CN116285442B - 负碳且自主调温的温致变色涂层及其制备方法与应用 - Google Patents
负碳且自主调温的温致变色涂层及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开一种负碳且自主调温的温致变色涂层及其制备方法与应用,包括质量份数如下的组分:1‑10份钛溶胶改性可逆变色微胶囊、60‑115份碳化胶凝材料、1‑50份高反射白色无机填料、1‑20份成膜剂、50‑120份水,可实现自主调温,有助于建筑节能,粘接力强。
Description
技术领域
本发明涉及建筑涂层技术领域,尤其涉及一种负碳且自主调温的温致变色涂层及其制备方法与应用。
背景技术
温室气体的过量排放导致温室效应日益加剧,碳捕捉和封存技术成为当下研究重点。
温致变色材料的光学性能及颜色随环境温度而变化,在建筑环境中显示出显着的节能潜力。温致变色材料的光谱反射率和发射率,与材料的表面温度有关。它们在高温下脱色以避免吸收阳光,并在低温下显示颜色以吸收阳光,以减少夏季建筑物的冷却负荷和冬季的供暖负荷,从而可实现建筑物与环境之间的智能交互。
目前已知的可逆温致变色涂层,其相变温度较高,不利于建筑节能,且涂层与建筑外墙基层结合力不强,易脱落。
发明内容
有鉴于此,本申请提供一种负碳且自主调温的温致变色涂层及其制备方法与应用,可实现自主调温,有助于建筑节能,粘接力强。
为达到上述技术目的,本申请采用以下技术方案:
第一方面,本申请提供一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:1-10份钛溶胶改性可逆变色微胶囊、60-115份碳化胶凝材料、1-50份高反射白色无机填料、1-20份成膜剂、50-120份水。
优选的,钛溶胶改性可逆变色微胶囊的制备方法如下:将可逆变色微胶囊超声分散于经溶胶凝胶法合成的钛溶胶中,再过滤干燥,即得钛溶胶改性可逆变色微胶囊。
优选的,可逆变色微胶囊包括芯材和包裹芯材的壁材,壁材为三聚氰胺甲醛树脂,芯材为隐色剂、显色剂及溶剂的混合物。
优选的,隐色剂为荧烷类染料。
优选的,钛溶胶改性可逆变色微胶囊的平均粒径为5-15μm,其变色温度为25-34℃。
优选的,碳化胶凝材料包括硅酸二钙、硅酸三钙、硅酸一钙及氧化镁、氧化钙、氢氧化钙中的一种或几种,碳化胶凝材料的平均粒径为0.1-120μm。
优选的,高反射白色无机填料包括纳米氧化铝、纳米金红石型二氧化钛、超细硫酸钡、二氧化锆中的一种或多种。
第二方面,本申请提供一种负碳且自主调温的温致变色涂层的制备方法,包括以下步骤:按质量份将钛溶胶改性可逆变色微胶囊、碳化胶凝材料、高反射白色无机颜填料、成膜剂、水混合搅拌均匀,得到浆体,将浆体涂覆于基体表面,利用碳化养护将浆体固化于基体表面,即得负碳且自主调温的温致变色涂层。
优选的,碳化养护的CO2浓度为10-100%,养护温度为-20-200℃,养护时间0.5-72h,碳化压力0.1-0.3MPa。
第三方面,本申请提供一种负碳且自主调温的温致变色涂层在建筑材料外层中的应用。
本申请的有益效果如下:
1.本方案采用无机改性的方法将有机的可逆变色微胶囊经钛溶胶改性,在可逆变色微胶囊表面负载二氧化钛,使其在可逆温致变色的同时提升变色微胶囊耐紫外老化能力,同时将变色微胶囊的表面进行改性增加其与无机的碳化胶凝材料的结合力,由于未改性的变色微胶囊为球状有机物,直接与无机材料结合性不好,制备出涂层出现部分掉粉,而经过钛溶胶无机改性过后,改变了其表面张力,使得与无机材料结合情况优于未改性前,同时解决涂层掉粉问题。。
2.本方案的负碳且自主调温的温致变色涂层将经钛溶胶改性的可逆变色微胶囊与碳化胶凝材料及高反射填料相结合,通过二氧化碳养护方式使其凝结硬化,制备出的涂层颜色响应温度的变化,可实现自主调温:夏季高温下脱色,可增强太阳反射率,减少夏季人为的冷却负荷;冬季低温下显示颜色,可增强太阳吸收率即减少太阳的反射率,减少冬季人为的供暖负荷,有助于建筑节能。
3.本方案的负碳且自主调温的温致变色涂层相变温度较低,制备过程消耗二氧化碳,节能环保,可广泛应用于四季分明地区建筑围墙外层,实现自主调温。
附图说明
图1为各涂层的温度曲线。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
原料制备
钛溶胶:将1份的钛酸四异丙酯与30份的无水乙醇混合后,以1~2d/s的速度滴加到0.8份醋酸和16份去离子水的混合溶液中,经搅拌48h;陈化72h。
本申请提供一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:1-10份钛溶胶改性可逆变色微胶囊、60-115份碳化胶凝材料、1-50份高反射白色无机填料、1-20份成膜剂、50-120份水;过量的钛溶胶改性可逆变色微胶囊成本较高,且对夏季反射阳光有影响,而用量过少则其颜色较浅,不利于冬季吸收可见光;碳化胶凝材料用量过多或者过少会影响涂层的致密度,进而影响涂层的碳化反应程度;高反射白色无机颜调料用量过少涂层的反射率过低,不利于夏季反射阳光,用量过度其反射率过高,不利于冬季集热。
可逆变色微胶囊制备采用原位聚合法,将壁材单体加入体系中,使聚合反应在芯材表面发生,从而将芯材包裹住,钛溶胶改性可逆变色微胶囊的制备方法如下:将可逆变色微胶囊超声分散于经溶胶凝胶法合成的钛溶胶中,再过滤干燥,即得钛溶胶改性可逆变色微胶囊;本方案使用钛溶胶改性后,可在微胶囊外层形成均匀的二氧化钛,吸收紫外线,从而增强其抗紫外耐久性。
可逆变色微胶囊制备采用原位聚合法,将壁材单体加入体系中,使聚合反应在芯材表面发生,从而将芯材包裹住,包括芯材和包裹芯材的壁材,壁材为三聚氰胺甲醛树脂,芯材为隐色剂、显色剂及溶剂的混合物。
隐色剂为荧烷类染料,包括热敏红6-(N-乙基-4-甲苯胺基)-2-甲基荧烷、热敏蓝1,2-苯并-6-二乙基氨基荧烷、热敏黄3,6-二甲氧基荧烷、热敏黑2-苯氨基-3-甲基-6-二丁氨基荧烷中的一种或几种。
钛溶胶改性可逆变色微胶囊的变色温度为25-34℃。
碳化胶凝材料包括硅酸二钙、硅酸三钙、硅酸一钙及氧化镁、氧化钙、氢氧化钙中的一种或几种,碳化胶凝材料的平均粒径为0.1-120μm,限制粒径是为了保证制备浆体均匀分散性问题,二者无关联,碳化胶凝材料粒径过小,一方面增加粉磨难度,另一方面浆体流动性受影响,碳化胶凝材料粒径过大,制备的浆体容易沉降。
高反射白色无机颜填料包括纳米氧化铝、纳米金红石型二氧化钛、超细硫酸钡、二氧化锆中的一种或多种。
本申请提供一种负碳且自主调温的温致变色涂层的制备方法,包括以下步骤:按质量份将钛溶胶改性可逆变色微胶囊、碳化胶凝材料、高反射白色无机颜填料、成膜剂、水混合搅拌均匀,得到浆体,将浆体涂覆于基体表面,利用碳化养护将浆体固化于基体表面,即得负碳且自主调温的温致变色涂层。
碳化养护的CO2浓度为10-100%,碳化压力0.1-0.3MPa,养护温度为-20-200℃,养护时间0.5-72h。
本申请提供一种负碳且自主调温的温致变色涂层在建筑材料外层中的应用,本涂层主要应用四季分明地区,-10℃-45℃。。
以下通过具体实施例对本方案进行进一步说明。
实施例1
一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:115份碳化胶凝材料,120份水、10份隐色剂为热敏红并经溶胶改性可逆变色微胶囊、50份高反射白色颜填料、20份成膜剂;其中碳化胶凝材料为硅酸二钙;高反射白色颜料为纳米氧化铝和纳米金红石型二者的组合,其质量比为1:1,成膜剂采用纯丙乳液。
一种负碳且自主调温的温致变色涂层的制备方法,将钛溶胶改性可逆变色微胶囊与高反射白色颜填料充分混合后,再与成膜剂及水混合均匀,最后再加入碳化胶凝材料,搅拌均匀后制备成均匀浆体,通过喷涂形式涂覆在基体表面,涂覆厚度为0.4mm,通过碳化养护方式使其凝结硬化,碳化养护的CO2浓度为100%,碳化压力为0.1Mpa,养护温度为25℃,养护时间24h,得到负碳且自主调温的温致变色涂层。
其中,钛溶胶改性可逆变色微胶囊的制备方法如下,将有机可逆温致变色微胶囊超声分散在制备合成的钛溶胶中,有机可逆温致变色微胶囊与钛溶胶质量比为1,其钛溶胶质量分数为2%,超声分散3h,之后滤出,40℃干燥12h备用。
实施例2
一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:85份碳化胶凝材料,78份水、6份隐色剂为热敏黄并经溶胶改性可逆变色微胶囊、25份高反射白色颜填料、9份成膜剂;其中碳化胶凝材料为C2S和C3S二者的混合;高反射白色颜料为纳米金红石型和超细硫酸钡二者的组合,其质量比为2:1,成膜剂采用纯丙乳液。
一种负碳且自主调温的温致变色涂层的制备方法,将钛溶胶改性可逆变色微胶囊与高反射白色颜填料充分混合后,再与成膜剂及水混合均匀,最后再加入碳化胶凝材料,搅拌均匀后制备成均匀浆体,通过喷涂的形式涂覆在基体表面,涂覆厚度为0.8mm,通过碳化养护方式使其凝结硬化,碳化养护的CO2浓度为60%,碳化压力为0.2Mpa,养护温度为25℃,养护时间12h,得到负碳且自主调温的温致变色涂层。
其中,钛溶胶改性可逆变色微胶囊的制备方法如下,将隐色剂为热敏黄的有机可逆温致变色微胶囊超声分散在制备合成的钛溶胶中,有机可逆温致变色微胶囊与钛溶胶质量比为0.5,其钛溶胶质量分数为3%,超声分散3h,之后滤出,40℃干燥12h备用。
实施例3
一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:60份碳化胶凝材料,50份水、1份隐色剂为热敏蓝并经钛溶胶改性可逆变色微胶囊、1份高反射白色颜填料、10份成膜剂;其中碳化胶凝材料为C2S、CS、C3S的混合;高反射白色颜填料为纳米金红石型、超细硫酸钡、纳米氧化铝三者的组合,其质量比为2:1:1,成膜剂采用硅丙乳液。
一种负碳且自主调温的温致变色涂层的制备方法,将钛溶胶改性可逆变色微胶囊与高反射白色颜填料充分混合后,再与成膜剂及水混合均匀,最后再加入碳化胶凝材料,搅拌均匀后制备成均匀浆体,通过喷涂的形式涂覆在基体表面,涂覆厚度为1mm,通过碳化养护方式使其凝结硬化,碳化养护的CO2浓度为30%,碳化压力为0.3Mpa,养护温度为25℃,养护时间6h,得到负碳且自主调温的温致变色涂层。
其中,钛溶胶改性可逆变色微胶囊的制备方法如下,将隐色剂为热敏蓝的有机可逆温致变色微胶囊超声分散在制备合成的钛溶胶中,有机可逆温致变色微胶囊与钛溶胶质量比为0.3,其钛溶胶质量分数为2.5%,超声分散3h,之后滤出,40℃干燥12h备用。
实施例4
一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:85份碳化胶凝材料,100份水、5份隐色剂为热敏黑并经钛溶胶改性可逆变色微胶囊、30份高反射白色颜填料、16份成膜剂;其中碳化胶凝材料为C2S、CS的混合;高反射白色颜填料为超细硫酸钡及纳米氧化铝二者的组合,其质量比为3:1,成膜剂采用苯丙乳液。
一种负碳且自主调温的温致变色涂层的制备方法,将钛溶胶改性可逆变色微胶囊与高反射白色颜填料充分混合后,再与成膜剂及水混合均匀,最后再加入碳化胶凝材料,搅拌均匀后制备成均匀浆体,通过喷涂的形式涂覆在基体表面,涂覆厚度为2mm,通过碳化养护方式使其凝结硬化,碳化养护的CO2浓度为10%,碳化压力为0.3Mpa,养护温度为25℃,养护时间24h,得到负碳且自主调温的温致变色涂层。
其中,钛溶胶改性可逆变色微胶囊的制备方法如下,将隐色剂为热敏黑的有机可逆温致变色微胶囊超声分散在制备合成的钛溶胶中,有机可逆温致变色微胶囊与钛溶胶质量比为0.2,其钛溶胶质量分数为3.5%,超声分散3h,之后滤出,40℃干燥12h备用。
实施例5
一种负碳且自主调温的温致变色涂层,包括质量份数如下的组分:90份碳化胶凝材料,70份水、6份隐色剂为热敏红并经钛溶胶改性可逆变色微胶囊、30份高反射白色颜填料、15份成膜剂;其中碳化胶凝材料为C2S、C3S的混合,高反射白色颜填料为超细硫酸钡,成膜剂采用硅丙乳液。
一种负碳且自主调温的温致变色涂层的制备方法,将钛溶胶改性可逆变色微胶囊与高反射白色颜填料充分混合后,再与成膜剂及水混合均匀,最后再加入碳化胶凝材料,搅拌均匀后制备成均匀浆体,通过喷涂的形式涂覆在基体表面,涂覆厚度为3mm,通过碳化养护方式使其凝结硬化,碳化养护的CO2浓度为100%,碳化压力为0.1Mpa,养护温度为25℃,养护时间6h,得到负碳且自主调温的温致变色涂层。
其中,钛溶胶改性可逆变色微胶囊的制备方法如下,将隐色剂为热敏红的有机可逆温致变色微胶囊超声分散在制备合成的钛溶胶中,有机可逆温致变色微胶囊与钛溶胶质量比为0.3,其钛溶胶质量分数为2.5%,超声分散3h,之后滤出,40℃干燥12h备用。
对比例1
一种涂层,其组分与制备方法与实施例1相同,所不同的是,将隐色剂为热敏红并经溶胶改性可逆变色微胶囊替换为氧化铁红颜料。
对比例2
一种涂层,其组分与制备方法与实施例1相同,所不同的是,不包括钛溶胶改性可逆变色微胶囊。
对比例3
一种涂层,其组分与制备方法与实施例4相同,所不同的是,将隐色剂为热敏黑并经钛溶胶改性可逆变色微胶囊替换为同色未改性的可逆变色微胶囊。
评价测试
将实施例及对比例所得涂层以相应的配比按照相同的搅拌制度涂于相同材料的水泥板材之上,按照相应的碳化养护制度,在相同的室内环境中进行相应时间的养护。使用紫外/可见/近红外分光光度计测试涂层的反射率,取相同涂层测温度为25℃时深色态以及温度在35℃时浅色态的光谱反射率;抗紫外老化性能通过在紫外老化试验箱中放置120h,使用色差仪记录各个样品与其初始状态下的色差值,与原始色差值越大,证明其紫外破坏越严重,结果如表1所示。用氙灯模拟太阳光,持续照射涂层1小时后,关掉氙灯,用电偶丝记录涂层温度随时间变化过程,如图1所示。
表1测试结果
本方案的涂层深色态反射率低,对可见光吸收多,涂层冬季可吸热,且浅色态反射率高,本方案高温下无色反射率较高,低温下有色相反射率相对较低,满足自主调温的目的,具体来看,实施例1和对比例1和对比例2的固定色涂层相比,掺入改性过的红色感温变色微胶囊后其涂层的深色态反射率要低于对比例1同色态的涂层,高温浅色态光谱反射率与对比例2不掺的感温变色材料的白色涂层相比,其反射率略低,说明即使涂层温升变色呈浅色态,感温变色颜料的加入对涂层反射率造成影响,对实施例1、实施例5、对比例1及2进行室内氙灯模拟太阳辐照,温度曲线如图1所示,从图中曲线可以看出,相对于同色氧化铁涂层,所制备的温变涂层其温度更低,即温度升高,相变浅色态时能够有效反射阳光;同时与不掺加感温变色的白色涂层对比,其温度略高,说明变色微胶囊的引入使得涂层有升温效果;对比实施例1和5,可以看出高反射白色颜填料的种类、含量影响温度效果。同时对比实施例4与对比例3,经过钛溶胶改性的可逆感温变色涂层其紫外耐久性要高于未经改性,同时经过改性的微胶囊与涂层中无机粉末更好的接触,相对于对比例3其粘结强度也有一定的提升。实施例1到实施例4,抗紫外老化性能与反应过程中钛溶胶质量分数,以及变色微胶囊与钛溶胶的质量比有关,其质量比越小,钛溶胶质量分数越高,其抗紫外老化能力越强。
以上,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种负碳且自主调温的温致变色涂层,其特征在于,包括质量份数如下的组分:1-10份钛溶胶改性可逆变色微胶囊、60-115份碳化胶凝材料、1-50份高反射白色无机填料、1-20份成膜剂、50-120份水;所述钛溶胶改性可逆变色微胶囊的制备方法如下:将可逆变色微胶囊超声分散于经溶胶凝胶法合成的钛溶胶中,再过滤干燥,即得所述钛溶胶改性可逆变色微胶囊。
2.根据权利要求1所述的负碳且自主调温的温致变色涂层,其特征在于,所述可逆变色微胶囊包括芯材和包裹所述芯材的壁材,所述壁材为三聚氰胺甲醛树脂,所述芯材为隐色剂、显色剂及溶剂的混合物。
3.根据权利要求2所述的负碳且自主调温的温致变色涂层,其特征在于,所述隐色剂为荧烷类染料。
4.根据权利要求1所述的负碳且自主调温的温致变色涂层,其特征在于,所述钛溶胶改性可逆变色微胶囊的平均粒径为5-15μm,其变色温度为25-34℃。
5.根据权利要求1所述的负碳且自主调温的温致变色涂层,其特征在于,所述碳化胶凝材料包括硅酸二钙、硅酸三钙、硅酸一钙及氧化镁、氧化钙、氢氧化钙中的一种或几种,所述碳化胶凝材料的平均粒径为0.1-120μm。
6.根据权利要求1所述的负碳且自主调温的温致变色涂层,其特征在于,所述高反射白色无机填料包括纳米氧化铝、纳米金红石型二氧化钛、超细硫酸钡、二氧化锆中的一种或多种。
7.一种如权利要求1-6任一项所述的负碳且自主调温的温致变色涂层的制备方法,其特征在于,包括以下步骤:按质量份将所述钛溶胶改性可逆变色微胶囊、碳化胶凝材料、高反射白色无机填料、成膜剂、水混合搅拌均匀,得到浆体,将所述浆体涂覆于基体表面,利用碳化养护将所述浆体固化于所述基体表面,即得所述负碳且自主调温的温致变色涂层。
8.根据权利要求7所述的制备方法,其特征在于,所述碳化养护的CO2浓度为10-100%,养护温度为-20-200℃,养护时间0.5-72h,碳化压力0.1-0.3MPa。
9.一种如权利要求1-6任一项所述的负碳且自主调温的温致变色涂层在建筑材料外层中的应用。
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