CN110387751A - 一种辐射自降温功能纤维织物及其制备方法 - Google Patents
一种辐射自降温功能纤维织物及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种辐射自降温功能纤维织物及其制备方法,其特征在于该功能纤维织物是在纤维织物表面依次涂布高反射铝银层和8~14μm红外强选择性吸收辐射涂层;8~14μm红外强选择性吸收辐射涂层由活性纳米功能组合物和含氟聚合物树脂溶液组成,其中所述的活性纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比1:(0.5~2):(0.5~2)混合并由硅烷偶联剂改性而成;含氟聚合物树脂溶液的固体组分质量占8~14μm红外强选择性吸收辐射涂层质量的10%~80%。本发明提供的功能纤维织物能够在太阳光照和无光照环境下发挥高效的辐射自降温功能,可广泛应用于建筑物、大功率装备外层披挂或用于制造自降温帐篷、功能衣物等领域。
Description
技术领域
本发明涉及一种辐射自降温功能纤维织物及其制备方法,属于功能复合纤维织物和热辐射技术领域。
背景技术
随着全球经济的不断发展,人类社会面临的能源需求越来越大,发展新型节能材料与技术,最大限度降低能源消耗,降低环境负荷,具有重要的经济和社会价值。辐射自降温是地面物体通过红外大气窗口将热量传递至外太空,进而降低自身温度的一种物理机制。在太阳光照条件下,物体表面温度的降低主要与几个方面密切相关:第一,对太阳光能量的吸收,要求物体表面对0.3~2.5μm太阳光要有尽可能高的反射;第二,对大气红外辐射能量的吸收,要求物体表面在非大气红外窗口区对周围环境中的大气红外能量有尽可能低的吸收;第三,通过红外窗口向大气环境中排出红外辐射,要求物体表面对8~14μm的红外光能量具有高的辐射;第四,自然空气下的热对流及热传导。
从现有公开报道来看,在无太阳光照条件下,利用辐射降温机制可以很好的实现物体自降温冷却,但是辐射降温材料在白天光照条件下的辐射自降温性能尚未满足实用要求。现有辐射自降温材料的制备主要有以下方式:(一)运用纳米光刻蚀和等离子沉积技术,构筑具有纳米微尺度结构的辐射降温器,辐射降温器的自降温性能虽好,但其制造工艺复杂、难度大、要求高,难以大规模、低成本生产。此外,还存在结构强度低、易破坏等不足之处;(二)将锐钛矿二氧化钛微粉、玻璃微球等无机功能物质与聚合物树脂均匀混合,并再其一侧表面上复合一定厚度的高反射金属铝或银膜以制成辐射自降温器,但由于选用的二氧化钛微粉、玻璃微球等无机功能物质在红外光谱区的选择性吸收辐射性能不强,制得的辐射自降温器难以获得较为理想的辐射自降温效果。
目前,常见的辐射自降温材料多为辐射自降温涂料,其对于涂刷基底的要求较高,一些表面粗糙、反射率低的物体难以有效应用。因此,开发既可以在白天和黑夜使用,同时能够大规模低成本生产的辐射自降温功能纤维织物非常必要也非常迫切。
发明内容
本发明的目的是提供一种能解决现有技术中存在缺陷的辐射自降温功能纤维织物,本发明的另一目的是提供上述辐射自降温功能纤维织物的制备方法。
为达到上述目的,本发明是通过以下技术方案实现的:一种辐射自降温功能纤维织物,其特征在于该功能纤维织物是在纤维织物表面依次涂布高反射铝银层和8~14μm红外强选择性吸收辐射涂层;8~14μm红外强选择性吸收辐射涂层由对可见-近红外太阳光透明且在8~14μm红外大气窗口具有强选择性吸收辐射特性的活性纳米功能组合物和在非红外大气窗口区透明的含氟聚合物树脂溶液组成,其中所述的活性纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比1:(0.5~2):(0.5~2)混合并由硅烷偶联剂改性而成;含氟聚合物树脂溶液的固体组分质量占8~14μm红外强选择性吸收辐射涂层质量的10%~80%。
优选上述高反射铝银层厚度为5~20μm,红外强选择性吸收/辐射涂层厚度为10~30μm。
优选所述的纤维织物为聚酯纤维织、聚酰胺纤维或聚氨酯纤维。上述高反射铝银层的光反射在80%以上,市场有售。
上述二氧化硅、稀土硅酸盐化合物和钼酸盐化合物分别在8~10μm、9~12μm和10~14μm范围内具有强的红外选择性吸收/辐射特性。其中稀土硅酸盐满足化学计量比SiO2-(0.5~2)RE2O3-(0~0.5)Na2O,RE为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc;碱土钼酸盐分子式为RMoO4,R为Mg、Ca、Sr或Ba。
优选上述的纳米稀土硅酸盐氧化物在9~12μm红外光谱区具有强选择性吸收/辐射特性(红外辐射吸收系数大于0.8),由以下方法制备得到:根据稀土硅酸盐化合物的化学计量比,准确称取纳米二氧化硅、稀土硝酸盐和硝酸钠,混合分散到乙醇水混合溶液中;在70~80℃水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再在600~900℃热处理3~12小时得到稀土硅酸盐化合物。
优选上述的纳米钼酸盐化合物在10~14μm红外光谱区具有强选择性吸收/辐射特性(红外辐射吸收系数大于0.8),由以下方法制备得到:根据钼酸盐化合物的化学计量比,准确称取钼酸铵和碱土金属硝酸盐,溶解到去离子水中;配置质量浓度为5%~10%柠檬酸溶液,搅拌滴加入到上述溶液中,调节pH至3.0~4.0,在70~80℃水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再800~1000℃热处理3~12小时后,即得到钼酸盐化合物。
优选所述含氟聚合物树脂溶液为聚氟乙烯PVF、聚偏氟乙烯PVDF、聚三氟氯乙烯PCTFE、聚四氟乙烯PTFEDE、聚四氟乙烯(PTFE)或聚偏氟乙烯-六氟丙烯(P(VDF-HFP))树脂溶液中的任意一种;含氟聚合物树脂溶液质量固含量为30%~60%。
本发明还提供了一种制备上述的辐射自降温功能纤维织物的方法,其具体步骤如下:
a.按照纳米功能组合物质量比例,称取一定量纳米二氧化硅、稀土硅酸盐化合物和碱土钼酸盐化合物粉体,以及质量为纳米功能组合物质量为0.01%~0.2%的硅烷偶联剂,一起加入高速研磨分散机中,在300~400转/分钟条件下处理2~6小时,即获得所需的活性纳米功能组合物;
b.按含氟聚合物树脂溶液的固体组分质量占8~14μm红外强选择性吸收辐射涂层质量的比例,称取活性纳米功能组合物和含氟聚合物树脂溶液,并一起加入纳米研磨分散机中按300~400转/分钟研磨分散处理3~12小时,即获得8~14μm红外强选择性吸收辐射涂层;
c.采用喷涂或涂布工艺,在纤维织物表面依次按一定厚度的涂布高反射铝银层和8~14μm红外强选择性吸收辐射涂层,经过自然干燥后,即获得一种辐射自降温功能纤维织物。
优选所述的硅烷偶联剂为KH560或KH570。
有益效果:
本发明提供的辐射自降温功能纤维织物,通过多层功能复合组装,使得普通纤维织物具备了优异的可见-近红外太阳光反射和8~14μm红外强选择性吸收/辐射特性,进而可以在太阳光照和无太阳光照环境下发挥高效的辐射自降温功能,为各类建筑物、大功率装备零能耗自主降温冷却和制造自降温帐篷、衣物等提供了新的技术途径,节能领域应用广泛。
附图说明
图1是实施例1中纳米二氧化硅的红外吸收/辐射谱图;
图2是实施例1中稀土硅酸盐化合物的红外吸收/辐射谱图;
图3是实施例1中钼酸钙化合物的可见-红外吸收/辐射谱图。
具体实施方式
为了更好的理解本发明,特例举以下实施例对本发明进行详细阐述,但本发明的内容绝不仅仅限于下面的实施例。
下述实施中所用含氟聚合物树脂溶液为聚四氟乙烯PTFE浓缩分散液(牌号为HGF-1,固含量为60%),商品化水性聚偏氟乙烯-六氟丙烯P(VDF-HFP)树脂(相对分子质量4.7×105,美国苏威公司产,固含量40%);纳米二氧化硅为麦克林市售产品,平均粒径30纳米或50纳米;高反射铝银层材料为银箭牌水性漂浮型银浆。
下述实施例中,所用纳米功能组合物采用以下制备工艺制得:
1)根据稀土硅酸盐化合物化学计量比,准确称取一定量纳米二氧化硅、可溶性稀土硝酸盐和硝酸钠等原料,均匀混合分散到乙醇水混合溶液中;在水浴70℃搅拌条件下蒸发溶剂得到凝胶;经120℃低温预烧处理6小时后,再800℃热处理12小时得到稀土硅酸盐化合物。
2)根据钼酸盐化合物分子式,准确称取一定量钼酸铵((NH4)2MoO4)和可溶性碱土金属硝酸盐原料,均匀混合溶解到去离子水中;配置10%柠檬酸溶液并逐滴加入到上述溶液中,边加边剧烈搅拌,用氨水调节pH至3.0,在水浴80℃搅拌条件下蒸发溶剂得到凝胶;经150℃低温预烧处理后3小时后,再在1000℃热处理6小时,即可得到钼酸盐化合物。
实施例1
一种辐射自降温功能纤维织物,其制备方法包括以下步骤:
1)按照纳米功能组合物质量比例1:1:1,称取30g纳米二氧化硅(红外吸收/辐射谱图如图1所示)、30g稀土硅酸盐化合物SiO2-La2O3-0.5Na2O(红外吸收/辐射谱图如图2所示)和30g钼酸钙CaMoO4粉体(红外吸收/辐射谱图如图3所示),以及0.045g的硅烷偶联剂HK560(质量为纳米功能组合物0.05%),一起加入高速研磨分散机中,以300转/分钟处理6小时,制得活性纳米功能组合物。
2)按红外强选择性吸收/辐射涂层中含氟树脂固体含量60%质量比例,称取50g步骤(1)制得的活性纳米功能组合物和225g PTFE含氟聚合物树脂溶液,并一起加入纳米研磨分散机中,以300转/分钟处理12小时,即可获得制备红外强选择性吸收/辐射涂层所需的辐射自降温含氟聚合物功能涂料。
3)在普通聚酯纤维织(涤纶)物表面依次喷涂工艺5μm厚高反射铝银层和25μm厚红外强选择性吸收/辐射涂层,经过自然干燥后,即可获得所需的辐射自降温功能纤维织物。
实施例2
一种辐射自降温功能纤维织物,其制备方法包括以下步骤:
1)按照纳米功能组合物质量比例1:1.5:0.5,称取30g纳米二氧化硅、45g稀土硅酸盐化合物SiO2-0.5La2O3-1.0Na2O和15g钼酸镁MgMoO4粉体,以及0.09g硅烷偶联剂HK560(质量为纳米功能组合物0.1%),一起加入高速研磨分散机中,在400转/分钟条件下处理2小时,制得活性纳米功能组合物。
2)按红外强选择性吸收/辐射涂层中含氟树脂固体含量40%质量比例,将步骤(1)制得的90g活性纳米功能组合物和100g PTFE含氟聚合物树脂溶液,并一起加入纳米研磨分散机中,以350转/分钟处理8小时,即可获得制备红外强选择性吸收/辐射涂层所需的辐射自降温含氟聚合物功能涂料。
3)在普通聚酰胺纤维(锦纶)织物表面,采用涂布方式依次复合10μm厚高反射铝银层和20μm厚红外强选择性吸收/辐射涂层,经过自然干燥后,即可获得所需的辐射自降温功能纤维织物。
实施例3
一种辐射自降温功能纤维织物,其制备方法包括以下步骤:
1)按照纳米功能组合物质量比例1:0.5:1,称取20g纳米二氧化硅、10g稀土硅酸盐化合物SiO2-0.5La2O3-0.1Gd2O3-0.5Na2O和20g钼酸钙CaMoO4粉体,以及0.05g硅烷偶联剂HK560(质量为纳米功能组合物0.1%),一起加入高速研磨分散机中,在350转/分钟条件下处理4小时,制得活性纳米功能组合物。
2)按红外强选择性吸收/辐射涂层中含氟树脂固体含量70%质量比例,将45g步骤(1)制得的活性纳米功能组合物和105g P(VDF-HFP)含氟聚合物树脂溶液,并一起加入纳米研磨分散机中,以400转/分钟研磨分散处理3小时,即可获得制备红外强选择性吸收/辐射涂层所需的辐射自降温含氟聚合物功能涂料。
3)在普通聚氨酯纤维(氨纶)织物表面通过喷涂工艺依次复合厚度为15μm涂布高反射铝银层和30μm红外强选择性吸收/辐射涂层,经过自然干燥后,即可获得所需的辐射自降温功能纤维织物。
实施例4
一种辐射自降温功能纤维织物,其制备方法包括以下步骤:
4)按照纳米功能组合物质量比例1:2:2,称取20g纳米二氧化硅、40g稀土硅酸盐化合物SiO2-0.5La2O3-0.5Y2O3-1.0Na2O和40g钼酸钙CaMoO4粉体,以及0.1g硅烷偶联剂HK560(质量为纳米功能组合物0.1%),一起加入高速研磨分散机中,在350转/分钟条件下处理4小时,制得活性纳米功能组合物。
5)按红外强选择性吸收/辐射涂层中含氟树脂固体含量50%质量比例,将50g步骤(1)制得的活性纳米功能组合物和100g P(VDF-HFP)含氟聚合物树脂溶液,并一起加入纳米研磨分散机中,以400转/分钟研磨分散处理3小时,即可获得制备红外强选择性吸收/辐射涂层所需的辐射自降温含氟聚合物功能涂料。
6)在普通聚氨酯纤维(氨纶)织物表面通过喷涂工艺依次复合厚度为10μm涂布高反射铝银层和25μm红外强选择性吸收/辐射涂层,经过自然干燥后,即可获得所需的辐射自降温功能纤维织物。
Claims (7)
1.一种辐射自降温功能纤维织物,其特征在于该功能纤维织物是在纤维织物表面依次涂布高反射铝银层和8~14μm红外强选择性吸收辐射涂层;8~14μm红外强选择性吸收辐射涂层由对可见-近红外太阳光透明且在8~14μm红外大气窗口具有强选择性吸收辐射特性的活性纳米功能组合物和在非红外大气窗口区透明的含氟聚合物树脂溶液组成,其中所述的活性纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比1:(0.5~2):(0.5~2)混合并由硅烷偶联剂改性而成;含氟聚合物树脂溶液的固体组分质量占8~14μm红外强选择性吸收辐射涂层质量的10%~80%。
2.根据权利要求1所述的一种辐射自降温功能纤维织物,其特征在于:所述高反射铝银层厚度为5~20μm,红外强选择性吸收/辐射涂层厚度为10~30μm。
3.根据权利要求1所述的一种辐射自降温功能纤维织物,其特征在于所述的纤维织物为聚酯纤维织、聚酰胺纤维或聚氨酯纤维。
4.根据权利要求1所述的一种辐射自降温功能纤维织物,其特征在于:其中稀土硅酸盐满足化学计量比SiO2-(0.5~2)RE2O3-(0~0.5)Na2O,RE为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc;碱土钼酸盐分子式为RMoO4,R为Mg、Ca、Sr或Ba。
5.根据权利要求1所述的一种辐射自降温功能纤维织物,其特征在于:所述含氟聚合物树脂溶液为聚氟乙烯、聚偏氟乙烯、聚三氟氯乙烯、聚四氟乙烯、聚四氟乙烯或聚偏氟乙烯-六氟丙烯树脂溶液中的任意一种;含氟聚合物树脂溶液的质量固含量为30%~60%。
6.一种制备如权利要求1所述的一种辐射自降温功能纤维织物的方法,其具体步骤如下:
a.按照纳米功能组合物质量比例,称取一定量纳米二氧化硅、稀土硅酸盐化合物和碱土钼酸盐化合物粉体,以及质量为纳米功能组合物质量为0.01%~0.2%的硅烷偶联剂,一起加入高速研磨分散机中,在300~400转/分钟条件下处理2~6小时,即获得所需的活性纳米功能组合物;
b.按含氟聚合物树脂溶液的固体组分质量占8~14μm红外强选择性吸收辐射涂层质量的比例,称取活性纳米功能组合物和含氟聚合物树脂溶液,并一起加入纳米研磨分散机中按300~400转/分钟研磨分散处理3~12小时,即获得8~14μm红外强选择性吸收辐射涂层;
c.采用喷涂或涂布工艺,在纤维织物表面依次按一定厚度的涂布高反射铝银层和8~14μm红外强选择性吸收辐射涂层,经过自然干燥后,即获得一种辐射自降温功能纤维织物。
7.根据权利要求6所述的方法,其特征在于所述的硅烷偶联剂为KH560或KH570。
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CN115573169B (zh) * | 2022-09-26 | 2023-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | 辐射降温水性喷剂、其制备方法及应用 |
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