CN104703934A - 孔中包含光催化微粒的介孔无机涂层 - Google Patents
孔中包含光催化微粒的介孔无机涂层 Download PDFInfo
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- CN104703934A CN104703934A CN201380041026.4A CN201380041026A CN104703934A CN 104703934 A CN104703934 A CN 104703934A CN 201380041026 A CN201380041026 A CN 201380041026A CN 104703934 A CN104703934 A CN 104703934A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
- C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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Abstract
本发明涉及一种衬底的涂层,尤其涉及一种抗反射涂层(ARCs)和自净涂层(SCCs)。所述涂层包含一个介孔的无机骨架,所述骨架内和/或骨架上含有光催化微粒,所述涂层的孔隙率大于50v/v%,优选的,大于55v/v%、60v/v%、65v/v%、70v/v%。
Description
本发明涉及一种衬底的涂层,尤其涉及一种抗反射涂层(ARCs)和自净涂层(SCCs)。本发明尤其涉及一种同时具有抗反射和自净功能的涂层,我们将其定义为自净抗反射涂层(SCARC)。
自从实验中首次实现降低光学界面的光反射以来,人们已经做了大量工作来不断地优化抗反射涂层的性能。虽然早已弄清所需的物理条件,但是在低折射率衬底上涂覆宽带抗反射涂层始终是个挑战。抗反射是通过两个(或多个)薄膜光学涂层界面间反射光的相消干扰实现的,单层抗反射涂层必须满足两个条件:(1)相位与相消干扰匹配,需要光学层厚度da等于入射光波长λ的四分之一:nardar=λ/4,(2)完全的相消干扰要求两个界面的反射波束具有相同的振幅,需要:nar=(n0ns)0.5,其中,nar、n0、nS分别代表抗反射涂层、媒介和衬底的折射率。
通过现代的沉积技术很容易满足第一个条件,但要满足第二个条件具有一定的难度:很多透明材料的折射率约为1.5左右,这就需要抗反射涂层的折射率nar≈1.22。只有采用具有非常高折射率的衬底(ns≈1.9),通常采用氟化镁(折射率为1.37)才能满足条件(2),而采用常用的玻璃和透明塑料为衬底,得到的光学性能很低。1
由于缺少具有足够低折射率的透明光学材料,因此在常用的光学衬底上制备抗反射涂层(ARCs)需要降低抗反射涂层的折射率nar而这只有通过在涂层中引入具有亚波长尺寸的孔来实现,这种材料-空气复合体的有效折射率可以通过多种有效媒介理论2,3如Bruggeman模型来估算。虽然研究级纳米结构的抗反射涂层已经接近完美了,但其耐磨性不足和由于纳米结构的污染而引发的光学可变性阻碍了它在商业化产品中的应用。为了满足户外应用,抗反射涂层需要具备结构稳定性和从环境污染中再生的特性,原则上,后者可以通过基于表面超疏水性或光催化性的自净ARCs实现。
超疏水表面在某种意义上来说是自净的,微粒污染物对它的的吸附很弱,可以轻易地用水冲洗掉。另一方面,光催化涂层不需要清洗媒介,而是通过光引发的氧化还原反应来分解有机污染物。从原理上来说光催化自净更为有利,在ARCs中添加光催化成分(以TiO2为代表),由于TiO2的高折射率(nTio2>2.5)成为主要的挑战。
人们已经提出多种将自净和抗反射结合的方案,包括在胶基ARC表面涂覆TiO2 4、共沉积TiO2和SiO2纳米粒子构造多孔ARC5、以及低折射率的TiO2和TiO2的双层结构6,7。但以上方法均需要高温处理步骤,限制了它们在弹性塑料衬底上的应用。此外,上述解决方案中的纳米级结构限制了可达到的孔隙率,因而限制了在不牺牲涂层有效折射率前提下可引入的TiO2的体积分数。
本发明提供了一种自净的并具有抗反射性的涂层,该涂层技术解决了先前技术的局限性。特别地,本发明的目的是提供一种具有有效抗反射功能的SCARC,所述SCARC至少包含:具有充分低的折射率、具有有效的自净能力两种特征,所述SCARC能够广泛应用于多种衬底。
相应地,本发明的第一个目的是提供一种衬底的涂层,所述涂层包含一种多孔的无机骨架,优选为介孔的无机骨架,所述骨架内和/或骨架上含有光催化微粒的。
本发明的第二个目的是提供一种衬底的涂层,所述涂层包含一种高孔隙率的、透明材料制成的、具有亚-光学长度尺度结构的骨架,所述骨架内和/或骨架上含有光催化微粒。
本发明的第三个目的是提供一种SCARC,所述涂层包含一种低折射率的透明衬底材料和一种光催化剂,所述涂层在厚度为80~150nm的透明衬底上在400nm~900nm波长范围内的光学透射率大于90%,比如,所述涂层在厚度约110nm的衬底上,在上述波长范围内的折射率小于1.3。
本发明的第四个目的是提供一种SCARC,所述涂层包含一种无机材料(例如含硅的材料,如铝硅酸盐)和二氧化钛。所述涂层在厚度为80~150nm的透明衬底上在400nm~900nm波长范围内的光学透射率大于90%,比如,所述涂层在厚度约110nm的衬底上,在632nm的折射率小于1.3。
进一步的,本发明还提供一种制备SCARC的前驱体混合物,所述混合物包含:
·一种牺牲聚合物的溶液
·一种包含可以形成无机骨架的前驱体材料
·光催化纳米晶体
更进一步的,本发明还提供一种制备SCARC的方法,所述制备方法包含如下步骤:
a)将如下物质形成混合液;
·一种牺牲聚合物的溶液
·一种包含可以形成无机骨架的前驱体材料
·光催化纳米晶体
b)将所述的混合液在溶液状态下进行处理,在衬底上形成涂层;
c)对涂层进行热处理或固化。
本发明还提供一种调节SCARC的折射率的方法,所述方法包含将如下物质形成混合液的步骤:
·一种牺牲聚合物的溶液(组分A)
·一种包含可以形成无机骨架的前驱体材料(组分B)
·光催化纳米晶体(组分C)
然后通过提高混合液中A:(B+C)的质量比和/或降低C:(B+A)的质量比来降低该混合液制备成的涂层的折射率。
所述涂层的孔隙率可以大于50v/v%,优选的,大于55v/v%、60v/v%、65v/v%、70v/v%、71v/v%、72v/v%、73v/v%。所述的孔可以是常规的,所述孔的孔径可以是1~100nm(即这里所用的介孔的定义范围),例如1~60nm,优选的,为2~55nm或5~100nm、10~95nm、20~85nm、20~80nm、20~75nm、20~65nm,更优选的为25~55nm。所述多孔涂层可能具有反蛋白石结构,以将紧密堆积的孔排列成纳米结构。
所述的光催化微粒可以是纳米微粒或纳米晶体。所述的光催化微粒可以包含二氧化钛。所述的光催化微粒可以由二氧化钛组成或包含二氧化钛。所述光催化微粒的主要尺寸可以小于10nm,例如小于5nm。所述微粒可以占涂层重量百分比最高可达75wt/wt%,例如最高可达50wt/wt%,优选的,占20~50wt/wt%、25~50wt/wt%。所述光催化微粒可以充分均一地分散于整个无机骨架中。
所述涂层在632nm或者可见光波长范围内的折射率可以小于1.3。并且/或者所述涂层在光学或透明衬底上,在400~900nm波长范围内的透光率可以超过90%。
所述混合液中的牺牲聚合物可以是一种两亲性聚合物。所述牺牲聚合物可以包含一种嵌段共聚物或由一种嵌段共聚物组成。所述嵌段共聚物可以包含一种两亲的前段序列,含有至少一种亲水组分和一种疏水组分,由于有选择性的分子间作用力,无机溶胶可以优先分布于其中一种嵌段。例如,高聚物结构为两嵌段聚(A-b-B)、三嵌段聚(A-b-B-b-A,A-b-B-b-C)或星型嵌段共聚物,其中A、B、C为化学性质不同的聚合物单元。所述嵌段共聚物可以为Am-Bn-Co的结构,其中A为疏水链段,C为亲水链段,B为连接单元(可以是一个聚合物链段),n可以是0或正整数。
所述疏水链段选自聚异戊二烯、聚丁二烯、聚二甲基硅氧烷、甲基苯基硅氧烷、C1-C4醇对应的聚丙烯酸酯、C3-C4醇对应的聚甲基丙烯酸酯、聚(乙烯-co-丁烯)、聚异丁烯、聚苯乙烯、聚环氧丙烷、聚环氧丁烷、聚乙烯乙酯、聚乳酸、聚氟代苯乙烯、聚磺化苯乙烯、聚羟基苯乙烯和功能类似物中的任意一种或任意多种,优选的为聚异戊二烯。
所述亲水链段选自聚氧化乙烯、聚乙烯醇、聚乙烯胺、聚乙烯嘧啶、聚丙烯酸、亲水性聚丙烯酸酯和聚丙烯酰胺、亲水性聚甲基丙烯酸酯、亲水性聚甲基丙烯酰胺、亲水性聚苯乙烯磺酸、聚氨基酸(如聚赖氨酸)、聚甲基丙烯酸羟乙酯、聚丙烯酸羟乙酯、聚甲基丙烯酸二甲氨基乙酯、聚(氨基酸)、聚(甲基丙烯酸羟乙酯)、聚(丙烯酸羟乙酯)、聚(甲基丙烯酸二甲氨基乙酯)、聚(五甲基二硅基苯乙烯)、多糖、聚(羟基聚异戊二烯)和功能类似物中的任意一种,优选的为聚氧化乙烯。
所述前驱体材料可以包含氟化物或氧化物和/或可形成氟化物或氧化物的物质。所述前驱体材料可以包含一种无机溶胶或由一种无机溶胶组成。所述无机溶胶包含一种低折射率的透明衬底材料如含氧或含氟化合物,优选的为氧化铝(n632nm=1.77)和/或二氧化硅(n632nm=1.54),最优选的为硅酸铝。也可以采用其他溶胶,如二氧化铪(n632..=1.89)、五氧化二钽(n632nm=1.81)、氟化钙(n632nm=1.43)、氟化镁(n632nm=1.37)等。优选的,用于制备无机骨架的本体材料的折射率小于2,更优选的,小于1.95、1.9、1.85、1.8、1.78、1.75、1.70、1.65、1.59、1.58、1.57、1.56、1.55。
所述光催化微粒,以二氧化钛纳米晶体为代表,可以通过与其他材料掺杂或共混的方式来提高其光催化活性。优选的材料体系包括三氧化钨、氧化锌、氧化锆、亚硫酸铬、聚金属氧酸盐,最优选的为二氧化钛基光催化剂(由于其耐光性好)。
在光学涂层中需要微孔的空间填充和钝化的低折射率透明材料,否则由于光催化材料的高折射率,会抑制透明衬底上SCARCs的形成。
制备骨架的方法多种多样,例如,可以通过加工将硅或其他含金属有机化合物如烷氧基化合物添加到溶胶中来提供金属源或硅源,如单独使用丁醇铝,或者将丁醇铝与其他物质混合使用。
醇盐和卤化物的替代品可以用做无机材料的前驱体。例如3-(2,3-环氧丙氧基)丙基三甲氧基硅烷、其他硅烷如烷基硅或芳基硅、各种的氧基硅烷(苯基蒽等)、其他聚合物材料如聚甲基倍半硅氧烷(PMSSQ)或聚(尿素甲基乙烯基)硅氮烷(PUMVS)等,可以单独使用也可以混合使用。
一开始就加入已经从溶液中结晶的光催化微粒如TiO2有几个优势:一方面,在薄膜沉积过程中不需要高温处理步骤使TiO2结晶;并且,在网络中可以形成清晰的光敏性TiO2热点。该方法可以作为TiO2添加方式的替代,而用TiO2前驱体对ARCs进行后处理会造成材料的额外沉积。这样,光催化微粒就会遍布于体系中,例如,在体系中均一分布,这表明刚磨损或破坏的光催化TiO2,斑点会显露出来。
优选的,所述TiO2微粒的主要尺寸小于10nm,更优选的,小于5nm,如小于4nm。
所述混合物中牺牲聚合物的质量百分比可以小于80wt/wt%,优选的,小于75、70、69、68、67、66、65wt/wt%,更优选的,小于50wt/wt%,如从10,11,12,13,14,15,16,17,18,19或20到80wt/wt%,比如占混合物的质量百分比为11~78wt/wt%、12~75wt/wt%、15~70wt/wt%或16~66wt/wt%。所述混合物中前驱体材料与高聚物的质量比为10:1~1:10,优选的为5:1~1:5,更优选的为3:1~1:3。
所述混合物中溶胶与光催化微粒如二氧化钛的质量比为10:1~1:10,优选的为5:1~1:5,更优选的为3:1~1:3。
本发明还包括提供同样涂层的或用相同混合物制成的衬底;所述衬底可以是由矿物质或塑料材料制得的。例如,所述衬底可以包含玻璃、石英、铟锡氧化物(ITO)、透明聚合物(可以是刚性的或弹性的)。所述涂层可以应用于太阳能电池板或太阳能收集器、光电的或其他电致发光设备、面板、显示器、光学仪器(如眼镜、望远镜、显微镜、镜头、反射镜等)、画框、展箱,等等。
所述涂层可以通过很多基于溶液沉积的技术实现,包括但不限于以下方式:单一衬底涂覆:如旋涂、浸涂、丝网印刷、喷墨印刷、移印,也可以是连续式卷对卷式技术,包括支棱衬刮刀(knife-over-the-edge)涂覆、弯月面涂覆、狭缝型挤压式涂覆、照相凹版涂覆、帘式、多层槽、斜板式涂覆和辊筒涂覆。随着科技的发展,其他的涂覆技术如柔性版印刷平版胶印、喷涂、电子照相、电子记录和磁记录技术也可以用于本发明。
所述方法可能还进一步包括对涂层进行温度低于250℃的热处理或固化,优选的,低于210℃、200℃、175℃、150℃、140℃。可选的或者进一步的,所述的方法还包括在步骤(c)之前将所有溶剂移除的步骤。可选的或者进一步的,所述的方法还包括去除残余聚合物组分以得到无机涂层的步骤。
本说明书中,骨架这个术语表示一个支撑框架,例如,一个框架结构包含多个连接和/或相互连接的框架所确定的空间,所述的框架可以包含规则和/或不规则的部分。特别地,所述涂层厚度为80~150nm,例如,85~145、90~140、95~135、100~130、105~125nm或者各自上限、下限的组合。如果只有自净是最关键的要求,而不是同时要求自净和光学透明度,所述涂层可以更厚些。
为了更充分地理解本发明,下面将通过实施例来进一步描述,其中的附图如下:
图1为本发明操作过程的示意图;
图2为本发明涂层的显微照片;
图3A-C为本发明的涂层的显微照片;
图4为折射率随高聚物分子量的变化图;
图5A和B为本发明涂层的光学透射率图;
图6为本发明的涂层的折射率随二氧化钛用量变化图;
图7A,B为根据本发明涂层的显微照片;
图8A-F为验证本发明涂层的自净功能的光谱;
图9A,B为表示本发明涂层的反应速率图;
图10A-E为本发明涂层自净功能效果图。
这里,我们提出表示抗反射和光催化作用相结合的一个新概念,它在一定程度上利用一种高分子量的嵌段共聚物聚(异戊二烯-b-氧化乙烯)(PI-b-PEO)与二氧化硅溶胶-凝胶化学相结合。一种二氧化硅(或其他无机化合物)溶胶加入到PI-b-PEO溶液中将其分成富PEO相。
将聚合物-溶胶溶液进行旋涂,使得无机材料形成一种类似反蛋白石的形貌,这表明发生了胶束的组装,可能是成膜过程中溶剂快速蒸发所致。
后续的热处理会诱导溶胶-凝胶的冷凝反应,使膜固化。最后,通过氧等离子体蚀刻除去聚合物主体,制得坚固、连续的无机膜,该膜的nc低至1.13。低的nc值是介观自组装的反蛋白石结构的结果。得到的超低折射率的薄膜可以用于装载含高折射率光催化微粒(如TiO2纳米晶体)的无机硅胶衬底支架(高达50wt%)。
将纳米晶体加入到溶胶溶液中会导致其分散于无机网络中,得到的经TiO2功能化的ARC的折射率(nar≈1.22)适于用做抗反射涂层,加入光催化中心后,会制得自净功能的涂层。此外,由于处理温度较低,该涂层尤其适合于柔性或刚性塑料衬底。
本发明的处理步骤示意图参照图1。
PI-b-PEO嵌段共聚物的溶液1,硅胶衬底溶胶2和TiO2纳米晶体3通过旋涂在玻璃衬底4上共沉淀,溶剂蒸发后形成一张初生态涂层5。其中的无机组分倾向于分布在氧化乙烯相,因此在两亲嵌段共聚物的自组装过程中结构定向。随后,在氧等离子体6中的反应刻蚀将聚合物7除去,得到无规分散着光催化TiO2纳米晶体的无机介孔网络8。调节光学涂层的厚度与折射率,使得相位和振幅匹配以达到对折射光最佳的相消干扰。
图2为本发明形成的介孔网络8的SEM图。图中清楚地展现出硅酸铝骨架2a具有反蛋白石型形貌特征,在骨架内和/或骨架上分布着TiO2晶体,优选的,TiO2晶体为均一分布。
为了进一步阐述本发明,下面结合以下实施例来说明。
实施例1-孔隙率的变化
嵌段共聚物的制备
根据Allgaier等人8的方法制备了一种聚合物量嵌段共聚物-聚(异戊二烯-b-氧化乙烯)(PI-b-PEO),并将其溶解于甲苯和正丁醇的的恒沸混合物中。
二氧化硅基溶胶的制备
由硅/铝烷基氧化物混合物(摩尔比9:1)的分步水解分别制备了一种铝硅酸盐溶胶,其中:2.8g的3-(2,3-环氧丙氧基)丙基三甲氧基硅烷(98%,Aldrich)、0.32g的仲丁醇铝(97%,Aldrich)和20mgKCl(Trace SELECT,Fluka)混合,并迅速置于冰水浴中,在第一步水解反应中,在0℃下,每隔5s逐滴加入0.135ml的10mM的HCl溶液,并搅拌15分钟。升温至室温后,再逐滴加入0.85ml的10mM的HCl溶液。
通过第一组实验来考察聚合物用量对形成涂层的形貌的影响。将有机无机比定义为初始溶液中聚合物的质量与形成的硅衬底料的质量比。溶液中的高聚物含量如下:
将各组分混合,例如,将高聚物溶于恒沸物中,再加入TiO2溶液,将溶胶搅拌后添加到混合溶液中。
在玻璃上制备涂层
通过旋涂(2000rpm,20s)的方式在载玻片上形成杂化膜,将铸制薄膜在一个电炉上通过逐渐升温到200℃(180min线性升温,30min保温)的方法热处理。最后一步,通过氧等离子体(30min,100W,0.33mbar,SIS Instruments,320PC RIE)进行反应离子刻蚀,将杂化膜中的有机组分除去。
制得的涂层如图3A到3C所示(对应于实施例1A到1C)。
扫描电子显微镜显示了相互连接的框架,该网络的形貌揭示了它可能的起始态。明晰的孔径和六边形排列印证了反蛋白石结构。反蛋白石结构是由牺牲胶束或胶体的紧密堆积形成的。不限于任何理论,我们假定该形貌的形成过程可能包含溶液中嵌段共聚物胶束的形成,更具体的,由胶体、致孔牺牲材料和致网无机材料形成的液体混合物在溶剂蒸发过程中自组装形成由PI核和PEO+溶胶衬底组成的蛋白石形貌。冷凝反应和聚合物的移除导致形成如图3所示的网络结构。由于胶束尺寸是由聚合物的构型决定的,因此可以通过改变原来的有机物和无机物的体积(或质量)比来在小范围内微调孔隙率。
得到的孔隙率的变化如图3A-C所示,其中,聚合物的含量从28w%增大到50w%。无机网络的孔径可以通过改变牺牲聚异戊二烯(PI)链段的分子量来控制。在本实施例中PI的分子量约为24.8kg/mol,对应得到的无机网络的孔径约33nm。
光谱椭偏仪测量结果表明,从28%到67%改变初始溶液中聚合物质量比,制得的薄膜的折射率最终可以在1.40<na<1.13的范围内变化(如图4所示)。
采用Bruggeman有效媒介估算法对二氧化硅型衬底(n=1.52)中的气孔网络进行估算,在na=1.13条件下,孔隙率为73%。
由于极低的折射率,该制备SCARCs的溶胶路线为嵌入光催化剂(特别是具有高折射率的光催化剂)提供了一种理想的衬底。
实施例2-孔径的变化
采用上述方法,可以在不同质量含量的聚合物溶液中制备涂层,举例如下:
图2展示了与实施例1有相似无机物含量但采用更大分子量的PI制备的薄膜的形貌。
本实施例采用的共聚物中PI链长增大为62.7kg/mol,增大的链长导致微孔的孔径变宽53nm,这种增长非常符合聚合物链在良溶剂中遵循的比例法则。当PI嵌段的分子量从24.8增大到62.7kg/mol时,致孔剂PI嵌段的回旋半径会增大到1.59倍,与用SEM图片的分析出来的孔径的结果一致。
实施例3-化学途径制备多空骨架的变化
在另一个实验中,改变多孔骨架的材料路线。大多数普通的制备低折射率的无机成分的方法会涉及水解反应的溶胶-凝胶化学反应和前驱体材料的冷凝反应。还有几种非水解的路线:在无水的有机溶剂中进行前驱体反应9。
我们采用另一种前驱体材料,聚甲基倍半硅氧烷(PMSSQ)共聚物10,而不是依照在这种情况下,将PMSSQ共聚物溶解于正丁醇,与嵌段共聚物溶液混合。后处理(热处理和蚀刻)过程见实施例1。在这种情况下,将PMSSQ共聚物溶解于正丁醇,与嵌段共聚物溶液混合。后处理(热处理和蚀刻)过程见实施例1。
实施例4-塑料衬底的制备
在PET上制备涂层
用旋涂法(2000rpm,20s)在预清洗的聚对苯二甲酸乙二醇酯(PET)片上涂覆一层杂化膜,将铸膜在电炉上采用逐渐升温到130℃(15min线性升温,5min保温时间)的方法热处理,之后将衬底相同条件下暴露于氧等离子体中30min。对于柔性衬底,搭建一个铝制样品架以进行双面涂覆。
已经证实采用上述技术,可以将二氧化钛或其他光催化微粒加入到涂层中,赋予涂层自净特征。由于孔隙率、孔径和光催化微粒的含量均可以改变,因此“调节”涂层的折射率和/或自净能力来满足特定的需求也成为可能。
实施例5-光催化TiO2纳米晶体的内含物
进一步做了一系列实验来研究二氧化钛含量增加对涂层性能的改变。采用实施例1中的方法制备如下溶液,并加工成涂层,具体的TiO2含量如下所示:
TiO2纳米晶体的制备
在稳定的氮气气氛和充分的搅拌下,将如下化合物连续地加入烧瓶中:5.75ml醇酒精、1mlTiCl4、19.2ml苯甲醇和0.23ml的1,3-丙二醇。将溶液加热到80℃并搅拌12个小时。随后,将溶质在乙醚(体积比1:10)中沉淀出来,以3500rpm的速率离心10min。得到的湿沉淀物在空气中干燥2小时,然后将其溶解于甲苯(72.84wt/wt%)和正丁醇(27.16wt/wt%)的混合恒沸物中。为了保持恒沸物溶液(20mg/ml)中TiO2纳米晶体浓度的稳定,充分烘干一部分沉淀物并加热到350℃来分析的TiO2质量含量。
考察了涂层的光学性能,结果如图5A和5B所示,如下:
图6展示了涂层的折射率随TiO2用量(wt/wt%)的变化关系。
用TiO2替代硅酸铝后,采用Bruggeman有效介质估算法计算的折射率与TiO2用量呈良好的比例关系。由于无机网络的孔隙率≈71%,高达50wt/wt%的TiO2可以替换成硅基网络,导致折射率从1.14(0wt/wt%TiO2)增大到1.19(25wt/wt%TiO2)、1.22(37.5wt/wt%TiO2)和1.26(50wt/wt%TiO2),具有非常好的透光率和清晰度(如非彩色的)光学性能。
实施例6
进一步地,我们做了一组实验来研究纳米晶体在二氧化硅型衬底中的分散情况。
采用不同聚合物和质量分数为50wt/wt%的TiO2制备了一系列涂层,涂层的高放大倍数透射电子显微照片如图7A(PI-b-PE034)和7B(PI-b-PE092)所示,图中的定标线条为20nm。
纳米晶体的分布是高分散的,其中纳米晶体的尺寸为3-4nm。有趣而且很重要的是,图片中没有发现聚集现象。广角X射线衍射研究进一步验证了上述结果,这表明纳米晶体微粒的尺寸为3.5±0.2nm,该结果是由[101]锐钛矿的峰值的谢乐(Scherrer)分析得到的。
实施例7-对污染物的光催化自净
我们进一步做了一组实验来测量涂层的自净能力。
硬脂酸的分解常被用做有机分子标志物来监控自净表面的光催化性能。硬脂酸易于在有机表面组装成均相层,它的分解可以用傅里叶变换红外光谱(FTIR)来检测。
为了在实验室里精确地模拟太阳光照射(AM 1.5),我们采用一个氙气灯并在光谱λ<375nm范围内校准其强度以匹配自然的太阳能密度,由于锐钛矿带隙≈3.3eV,在该光谱范围内,TiO2会吸收光。
图8A-F显示了两种不同孔径(a-c:33nm,d-f:53nm)的ARCs上吸附的硬脂酸的分解情况,每个ARC中TiO2的用量为25-50wt/wt%,采集了FTIR吸收光谱并经过传输和基线校正。在光谱范围为2800-3000cm-1内,硬脂酸出现三个峰:在2958cm-1处的吸收峰为甲基中C-H键的非对称面内拉伸震动,而2923cm-1和2853cm-1两处的吸收峰分别对应于-CH2-中C-H键的对称和非对称拉伸震动。三个吸收峰下的综合面积,规范为辐照前的值,作为SCARC表面的硬脂酸稳定性的衡量值。
TiO2用量为25wt%的样品对应的硬脂酸的分解相对较慢,而TiO2用量为37.5和50wt%的样品对应的FTIR信号迅速降低。所有样品的综合峰衰减的动力学均显示出零级反应特征(如图9所示,其中图9A对应于PI-b-PEO34,孔径约为33nm;图9A对应于PI-b-PEO92,孔径约为53nm)。TiO2用量较大(如37.5和50.0wt/wt%)时,孔径小的样品性能比孔径大的样品性能好(如时间常数较小)。
各个样品的测试结果如下所示:
作为对照,我们用硬脂酸涂覆纯硅酸铝作为参照做了一组平行实验,结果表明,3小时的辐照后,没有出现FTIR吸收强度减小的现象。而现有技术参照样品显示出明显更低的反应速率(0.15×1013mol/min)。
实施例8-光催化移除指纹残留
为了证明本发明制备的光学涂层在严重的肉眼可见的污染情况下仍然能够保持其功能,我们用指纹污染样品并暴露在模拟太阳光(AM 1.5)中。
作为对照,将一个空白的硅衬底样品和一个预先涂覆过上述自净抗反射涂层的硅衬底样品比较。采用完全相同的指纹作用于两个样品,两个受污染的样品及其在模拟太阳光照射120min后的光学外观对比如图10所示。纯的硅样品(a)还有肉眼可见的污染,指纹的纹路清晰可见;相比之下,涂覆了本发明涂层的样品已经完全恢复,没有明显的指纹残留。自净的时间演变机理如图10b-e的照片所示。
图10b-e的照片显示涂覆了自净抗反射涂层的样品在自净过程中的不同阶段:(a)对样品施加了指纹污染,(b)模拟太阳光照射30min后,(c)模拟太阳光照射60min后,(d)模拟太阳光照射120min后。样品(a)没有任何进一步处理,而照片b-d中的样品在60min后被置于短暂溢出的水中,来进一步模拟被雨水冲洗,对比样品(a)和(e)得出,虽然冲洗能促进自净过程,但它并不是必须的。
显然的,由于该涂层无需其他助剂(如水)就可以实现自净功能,该涂层能应用于很多潜在的领域(如室内和/或水敏感环境中)。
综上所述,本发明已经清楚地证明能够制备出一种有效的具有有用(useful)折射率和光学透射率特征的SCARC,还阐明了可以通过调整涂层的各种参数使之适应于多种应用场合。此外,由于不需要高温热处理过程,本发明的涂层可以应用于种类繁多的衬底上,如塑料(刚性或柔性均可)或玻璃。
实验证明冲洗不是保证自净功能的必要条件,这意味着本涂层可以应用于很宽范围的湿敏性环境中。
Claims (42)
1.一种用于衬底的涂层,其特征在于,所述的涂层包含介孔无机骨架,在所述介孔无机骨架其中和/或其上含有光催化微粒,所述涂层的孔隙率大于50v/v%,优选的,超过55v/v%、60v/v%、65v/v%、70v/v%。
2.根据权利要求1所述的涂层,其特征在于,所述的无机骨架具有反蛋白石形貌。
3.根据权利要求1或2所述的涂层,其特征在于,所述的孔的孔径为1~100nm。
4.根据权利要求1-3任一项所述的涂层,其特征在于,所述的光催化微粒的主要尺寸小于10nm,优选的小于5nm。
5.根据权利要求1-3任一项所述的涂层,其特征在于,所述的光催化微粒占涂层总质量的75wt/wt%,优选的,占涂层总质量的50wt/wt%。
6.根据权利要求1-3任一项所述的涂层,其特征在于,所述的光催化微粒占涂层总质量的25~50wt/wt%。
7.根据权利要求1-3任一项所述的涂层,其特征在于,所述的光催化微粒充分均一地分布于整个无机骨架中。
8.根据权利要求1-3任一项所述的涂层,其特征在于,所述的光催化微粒包含二氧化钛。
9.根据权利要求1-3任一项所述的涂层,其特征在于,所述的涂层在可见光波长范围内的折射率小于1.3。
10.根据权利要求1-3任一项所述的涂层,其特征在于,所述的涂层在光学衬底上对400~900nm波长的透光率大于90%,所述的光学衬底优选玻璃或聚对苯二甲酸乙二醇酯。
11.一种自净抗反射涂层,其特征在于,所述的涂层包含一种无机材料,所述的无机材料优选含二氧化硅的材料,更优选的无机材料为硅酸铝、二氧化钛,所述的涂层在厚度为80~150nm的光学衬底上对400~900nm波长的透光率大于90%,所述光学衬底的厚度优选为110nm,所述的涂层在可见光波长范围内的折射率小于1.4,优选的小于1.35,更优选的小于1.3。
12.一种用于自净抗反射涂层的前驱体混合物,其特征在于,所述的混合物包含:
·一种牺牲聚合物的溶液;
·一种包含可形成无机骨架的前驱体材料;
·光催化纳米晶体。
13.根据权利要求12所述的混合物,其特征在于,所述的牺牲聚合物为嵌段共聚物。
14.根据权利要求13所述的混合物,其特征在于,所述的嵌段共聚物为两亲性嵌段共聚物。
15.根据权利要求13或14所述的混合物,其特征在于,所述的嵌段共聚物的结构为Am-Bn-Co型,其中A是一种疏水链段,C是一种亲水链段,B是一个连接单元,n为0或正整数。
16.根据权利要求14或15所述的混合物,其特征在于,所述的疏水链段选自聚异戊二烯、聚丁二烯、聚二甲基硅氧烷、甲基苯基硅氧烷、聚丙烯酸酯(C1-C4的醇)、聚甲基丙烯酸酯(C3-C4的醇)、聚(乙烯-co-丁烯)、聚异丁烯、聚苯乙烯、聚环氧丙烷、聚环氧丁烷、聚乙烯乙酯、聚乳酸、聚氟代苯乙烯、聚磺化苯乙烯、聚羟基苯乙烯的任意一种或任意多种。
17.根据权利要求14-16任一项所述的混合物,其特征在于,所述的疏水链段为聚异戊二烯。
18.根据权利要求14-17任一项所述的混合物,其特征在于,所述的亲水链段选自聚氧化乙烯、聚乙烯醇、聚乙烯胺、聚乙烯嘧啶、聚丙烯酸、聚甲基丙烯酸、亲水性聚丙烯酸酯和聚丙烯酰胺、亲水性的聚甲基丙烯酸酯、亲水性的聚甲基丙烯酰胺、亲水性的聚苯乙烯磺酸、聚氨基酸、聚甲基丙烯酸羟乙酯、聚丙烯酸羟乙酯、聚甲基丙烯酸二甲氨基乙酯、聚五甲基二硅基苯乙烯、多糖、聚(羟基聚异戊二烯)中的任意一种或任意多种。
19.根据权利要求18所述的混合物,其特征在于,所述的亲水链段为聚氧化乙烯。
20.根据权利要求12-19任一项所述的混合物,其特征在于,所述的前驱体材料包含氟化物或氧化物和/或可形成氟化物或氧化物的物质。
21.根据权利要求12-20任一项所述的混合物,其特征在于,所述的前驱体材料是无机溶胶。
22.根据权利要求21所述的混合物,其特征在于,所述的无机溶胶包含氧化铝和/或二氧化硅。
23.根据权利要求12-22任一项所述的混合物,其特征在于,所述的前驱体材料是含硅的有机化合物,优选含硅的聚合物。
24.根据权利要求12-23任一项所述的混合物,其特征在于,所述的光催化微粒包含二氧化钛。
25.根据权利要求12-24任一项所述的混合物,其特征在于,所述的光催化微粒为纳米晶体。
26.根据权利要求12-25任一项所述的混合物,其特征在于,所述的光催化微粒的主要尺寸小于10nm,优选的小于5nm。
27.根据权利要求12-26任一项所述的混合物,其特征在于,所述的牺牲聚合物占混合物的质量比小于80wt/wt%,优选的小于70wt/wt%,更优选的占混合物质量的15~66wt/wt%。
28.根据权利要求12-27任一项所述的混合物,其特征在于,所述的前驱体材料与聚合物的质量比为3:1~1:3。
29.根据权利要求12-28任一项所述的混合物,其特征在于,所述的溶胶与二氧化钛的质量比为3:1~1:3。
30.一种衬底,其特征在于,所述的衬底上涂覆权利要求1-11任一项所述涂层,和/或所述的衬底由权利要求13-30任一项所述的混合物形成。
31.根据权利要求30所述的衬底,其特征在于,所述衬底由一种矿物质或塑料材料形成。
32.一种SCARC的制备方法,其特征在于,包括如下步骤:
a)将如下物质混合成混合物:
·一种牺牲聚合物的溶液;
·一种包含可形成无机骨架的前驱体材料;
·光催化纳米晶体;
b)溶液状态下处理所述的混合物,在衬底上形成涂层;
c)对步骤b)所述的涂层进行热处理。
33.根据权利要求32所述的制备方法,其特征在于,步骤b)的具体实施涂覆方法选自旋涂、浸涂、丝网印刷、喷墨印刷、移印、连续式卷对卷技术,所述的连续式卷对卷技术优选支棱衬刮刀涂覆、弯月面涂覆、狭缝型挤压式涂覆、照相凹版涂覆、帘式、多层槽、斜板式涂覆和辊筒涂覆。
34.根据权利要求32或33所述的制备方法,其特征在于,所述的制备方法还进一步包括对涂层进行热处理或固化的步骤,所述的热处理或固化的温度低于250℃,优选的低于210℃、200℃、175℃、150℃、140℃。
35.根据权利要求32-34任一项所述的制备方法,其特征在于,所述的制备方法还包括在步骤c)之前除去任意溶剂的步骤。
36.根据权利要求32-35任一项所述的制备方法,其特征在于,所述的制备方法包括除去残留的聚合物组分只留下无机涂层的步骤。
37.一种调节SCARC的折射率的方法,其特征在于,所述方法包括:将如下物质混合成混合物:
·一种牺牲聚合物的溶液(组分A)
·一种包含可形成无机骨架的前驱体材料(组分B)
·光催化纳米晶体(组分C)
增大混合物中A:(B+C)的质量比和/或减小C:(B+A)的质量比来降低该混合物形成的涂层的折射率。
38.根据权利要求37所述的方法,其特征在于,所述组分A为嵌段共聚物,优选的,为两亲性嵌段共聚物。
39.根据权利要求37或38所述的方法,其特征在于,所述的组分B为无机溶胶,优选的为包含二氧化硅的无机溶胶,更优选的为包含二氧化硅和/或氧化铝的无机溶胶。
40.根据权利要求37-39任一项所述的方法,其特征在于,所述的组分C为二氧化钛微粒,优选的为二氧化钛纳米晶体。
41.一种如同上文中界定的涂层或混合物。
42.一种如同上文中界定的制备方法。
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CN102317228B (zh) * | 2009-01-12 | 2015-11-25 | 清洁阳光能源有限公司 | 具有自清洁减反射涂层的基材及其制备方法 |
JP2011072935A (ja) * | 2009-09-30 | 2011-04-14 | Toto Ltd | 光触媒塗装体およびそのための光触媒コーティング液 |
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- 2012-07-11 GB GBGB1212361.8A patent/GB201212361D0/en not_active Ceased
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2013
- 2013-07-11 EP EP13739263.5A patent/EP2872456A1/en not_active Withdrawn
- 2013-07-11 CN CN201380041026.4A patent/CN104703934A/zh active Pending
- 2013-07-11 KR KR20157003192A patent/KR20150036421A/ko not_active Application Discontinuation
- 2013-07-11 WO PCT/GB2013/051841 patent/WO2014009731A1/en active Application Filing
- 2013-07-11 JP JP2015521067A patent/JP2015528034A/ja active Pending
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2015
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CN1662465A (zh) * | 2002-04-17 | 2005-08-31 | 法国圣戈班玻璃厂 | 有自洁式涂层的基材 |
DE102007043651A1 (de) * | 2007-09-13 | 2009-03-26 | Siemens Ag | Silizium/Titandioxid-Schicht mit verbesserten Oberflächeneigenschaften |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107901545A (zh) * | 2017-10-30 | 2018-04-13 | 广东欧珀移动通信有限公司 | 壳体制作方法、壳体及电子设备 |
CN111921548A (zh) * | 2019-05-13 | 2020-11-13 | 通用汽车环球科技运作有限责任公司 | 多功能自清洁表面层及其形成方法 |
US11772086B2 (en) | 2019-05-13 | 2023-10-03 | GM Global Technology Operations LLC | Multifunctional self-cleaning surface layer and methods of forming the same |
CN111849219A (zh) * | 2019-09-23 | 2020-10-30 | 法国圣戈班玻璃公司 | 一种涂料分散液,其制备方法、由其获得的产品 |
CN111812753A (zh) * | 2020-06-01 | 2020-10-23 | 湖南大学 | 一种硅基底3-6μm红外窗口片 |
Also Published As
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JP2015528034A (ja) | 2015-09-24 |
WO2014009731A1 (en) | 2014-01-16 |
US20150376441A1 (en) | 2015-12-31 |
KR20150036421A (ko) | 2015-04-07 |
EP2872456A1 (en) | 2015-05-20 |
GB201212361D0 (en) | 2012-08-22 |
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