CN115595796B - 一种辐射制冷纤维及其制备方法、织物 - Google Patents
一种辐射制冷纤维及其制备方法、织物 Download PDFInfo
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- CN115595796B CN115595796B CN202211315318.XA CN202211315318A CN115595796B CN 115595796 B CN115595796 B CN 115595796B CN 202211315318 A CN202211315318 A CN 202211315318A CN 115595796 B CN115595796 B CN 115595796B
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Abstract
本发明公开了一种辐射制冷纤维及其制备方法、织物,该辐射制冷纤维包括基体树脂,基体树脂内部填充有大气窗口高发射率的填料,填料内部包覆有辐射制冷层状复合纤维芯,辐射制冷层状复合纤维芯包括基膜层、封装膜层以及封装在二者之间的太阳光谱波段高反射率金属膜层。本发明的辐射制冷纤维及其制备方法、织物具有透气性好、柔软性佳、降温效果优、厚度可控性强和成本低廉的特点。
Description
技术领域
本发明设计辐射制冷材料技术领域,具体是指一种辐射制冷纤维及其制备方法、织物。
背景技术
太阳辐射到达地球表面,使地球表面温度升高,而在夜间,地球向外太空辐射自身的热量,从而使地球温度维持在适宜人生活的范围,因为有大气层的存在,不但阻挡了部分到达地球表面的太阳辐射,同时阻挡了部分地球辐射的热量,从而使地球昼夜温差维持在适宜人生存的范围。而大气层同样在地球向外太空辐射能量中,对8-13um波长的辐射能量具有低吸收的特点,波长8-13um被称为大气窗口。辐射制冷材料是指对太阳光谱具有高反射,对大气窗口具有高发射的材料。例如在撒哈拉沙漠的银蚁可以在夏季高温的沙漠生存,得益于其皮肤表面具有辐射制冷材料的光谱特征,其具有在太阳波段高反射,在远红外波段高发射的特点,因此,设计一种类似银蚁皮肤的衣物用于抵御夏季高温成为未来新材料发展的重要方向之一。辐射制冷材料提出了一种利用外太空冷源的方式,通过大气窗口将地球表面热量辐射向外太空。辐射制冷技术通过材料的选择和结构设计,可以实现在太阳光谱波段高反射,在大气窗口高发射的光谱特性,一方面阻挡太阳热量输入,另一方面同时将自身热量以大气窗口波段电磁波的形式排放到外太空,从而实现自身降温的目的,可实现零能耗降温。辐射制冷技术是目前一种被动式的制冷方式,其利用外太空的冷源,不主动消耗能源,具有高效清洁的特点,辐射制冷材料目前已经公共建筑、工业厂房、粮食仓储、户外电柜、石化储罐等广泛应用,其降温节能效果显著。如将其制备成纤维做成衣物,可成为夏日户外最佳降温方式,为夏日个人热管理提供了一种新的技术路径,是未来智能服装的发展方向之一。
美国Yuan Yang教授采用相位反转方法,制备了一种含氟的混合溶液,其具备微米和纳米级的微孔,利用微纳孔可以有效散射太阳辐射,实现对太阳辐射的高反射的效果,同时氟类涂层可在大气窗口8-13um波长具有高发射的特点,制备300um的涂层实现96%的高太阳光反射率和大气窗口97%的高发射率,在阳光下测试,可使物体温度下降约6℃,产生约96W/m2的制冷功率。但其制备方法复杂,且所需辐射制冷层较厚,无法用于柔软的织物面料。中国专利CN111393915A公开了一种辐射制冷材料,将氧化铝纳米粒子涂在纤维织物上,织物和涂层构成了辐射制冷织物,其可以实现在太阳光下辐射自降温功能,但其因涂层属于无机粒子影响了纤维的柔软性。中国专利CN 111560672 B公开了一种辐射制冷功能复合纱及其面料,先制备沾满微纳颗粒的无纺布条带和具有冷感的无纺布条带,其微纳颗粒具有辐射制冷功能,然后将两种条带制成复合纤维条带,在制备成纱芯,最厚加工成复合纱,其利用浸轧法和包覆法,制备的辐射制冷复合纱及其面料可实现降温的效果,方法简单,流程短的问题,但其日间辐射制冷的效果较差。中国专利CN1134453108B公开了一种镀银尼龙纤维的制备方法,其采用化学镀银的方法,将银镀在尼龙纤维的表面,得到镀银纤维,但其主要用于导电、电磁屏蔽、抗菌等领域,其大气窗口发射率很低,太阳光谱反射率低,镀银纤维产品无法用于降温方向。
综上所述,现有辐射制冷材料用于织物面料存在以下缺点:1、采用涂层或者填料添加形式制备的面料,因填料多为无机粒子,造成织物的透气性和舒适性较差;2、静电纺丝等方法工艺复杂、成本高;3、利用熔融纺丝或包覆的方法制备的辐射制冷纤维,在包覆树脂中添加了反射填料,因填料比例添加过大会影响纤维柔韧性,而在较低填充量下,其反射率偏低,造成的日间辐射制冷效果不理想较差;4、采用微纳孔方法制备的辐射制冷纤维其制备孔的工艺较难控制,其主要利用微纳孔对光线的多次散射来达到高反射率的原理,因此需要一定厚度才能达到较高反射率,因此其纤维直径偏大。
发明内容
本发明的目的是提供一种辐射制冷纤维及其制备方法、织物,具有透气性好、柔软性佳、降温效果优、厚度可控性强和成本低廉的特点。
本发明可以通过以下技术方案来实现:
本发明公开了一种辐射制冷纤维,包括壳层和包覆在壳层内部的芯层,壳层为大气窗口高发射率层,该大气窗口高发射率层包括基体树脂及均匀分散在基体树脂的大气窗口高发射率填料;芯层为层状复合纤维芯,层状复合纤维芯包括依次设置在镀膜基膜层上的太阳光谱波段高反射率金属膜层和封装膜层。
其中纤维芯层中的金属镀层起到了太阳光热量的高反射作用,而封装层避免了超薄金属镀层易氧化,后续纤维加工过程易剥落。外层包覆的大气窗口高发射率层设计,可以进一步提高大气窗口的发射率,因大气窗口发射率与发射层的厚度相关,并添加的大气窗口高发射率填料可进一步提高发射率,同时外围包覆的结构设计可以解决层壮纤维芯横截面金属层易氧化的问题。
进一步地,太阳光谱波段高反射率金属膜层与封装膜层之间设置有封装胶粘剂膜层。该封装胶粘剂膜层要求具有太阳光谱低吸收率<5%,同时具有金属层和封装膜层良好粘接力。
进一步地,太阳光谱波段高反射率金属膜层的材质为金属或其合金混合物,金属选自于银、铝、金、铬、铜、不锈钢、和/或镍中的一种或两种以上。优选银、铝作为反射金属材质。
进一步地,镀膜基膜层、封装膜层、基体树脂的材质选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯、聚丙烯酸酯、聚丙烯、聚氨酯、聚酰胺、聚乙烯、ABS塑料、聚碳酸酯、聚氯乙烯、聚四氟乙烯、聚三氟氯乙烯、聚氟乙烯、聚偏氟乙烯、聚己二醇、聚偏二氯乙烯、聚全氟乙丙烯、乙烯-四氟乙烯共聚物、聚乙烯醇中的一种或者两种以上。镀膜基膜层和封装膜层优选PET、PC、ABS、TPU,基体树脂优选PVDF、PMMA、ETFE、TPU。
进一步地,封装胶粘剂膜层的材质为单组分或双组分的聚氨酯类、丙烯酸酯类、有机硅类和/或环氧树脂类。
进一步地,填料选自TiO2、SiO2、BaSO4、SiC中的一种或两种以上;大气窗口高发射率填料添加比例为大气窗口高发射率填料和基体树脂质量总和的0.1-30wt%,优选0.1-10%。
进一步地,太阳光谱波段高反射率金属膜层的表面镀覆有金属封装层,金属封装层的材质为AZO、ITO、TiO2、SiO2、Si3N4、Nb2O5、NiCr、Ta2O5和/或NiCrNX中的一种或两种以上;其厚度在0.5-30nm。该金属封装层同时具有种子层的作用,可有效提高镀层附着力和耐候性。
本发明的另外一个方面在于保护上述辐射制冷纤维的制备方法,包括以下步骤:
S1、太阳光谱波段高反射率金属膜层的镀膜:将太阳光谱波段高反射率金属膜层镀覆在镀膜基膜层上;
S2、辐射制冷层状复合薄膜封装:然后通过涂布复合工艺,用封装胶粘剂膜层将封装膜层对太阳光谱波段高反射率金属膜层进行复合封装形成层状复合薄膜;
S3、辐射制冷层状复合纤维芯的膜裂制备:通过膜裂法生产工艺将层状复合薄膜制备成层状复合纤维芯;
S4、辐射制冷纤维的外包覆:通过纤维包覆工艺,将辐射制冷层状复合纤维芯包覆在内部填充有大气窗口高发射率填料的基体树脂内部,制得辐射制冷纤维。
进一步地,辐射制冷层状复合纤维芯为扁状芯带,扁状芯带的厚度为2-800um,优选3-80um,宽度为2-800um,优选3-500um;基体树脂的厚度为1-200um;镀膜基膜层的厚度为6-150um,优选23-75um;太阳光谱波段高反射率金属膜层的厚度为10-250nm,封装膜层的厚度为6-150um,优选6-75um。
优选地,在步骤S1太阳光谱波段高反射率金属膜层的镀膜中,镀膜工艺为真空磁控溅射、离子束、电镀、真空蒸发镀膜和/或化学镀中的一种或二种以上。优选真空磁控溅射、真空蒸发镀膜方式或两种方式结合。
优选地,步骤S4辐射制冷纤维的外包覆工艺为熔融包覆。
优选地,基体树脂还包括助剂,助剂为紫外阻隔剂、抗氧剂、抗菌剂、和/或色粉。
本发明的另外一个方面在于保护上述辐射制冷纤维编织而成的织物。
本发明一种辐射制冷纤维及其制备方法、织物,具有如下的有益效果:
本发明将易规模化生产的高反射率的超薄太阳光谱波段高反射率金属膜层作为反射层,超薄金属作为反射层其反射率相比于添加反射填料的工艺路线更高,且不会影响纤维的柔软性,而微纳孔工艺路线需要较厚的厚度才能达到较高反射率,无法得到很细纤维,所得织物柔软性差。
本发明包覆大气窗口高发射率填料的基体树脂的结构,形成纤维多层的芯核结构,并且可调节任意层的厚度,来调节反射率和大气窗口发射率。该制备方法的纤维不仅具有优异的辐射制冷性能,同时具备纤维的柔软性,可以采用各种编织方法和纱支密度来编织各类布料,并可调整织物的孔隙率,相比采用辐射制冷涂层涂布在织布表面的方案具有更好的透气性。本发明制备纤维结构相比于微纳孔制备纤维、静电纺丝和纤维镀膜等工艺路线,生产工艺更加简单,质量更容易控制且生产成本更低。本发明将大气窗口高发射率树脂作为外皮的结构设计可以最大限度的提升降温效果,并且可以保护内芯的太阳光谱波段高反射率金属膜层氧化,用此纤维制备的织物,具有优异的降温效果,同时具有良好的导热性、透气性、电磁屏蔽特性。
附图说明
图1为本发明辐射制冷纤维的横截面示意图;
图2为本发明实施例1制备的辐射制冷纤维编织成织物的太阳光谱反射率曲线;
图3为本发明实施例1制备的辐射制冷纤维编织成织物的大气窗口发射率曲线;
图4为本发明实施例4和对比例1大气窗口发射率对比曲线;
图5为本发明实施例4和对比例2太阳光谱反射率对比曲线;
图中:11为镀膜基膜层;12为太阳光谱波段高反射率金属膜层;13为封装胶粘剂膜层;14为封装膜层;21为基体树脂;22为填料。
具体实施方式
为了使本技术领域的人员更好地理解本发明的技术方案,下面结合实施例及附图对本发明产品作进一步详细的说明。
如图1所示,本发明公开了一种辐射制冷纤维,包括基体树脂21,基体树脂21内部填充有大气窗口高发射率填料22,填料22内部包覆有辐射制冷层状复合纤维芯,辐射制冷层状复合纤维芯包括镀膜基膜层11、封装膜层14以及封装在二者之间的太阳光谱波段高反射率金属膜层12。
如图1所示,太阳光谱波段高反射率金属膜层12与封装膜层14之间设置有封装胶粘剂膜层13。
进一步地,太阳光谱波段高反射率金属膜层与封装膜层之间设置有封装胶粘剂膜层。该封装胶粘剂膜层要求具有太阳光谱低吸收率<5%,同时具有金属层和封装膜层良好粘接力。
进一步地,太阳光谱波段高反射率金属膜层的材质为金属或其合金混合物,金属选自于银、铝、金、铬、铜、不锈钢、和/或镍中的一种或两种以上。优选银、铝作为反射金属材质。
进一步地,镀膜基膜层、封装膜层、基体树脂的材质选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯、聚丙烯酸酯、聚丙烯、聚氨酯、聚酰胺、聚乙烯、ABS塑料、聚碳酸酯、聚氯乙烯、聚四氟乙烯、聚三氟氯乙烯、聚氟乙烯、聚偏氟乙烯、聚己二醇、聚偏二氯乙烯、聚全氟乙丙烯、乙烯-四氟乙烯共聚物、聚乙烯醇中的一种或者两种以上。镀膜基膜层和封装膜层优选PET、PC、ABS、TPU,基体树脂优选PVDF、PMMA、ETFE、TPU。
进一步地,封装胶粘剂膜层的材质为单组分或双组分的聚氨酯类、丙烯酸酯类、有机硅类和/或环氧树脂类。
进一步地,填料选自TiO2、SiO2、BaSO4、SiC中的一种或两种以上;大气窗口高发射率填料添加比例为大气窗口高发射率填料和基体树脂质量总和的0.1-30wt%,优选0.1-10%。
进一步地,太阳光谱波段高反射率金属膜层的表面镀覆有金属封装层,金属封装层的材质为AZO、ITO、TiO2、SiO2、Si3N4、Nb2O5、NiCr、Ta2O5和/或NiCrNX中的一种或两种以上;其厚度在0.5-30nm。该金属封装层同时具有种子层的作用,可有效提高镀层附着力和耐候性。
进一步地,辐射制冷层状复合纤维芯为扁状芯带,扁状芯带的厚度为2-800um,优选3-80um,宽度为2-800um,优选3-500um;基体树脂的厚度为1-200um;镀膜基膜层的厚度为6-150um,优选23-75um;太阳光谱波段高反射率金属膜层的厚度为10-250nm,封装膜层的厚度为6-150um,优选6-75um。
优选地,在步骤S1太阳光谱波段高反射率金属膜层的镀膜中,镀膜工艺为真空磁控溅射、离子束、电镀、真空蒸发镀膜和/或化学镀中的一种或二种以上。优选真空磁控溅射、真空蒸发镀膜方式或两种方式结合。
优选地,步骤S4辐射制冷纤维的外包覆工艺为熔融包覆。
优选地,基体树脂还包括助剂,助剂为紫外阻隔剂、抗氧剂、抗菌剂、和/或色粉。
本发明的另外一个方面在于保护上述辐射制冷纤维编织而成的织物。
实施例1
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为75um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为75um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制5um,得到的复合膜,厚度为155um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为200um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PMMA树脂99%,TiO2填料0.5%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为30um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,其光谱曲线见图2,从图中可以看出在太阳光谱波长250-2500nm,整体反射率均非常高,在紫外波段250-35nm,具有较高吸收率,添加的紫外阻隔剂可以防止基体树脂的老化。所得纤维及织物的光谱曲线见图3,从图中可以看到在远红外波长2.5-25um具有一定的光谱选择性,在大气窗口波长8-13um,其发射率达到92%,而在非窗口波长,其发射率低,良好的光谱选择性具有更好的辐射制冷效果。纤维断裂伸长率100%,编织的孔隙率为2%,织物的厚度为190-230um。
实施例2
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为75um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为75um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制5um,得到的复合膜,厚度为155um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为200um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂99%,TiO2填料0.5%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为30um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,大气窗口发射率为92%,编织的孔隙率为2%,织物的厚度为200-230um。
实施例3
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为75um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为75um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制5um,得到的复合膜,厚度为155um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为200um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂98.5%,TiO2填料1%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,大气窗口发射率为95%,编织的孔隙率为2%,织物的厚度为200-230um。
实施例1与实施例2对比,其辐射制冷树脂的基体树脂由PMMA更换为PVDF,碳氧双键(C=O)和碳氟键(C-F)在8-13um波长都具有较强的振动吸收,因此更换辐射制冷基体树脂后,对其大气窗口发射率影响不大。实施例2和实施例3对比,辐射制冷树脂的包覆厚度从30um提高到70um,辐射制冷填料的比例从0.5%提高到1%,所得辐射制冷纤维的大气窗口发射率从92%提高到95%。数据表明,通过调节大气窗口高发射率辐射制冷树脂的厚度以及填料的比例,可以提高辐射制冷纤维的大气窗口发射率。
实施例4
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为23um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为23um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制3um,得到的复合膜,厚度为52um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为100um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂98.5%,TiO2填料1%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为93%,大气窗口发射率为95%,编织的孔隙率为2%,织物的厚度为120-170um。
实施例5
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为23um的PET薄膜上,沉积厚度为100nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为23um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制3um,得到的复合膜,厚度为49um的复合膜,复合膜上下两面的太阳光反射率都≥93%;然后通膜裂法将复合薄膜切割成宽度为100um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂98.5%,TiO2填料1%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为90%,大气窗口发射率为95%,编织的孔隙率为2%,织物的厚度为120-170um。
实施例6
将太阳波段高反射率金属Al通过真空磁控镀膜的方法沉积在厚度为23um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为23um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制3um,得到的复合膜,厚度为49um的复合膜,复合膜上下两面的太阳光反射率都≥81%;然后通膜裂法将复合薄膜切割成宽度为100um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂98.5%,TiO2填料1%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为80%,大气窗口发射率为95%,编织的孔隙率为2%,织物的厚度为120-170um。
实施例7
先将1-2nm厚的种子层ITO通过真空磁控镀膜的镀在厚度为23um的PET薄膜上,再将太阳波段高反射率金属Ag方法沉积在ITO薄膜上,沉积厚度为150nm,再将1-2nm的封装层ITO镀在金属银上,形成ABA结构的镀层结构;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为23um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制3um,得到的复合膜,厚度为49um的复合膜,复合膜上下两面的太阳光反射率都≥81%;然后通膜裂法将复合薄膜切割成宽度为100um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂98.5%,TiO2填料1%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,大气窗口发射率为95%,编织的孔隙率为2%,织物的厚度为120-170um。
实施例4相比与实施例3减薄镀膜基材的厚度,可使纤维直径更小,所得织物的厚度从200-230um降低到120-170um,在具有相同太阳光反射率和大气窗口发射率下,纤维更柔软,织物的克重更低,纤维编织物更轻薄,人体穿着舒适性更好。实施例5相比实施例4,镀银的厚度从150nm减少到100nm,所得纤维织物的太阳光发射率从92%降低到90%,大气窗口的发射率不变,实施例6相比与实施例4,将镀膜的金属从Ag更换为Al后,其太阳光反射率从92%降低到80%,但其成本更低,可根据市场需要调整金属层的厚度和材质来控制太阳光反射率的高低和辐射制冷纤维的成本。实施例7相比与实施例4,其镀膜结构从单独金属Ag层调整为ITO/Ag/ITO结构,其银的耐腐蚀性大幅提高,大幅减少了银在辐射制冷纤维制备过程的氧化腐蚀的可能性。
实施例8
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为75um的PVC薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为75um厚度的PVC薄膜与镀膜PVC的镀层面进行复合,涂胶厚度控制5um,得到的复合膜,厚度为155um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为200um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由TPU树脂99%,SiO2填料0.5%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为30um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,大气窗口发射率为92%,纤维断裂伸长率500%,编织的孔隙率为2%,织物的厚度为190-230um。
实施例9
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为75um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为75um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制5um,得到的复合膜,厚度为155um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为200um的纤维,再通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由TPU树脂99%,SiO2填料0.5%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为92%,大气窗口发射率为94%,纤维断裂伸长率300%,编织的孔隙率为2%,织物的厚度为190-230um。
实施例8相比于实施例1,其镀膜基材选用断裂伸长率高的PVC材质,实施例8、实施例9相比与实施例1所用辐射制冷树脂也选用断裂伸长率高的TPU材质。所得辐射制冷纤维的断裂伸长率从100%提高到300%和500%,可以通过镀膜基材和辐射制冷树脂的材质选择,实现辐射制冷纤维的高弹性,所制备的衣物具备一定的弹性,其织物用品可用于户外运动服装,既提高了织物的弹性,又可实现降温的效果。
对比例1
将太阳波段高反射率金属Ag通过真空磁控镀膜的方法沉积在厚度为23um的PET薄膜上,沉积厚度为150nm;然后采用耐候性好的聚氨酯胶粘剂将封装的厚度为23um厚度的PET薄膜与镀膜PET的镀层面进行复合,涂胶厚度控制3um,得到的复合膜,厚度为52um的复合膜,复合膜上下两面的太阳光反射率都≥94%;然后通膜裂法将复合薄膜切割成宽度为100um的纤维,将制备的反射纤维按所需的编织方式做成织物。
本实施例制备得到的纤维及织物的太阳光反射比为93%,大气窗口发射率为12%,编织的孔隙率为2%,织物的厚度为50-100um。
对比例2
用直径为30um尼龙纤维通过纤维熔融包覆工艺,将辐射制冷树脂包覆在纤维表面,辐射制冷树脂是有由PVDF树脂99%,SiO2填料0.5%,uv吸收剂0.4%,抗氧剂0.1%组成,包覆的厚度为70um,最后将制备的辐射制冷纤维按所需的编织方式做成织物。
本实施例制备得到的辐射制冷纤维及织物的太阳光反射比为8%,大气窗口发射率为94%,编织的孔隙率为2%,织物的厚度为100um。
对比例3
本实施例涉及直径为190um的尼龙纤维及织物,其太阳光反射比为8%,大气窗口发射率为12%。
对比例1与实施例4相比,对比例1没有大气窗口高发射率的结构设计,发射率对比曲线见图4,其无法实现日间和夜间辐射降温的效果,对比例2相比与实施例4,对比例2没有高反射的金属层,反射率对比曲线见图5,其只有大气窗口的高发射层,可以实现在夜间的降温,但无法实现日间降温的效果,但降温效果优于常规的尼龙纤维对比例3。
以上各实施例和对比例的降温测试见表1:
表1、性能测试结果
上述实施例仅为本发明的具体实施例,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些显而易见的替换形式均属于本发明的保护范围。
Claims (9)
1.一种辐射制冷纤维,包括壳层和包覆在壳层内部的芯层,其特征在于:所述壳层为大气窗口高发射率层,该大气窗口高发射率层包括基体树脂及均匀分散在基体树脂的大气窗口高发射率填料;所述芯层为层状复合纤维芯,层状复合纤维芯包括依次设置在镀膜基膜层上的太阳光谱波段高反射率金属膜层和封装膜层;
所述大气窗口高发射率层的基体树脂、封装膜层、镀膜基膜层的材质选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯、聚丙烯酸酯、聚丙烯、聚氨酯、聚酰胺、聚乙烯、ABS塑料、聚碳酸酯、聚氯乙烯、聚四氟乙烯、聚三氟氯乙烯、聚氟乙烯、聚偏氟乙烯、聚己二醇、聚偏二氯乙烯、聚全氟乙丙烯、乙烯-四氟乙烯共聚物、聚乙烯醇中的一种或者两种以上混合物。
2.根据权利要求1所述的辐射制冷纤维,其特征在于:所述太阳光谱波段高反射率金属层与所述封装膜层之间设置有封装胶粘剂膜层。
3.根据权利要求1所述的辐射制冷纤维,其特征在于:所述太阳光谱波段高反射率金属膜层的材质为金属或金属合金,所述金属选自于银、铝、金、铬、铜、镍中的一种或两种以上合金。
4.根据权利要求2所述的辐射制冷纤维,其特征在于:所述封装胶粘剂膜层的材质为聚氨酯类、丙烯酸酯类、有机硅类和/或环氧树脂类。
5. 根据权利要求1所述的辐射制冷纤维,其特征在于:所述大气窗口高发射率填料选自TiO2 、SiO2、BaSO4、SiC中的一种或两种以上;所述大气窗口高发射率填料添加比例为大气窗口高发射率填料和基体树脂质量总和的0.1-30wt%。
6. 根据权利要求1所述的辐射制冷纤维,其特征在于:所述太阳光谱波段高反射率金属膜层的表面镀覆有金属封装层,所述金属封装层的材质为AZO、ITO、TiO2 、SiO2、Si3N4、Nb2O5、NiCr、Ta2O5中的一种或两种以上。
7.一种权利要求2所述辐射制冷纤维的制备方法,其特征在于包括以下步骤:
S1、太阳光谱波段高反射率金属膜层的镀膜:将太阳光谱波段高反射率金属膜层镀覆在镀膜基膜层上;
S2、辐射制冷层状复合薄膜封装:然后通过涂布复合工艺,用封装胶粘剂膜层将封装膜层对太阳光谱波段高反射率金属膜层进行复合封装形成层状复合薄膜;
S3、辐射制冷层状复合纤维芯的膜裂制备:通过膜裂法生产工艺将层状复合薄膜制备成层状复合纤维芯;
S4、辐射制冷纤维的外包覆:通过纤维包覆工艺,将辐射制冷层状复合纤维芯包覆在内部填充有大气窗口高发射率填料的基体树脂内部,制得辐射制冷纤维。
8.根据权利要求7所述的辐射制冷纤维的制备方法,其特征在于:
在步骤S1太阳光谱波段高反射率金属膜层的镀覆中,镀覆工艺为真空磁控溅射、离子束、电镀、真空蒸发镀膜和/或化学镀中的一种或二种以上结合;
步骤S4辐射制冷纤维的外包覆工艺为浸润包覆和/或熔融包覆;
所述基体树脂还包括助剂,所述助剂为紫外阻隔助剂、抗氧剂、抗菌剂和/或色粉。
9.一种由权利要求1-6任一项所述辐射制冷纤维编织而成的织物。
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