麗G80。整個堆疊之蒸氣透過率係經測定為100 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 26
測試三個層之堆疊。如實例19中描述,頂層係疏水40d編織聚醯胺織物。如實例21中描述,中間層係新雪麗G80。如實例18中描述,底層係親水40d編織聚醯胺織物。整個堆疊之蒸氣透過率係經測定為90 g/hr/m2
。整個堆疊之水柱突破壓力係經測定為50 cm水頭。實例 27
測試三個層之堆疊。如實例20中描述,頂層係無任何表面改變之40d編織聚醯胺織物。如實例21中描述,中間層係新雪麗G80。如實例20中描述,底層係無任何表面改變之40d編織聚醯胺織物。整個堆疊之蒸氣透過率係經測定為90 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 28
在酸蝕刻中點蝕不銹鋼網層及然後用無膠結結構氧化錳陶瓷表面修飾塗覆,在約60℃至80℃之溫度下將其沈積於硝酸錳及相似量之六亞甲四胺或尿素之25至75 mM水溶液中歷時約60至240分鐘之時間週期。然後在約400℃至600℃之溫度下將該網煆燒約1小時,產生表面親水性質。水接觸角係經由不濡液滴方法量測為小於5度。將該網放置於具有約1 cm去離子水之杯中。2分鐘後,毛細管上升係經測定為液位上方約3 cm。毛細管上升係如PCT申請案第PCT/US19/65978號(參見,例如,圖1A至1C)中描述測定。蒸氣透過率係經測定為130 g/hr/m2
。水柱突破壓力係經測試且該層無法支撐水柱之任何可量測高度。實例 29
用包含氧化鎂之陶瓷材料塗覆鋁網層,在約60℃至80℃之溫度下將其沈積於硝酸鎂及相似量之六亞甲四胺之25至75 mM水溶液中歷時約30至90分鐘之時間週期。然後在約300℃至600℃之溫度下將該網煆燒約1小時,藉此產生表面親水性質。水接觸角係經量測為小於5度經由不濡液滴方法。將該層放置於具有約1 cm去離子水之杯中。2分鐘後,毛細管上升係經測定為液位上方約5 cm。蒸氣透過率係經測定為約150 g/hr/m2
。水柱突破壓力係經測試;該層無法支撐水柱之任何可量測高度。實例 30
用約250 nm鋁噴濺編織聚酯織物及編織耐綸織物。將該織物切割成小塊並用3種不同之陶瓷材料塗覆:a)基於氧化鎂/氫氧化鎂之陶瓷,b)及基於氧化錳/氫氧化錳之陶瓷,c)及氧化鋅/氫氧化鋅之陶瓷。所有三種陶瓷均含有一定量之氧化鋁/氫氧化鋁。該等陶瓷係以與實例1中描述之方法相似之方法沈積(針對該陶瓷中發現之各個別陽離子,使用2+金屬硝酸鹽或金屬硫酸鹽)。測試樣品之接觸角並顯示小於15度之接觸角。然後將經陶瓷修飾之織物浸塗於十六烷基膦酸於異丙醇中或十六烷基三乙氧基矽烷於乙醇中之稀釋浴(0.1%至1%)內。在矽烷之情況下,有時使用少量之乙酸觸媒。然後再次量測樣品之接觸角並顯示約150至160度之接觸角。水蒸氣穿透率係於未經修飾之織品之量測誤差內。實例 31
用基於氧化鋅之陶瓷藉由在室溫下將該織物在約200至500 mM硫酸鋅、約50至150 mM過硫酸鉀及約1.2至1.7莫耳氫氧化銨之浴中浸漬約5至60分鐘塗覆編織聚酯、聚醯胺及Tencel織物。氧化鎳沈積物亦藉由用硫酸鎳代替硫酸鋅於聚酯上產生。氧化錳沈積物亦藉由用硫酸錳代替硫酸鋅及用高錳酸鹽代替過硫酸鹽於聚酯上產生。然後在約105℃至約140℃之溫度下將此等樣品乾燥約1至2小時之持續時間。測試該等樣品之接觸角並顯示小於15度之接觸角。然後將經陶瓷修飾之織物浸塗於十六烷基膦酸於異丙醇中或十六烷基三乙氧基矽烷於乙醇中之稀釋浴(0.1%至1%)內。在矽烷之情況下,有時使用少量之乙酸觸媒。然後再次量測該等樣品之接觸角並顯示約150至160度之接觸角。實例 32
在約室溫至約80℃之溫度下將編織聚醯胺及聚酯織物浸入約5至200 mM之高錳酸鉀及約10至400 mM之氫氧化銨之水浴中歷時約5分鐘至約1小時。高錳酸鹽與氫氧化銨之典型比率係約1至2。然後容許將基板乾燥及然後用包含氧化錳/氫氧化錳、氧化鋅/氫氧化鋅或氧化鎂/氫氧化鎂之結構陶瓷層沈積,藉由在約60℃至80℃之溫度下將該基板浸漬於金屬(Mn、Zn或Mg)硝酸鹽及相似量之六亞甲四胺之25至150 mM水溶液中歷時約5至90分鐘之時間週期。然後在約100℃至250℃之溫度下將該網乾燥約1小時。該等樣品之此等接觸角係經量測並測定為小於約15度。然後將經陶瓷修飾之織物浸塗於十六烷基膦酸於異丙醇中或十六烷基三乙氧基矽烷於乙醇中之稀釋浴(0.1%至1%)內。在矽烷之情況下,有時使用少量之乙酸觸媒。然後再次量測該等樣品之接觸角並顯示約150至160度之接觸角。
儘管出於清楚瞭解之目的,已藉由闡述及實例相當詳細地描述前述發明,但熟習此項技術者應知曉可實踐某些變化及修飾而不背離本發明之精神及範圍,本發明之精神及範圍係以隨附申請專利範圍描繪。因此,描述不應解釋為限制本發明之範圍。
本文引用之所有公開案、專利及專利申請案係出於所有目的以全文引用之方式併入本文中且該引用之程度就如同將各個別公開案、專利或專利申請案以引用之方式明確且個別地併入本文中。
圖1顯示用於醫用繃帶中之材料之層之總成之例示性實施例。
圖2顯示用於高性能外衣中之材料之層之總成之例示性實施例。
圖3顯示用於管道絕緣中之材料之層之總成之例示性實施例。
圖4顯示用於醫用石膏中之材料之層之總成之例示性實施例。
圖5顯示用於醫療/手術服中之材料之層之總成之例示性實施例。
Claims (43)
- 一種包含頂表面及底表面之材料之總成,其包含: (a)包含一或多種功能性質之材料之x個 At 層,其中該等At 層包含包括該頂表面之最上層; (b)包含一或多種功能性質之材料之y個 Ab 層,其中該等Ab 層包含包括該底表面之最底層;及 (c)在x個 A層與y個 A層之間的絕緣或結構材料之z個 B層, 其中x、y及z係相同或不同的層數, 其中該等At 層及該等Ab 層各包含位於基板上之無膠結陶瓷材料, 且其中位於各At 層及/或各Ab 層上之該陶瓷材料係相同或不同的。
- 如請求項1之總成,其中該無膠結陶瓷材料主要係結晶質。
- 如請求項1之總成,其中該陶瓷材料包含金屬氧化物、金屬氧化物之水合物、金屬氫氧化物及/或金屬氫氧化物之水合物。
- 如請求項3之總成,其中該陶瓷材料包含金屬氫氧化物,且其中該金屬氫氧化物中之至少一部分包含層狀雙氫氧化物。
- 如請求項1至4中任一項之總成,其中該陶瓷係奈米結構化陶瓷。
- 如請求項1之總成,其中用於至少一個At 層及/或至少一個Ab 層之該基板包含選自以下之材料:作為編織、非編織或針織物之合成或天然織物、金屬網、金屬篩、金屬布、合成或天然聚合物材料或膜。
- 如請求項6之總成,其中用於至少一個At 層之該基板及用於至少一個Ab 層之該基板,或用於至少兩個At 層之該基板,或用於至少兩個Ab 層之該基板包含選自以下之不同材料:作為編織、非編織或針織物之合成或天然織物、金屬網、金屬篩、金屬布、合成或天然聚合物材料或薄膜。
- 如請求項1之總成,其中各At 及/或Ab 層包含選自以下之一或多種功能性質:冰或冷凝物操作、防冰、防霜凍、超疏水性、超親水性、抑制微生物生長、耐腐蝕性、電磁調製、熱調製、阻燃性、透氣性、動態抗風性、顏色、吸收性、阻隔性、維護性質、美學性質、氣味控制、耐磨性、機械性質、表面摩擦、手感、耐久性或其組合。
- 如請求項8之總成,其中x及/或y係大於1,且其中各At 及/或Ab 層包含與其他At 及/或Ab 層不同之功能性質。
- 如請求項8之總成,其中包含該頂表面之最上層及包含該底表面之最底層包含相同之功能性質。
- 如請求項8之總成,其中包含該頂表面之最上層及包含該底表面之最底層包含不同之功能性質。
- 如請求項1之總成,其中至少一個At 及/或至少一個Ab 層包含賦予一或多種功能性質之表塗層材料,且其中由該表塗層材料賦予之至少一種功能性質之量級比由直接沈積於不包含該陶瓷材料之相同基板上之相同表塗層材料所賦予之相同功能性質更大。
- 如請求項1之總成,其中至少一個At 及/或至少一個Ab 層包含表塗層材料,且其中該陶瓷材料及該表塗層材料協同賦予之一或多種功能性質之量級比由獨立沈積於相同基板表面上之該陶瓷材料或該表塗層材料所賦予之相同功能性質更大。
- 如請求項1之總成,其中位於至少一個At 及/或至少一個Ab 層上之該無膠結陶瓷材料係部分填充之多孔結構。
- 如請求項14之總成,其中該陶瓷材料之孔係經第二陶瓷材料或經具有頭部基團及尾部基團之分子部分填充。
- 如請求項1之總成,其中各B層包含選自以下之一或多種結構性質:熱阻、電阻、結構支撐、機械墊充及流體輸送特性或其組合。
- 如請求項1之總成,其中一或多個B層包含選自以下之陶瓷材料:玻璃纖維、鬆散陶瓷及其他無機材料。
- 如請求項1至4及6至17中任一項之總成,其中將該總成併入以下內:高性能外衣、醫用繃帶、醫用石膏、手術服、過濾或分離介質、包裝材料、醫院床上用品、吸收性織物、防護面具、防護外衣、建築織物或土工織物。
- 一種管道絕緣或保護材料,其包含如請求項1之總成, 其中一或多個At 層包含疏水或超疏水功能性質,其中一或多個B層包含熱絕緣、保護或結構性質,且 其中一或多個Ab 層包含親水或超親水功能性質。
- 如請求項19之管道絕緣或保護材料, 其中該總成圍繞管道, 其中該最底Ab 層係與該管道接觸,及 其中該最上At 層係與周圍環境接觸。
- 如請求項19或20之管道絕緣或保護材料,其中一或多個At 及/或一或多個Ab 層包含陶瓷塗覆之編織材料。
- 如請求項21之管道絕緣或保護材料,其中該編織材料係選自:不銹鋼合金編織材料、碳鋼合金編織材料、鋁合金編織材料及織物。
- 如請求項19或20之管道絕緣或保護材料,其中至少一個B層包含選自以下之材料:玻璃纖維、碳化矽、陶瓷纖維絕緣、聚矽氧或聚矽氧發泡體、礦棉、玄武岩、氣泡玻璃、聚醯亞胺、矽酸鈣及二氧化矽。
- 一種管道,其由如請求項19至23中任一項之管道絕緣或保護材料包圍。
- 一種織物材料,其包含如請求項1之總成, 其中一或多個At 層包含疏水或超疏水功能性質,其中一或多個B層包含熱絕緣、保護或結構性質,且 其中一或多個Ab 層包含親水或超親水功能性質。
- 如請求項25之織物材料,其中一或多個At 及/或一或多個Ab 層之該基板包含編織材料。
- 如請求項26之織物材料,其中該編織材料係選自:織物、聚醯胺、聚酯、聚合物基板或膜、纖維素材料、棉、羊毛、不銹鋼合金編織材料及鋁合金編織材料。
- 如請求項25之織物材料,其中一或多個At 及/或一或多個Ab 層之該基板包含耐綸或聚對酞酸乙二酯(PET)。
- 如請求項25至28中任一項之織物材料,其中一或多個B層包含選自以下之材料:聚酯、毛片、羊毛、羽毛、絨毛及其他主要有機材料。
- 一種包含頂表面及底表面之材料之總成,其包含: (a)包含一或多種功能性質之材料之x個 A層,其中該等A層包含包括該頂表面之最上層, 其中該等A層各包含位於基板上之無膠結陶瓷材料;及 (b)絕緣或結構材料之z個 B層, 其中該等B層包含包括該底表面之最底層,且 其中x及z係相同或不同的層數。
- 一種包含頂表面及底表面之材料之總成,其包含: (a)包含一或多種功能性質之材料之x個 At 層,其中該等At 層包含包括該頂表面之最上層;及 (b)包含一或多種功能性質之材料之y個 Ab 層,其中該等Ab 層包含包括該底表面之最底層, 其中該等At 層及該等Ab 層各包含位於基板上之無膠結陶瓷材料, 其中位於該等At 層上之陶瓷材料不同於位於該等Ab 層上之陶瓷材料, 且其中x及y係相同或不同的。
- 如請求項30或31之總成,其中該陶瓷材料主要係結晶質。
- 如請求項30或31之總成,其中該陶瓷材料包含金屬氧化物、金屬氧化物之水合物、金屬氫氧化物及/或金屬氫氧化物之水合物。
- 如請求項33之總成,其中該陶瓷材料包含金屬氫氧化物,且其中該金屬氫氧化物中之至少一部分包含層狀雙氫氧化物。
- 如請求項30或31之總成,其中該陶瓷係奈米結構化陶瓷。
- 如請求項30之總成,其中至少一個A層包含賦予一或多種功能性質之表塗層材料,且其中由該表塗層材料所賦予之至少一種功能性質之量級比由直接沈積於不包含該陶瓷材料之相同基板上之相同表塗層材料所賦予之相同功能性質更大。
- 如請求項30之總成,其中至少一個A層包含表塗層材料,且其中該陶瓷材料及該表塗層材料協同賦予之一或多種功能性質之量級比由獨立沈積於相同織物表面上之該陶瓷材料或該表塗層材料所賦予之相同功能性質更大。
- 如請求項30之總成,其中位於至少一個A層上之該無膠結陶瓷材料係部分填充之多孔結構。
- 如請求項38之總成,其中該陶瓷材料之孔係經第二陶瓷材料或經具有頭部基團及尾部基團之分子部分填充。
- 如請求項31之總成,其中至少一個At 及/或至少一個Ab 層包含賦予一或多種功能性質之表塗層材料,且其中由該表塗層材料所賦予之至少一種功能性質之量級比由直接沈積於不包含該陶瓷材料之相同基板上之相同表塗層材料所賦予之相同功能性質更大。
- 如請求項31之總成,其中至少一個At 及/或至少一個Ab 層包含表塗層材料,且其中該陶瓷材料及該表塗層材料協同賦予之一或多種功能性質之量級比由獨立沈積於相同織物表面上之該陶瓷材料或該表塗層材料所賦予之相同功能性質更大。
- 如請求項31之總成,其中位於至少一個At 及/或至少一個Ab 層上之該無膠結陶瓷材料係部分填充之多孔結構。
- 如請求項42之總成,其中該陶瓷材料之孔係經第二陶瓷材料或經具有頭部基團及尾部基團之分子部分填充。
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CN109321803B (zh) * | 2018-11-30 | 2021-03-23 | 苏州艾默特材料技术有限公司 | 一种具有多孔陶瓷涂层的加热元件 |
BR112021011408A2 (pt) * | 2018-12-12 | 2021-08-31 | Nelumbo Inc. | Materiais de modificação de superfície cerâmica e métodos de uso destes |
CN109761638A (zh) * | 2019-02-15 | 2019-05-17 | 江苏埃梯恩膜过滤技术有限公司 | 一种在金属、陶瓷、搪瓷或玻璃基材上制备多孔陶瓷层的方法 |
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