CN112140651A - 一种真空型柔性绝热夹层及其制备方法与应用 - Google Patents

一种真空型柔性绝热夹层及其制备方法与应用 Download PDF

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CN112140651A
CN112140651A CN202011062077.3A CN202011062077A CN112140651A CN 112140651 A CN112140651 A CN 112140651A CN 202011062077 A CN202011062077 A CN 202011062077A CN 112140651 A CN112140651 A CN 112140651A
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film
fiber
heat insulation
vacuum
layer
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武湛君
崔运广
牛慕绮
严佳
陈铎
李世超
王宏宇
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Dalian University of Technology
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Abstract

本发明公开了一种真空型柔性夹层及其制备方法与应用。包括隔热层、紧贴隔热层外部的保护层；隔热层由薄膜‑气凝胶毡真空块、热反射层和低温隔热纸构成，其中热反射层和低温隔热纸在真空薄膜层外交替铺层；保护层由纤维衬布和纤维增强薄膜两部分。其中，反射层为双面镀铝的超薄聚酯膜；所用薄膜是一种透气性极小的聚合物。本发明采用的是多层绝热结构与薄膜‑气凝胶毡真空块交替铺设的方式制成，其质轻高强、加工容易、绝热性能极佳，能在‑200℃～300℃温度环境范围内使用，能够用作柔性板材、柔性管材以及硬质轻质板材，具有很大的灵活使用性。

Description

一种真空型柔性绝热夹层及其制备方法与应用
技术领域
本发明涉及一种隔热夹层，尤其涉及一种真空型柔性绝热夹层及其制备方法与应用。
背景技术
随着航空航天科学技术的发展，低温推进剂液氧、液氢、液化天然气的应用越来越广泛。而无论是液氧、液氢、液化天然气的储存还是输送都需要隔热性能优异的隔热材料，目前，用于低温液体贮箱的绝热方式多为被动热防护措施，即采用热控涂层、隔热填充材料等方式，使得整体结构笨重、安全问题难以保证，而且热防护效果并不是很好。因此，真空绝热夹层的设计研究成为航空低温领域的一项重要内容。另外，目前用于液氧、液氢、液氮、液化天然气等低温液体的输送管道多为高真空金属绝热管道，这种管道虽然有较高的绝热性能，但是由于金属比重大，在航空航天轻量化发展方向上并不占优势，更重要的是金属管道在置放、连接、拆卸和转移过程中占用空间较大且操作不便，实际操作使用时十分麻烦，不但浪费很大人力，还浪费很长时间。
发明内容
为解决上述问题，本发明的目的在于提供一种真空型柔性绝热夹层及其制备方法与应用，与其他绝热结构相比除了绝热性能优异，甚至达到绝热层外部不结冰不结霜外，还能有效减轻自身重量并且在超低温环境下依然具有一定的韧性。
为了达到上述目的，本发明提供了一种真空型柔性绝热夹层，其结构分为隔热层和保护层两部分；所述隔热层由薄膜-气凝胶毡真空块、热反射层和低温隔热纸层叠而成；所述保护层由纤维增强薄膜和纤维衬布铺叠而成。所述真空型柔性绝热夹层的中间层为薄膜-气凝胶毡真空块，由中间层向两侧的外层分别依次为低温隔热纸、热反射层、纤维增强薄膜和纤维衬布；
所述纤维衬布和纤维增强薄膜构成保护层，所述热反射层、低温隔热纸和薄膜-气凝胶毡真空块构成隔热层，所述纤维衬布至少为1层，所述纤维增强薄膜为1～30层，优选为30层；所述热反射层为1～30层，优选为30层；所述低温隔热纸为1～30层，优选为30层；所述薄膜-气凝胶毡真空块至少为1层。
进一步地，所述纤维衬布厚度为0.1mm～0.3mm；所述纤维衬布可以按照使用环境条件选用玻璃纤维衬布、碳纤维衬布、聚酯纤维衬布或尼龙纤维衬布等；所述纤维衬布提供一定的强度并保护内部的薄膜结构。
进一步地，所述纤维增强薄膜是由薄膜和纤维编织物组成；所述纤维编织物可以按照使用环境条件选用玻璃纤维、碳纤维、尼龙纤维或聚酯纤维等；所述纤维编织物的厚度为0.01～0.03mm；所述薄膜为含氟聚合物薄膜；所述薄膜包括含氟聚合物—聚四氟乙烯、聚三氟氯乙烯和聚偏氟乙烯中的一种或几种；所述薄膜厚度为0.04mm～0.06mm；所述纤维增强薄膜能提供一定的强度和气密性。
进一步地，所述热反射层是厚度为0.005～0.01mm的双面镀铝聚酯薄膜，所述双面镀铝聚酯薄膜的镀铝层厚度500nm最优。
进一步地，所述低温隔热纸厚度为0.02mm～0.05mm。
进一步地，所述薄膜-气凝胶毡真空块由薄膜、气凝胶毡和吸附剂组成；所述薄膜包括高模量聚乙烯薄膜、聚酯类薄膜；所述薄膜袋的厚度为0.01mm～0.03mm；所述气凝胶毡的厚度为3mm～5mm；所述吸附剂为氧化钯和5A分子筛按照质量比1：2.8～3.4混合。纤维衬布提供一定的强度和保护内部薄膜；纤维增强薄膜是一种透气性极小的聚合物薄膜，除了提供一定强度外还能防止外部气体分子深入结构内部。
进一步地，所述氧化钯和5A分子筛为保证薄膜-气凝胶毡真空块的真空度。
本发明还提供了一种真空型柔性绝热夹层的制备方法，包括如下步骤：
a)筛选制备真空型柔性绝热夹层的材料
筛选依据：按照不同工况，筛选满足使用条件的材料来制备真空型柔性绝热夹层，比如若用于液化天然气输送管道时，真空型柔性绝热夹层所筛选的材料必须满足在-161℃时正常使用，并且具有一定的柔韧性；若用于液氧输送管道时，所选材料除了耐低温以及具有工作韧性之外，所用材料还必须满足液氧相容要求。
b)制备包含有吸附剂的薄膜-气凝胶毡真空块；
c)将0.02mm～0.05mm厚的低温隔热纸1～30层，放入烘箱中，50℃～70℃，保持60～80分钟，然后对称铺叠到薄膜-气凝胶毡真空块的上、下表面；
d)将热反射层对称铺叠到低温隔热纸的上、下表面，所述热反射层为0.005mm～0.01mm厚的双面镀铝超薄聚酯薄膜1～30层，镀铝厚度500nm最优；放入烘箱中，70℃～80℃，保持60～80分钟，制得隔热层；
e)按照纤维与含氟聚合物薄膜克重比1：9.7～10.3的比例，把纤维铺放在两层或多层含氟聚合物薄膜之间，利用热压机或挤塑机进行挤压成型，制成纤维增强薄膜；所述纤维包括玻璃纤维、碳纤维、尼龙纤维或聚酯纤维，所述含氟聚合包括聚四氟乙烯、聚三氟氯乙烯和聚偏氟乙烯中的一种或几种；
f)采用0.1mm～0.3mm厚的玻璃纤维、尼龙纤维或者聚酯纤维中的一种或两种作为纤维衬布，铺叠在纤维增强薄膜上、下表面，制得保护层；
g)将保护层对称铺在隔热层上、下两表面，进行烘干、热压处理，得到真空型柔性绝热夹层。
进一步地，所述薄膜-气凝胶毡真空块的制备方法包括如下步骤：
①将氧化钯与5A分子筛按照质量比1：2.8～3.4混合均匀，形成吸附剂；
②将吸附剂按质量比1：2～6分别塞填到气凝胶毡中以及均匀涂撒到气凝胶毡表面；所述气凝胶毡厚度为3mm～5mm，密度为0.1～0.3g/cm3，导热系数为0.017～0.02W/(m.K)；
③将上述处理后的气凝胶毡与薄膜袋一起放入烘箱中50℃～70℃，保持40～60分钟，所用薄膜袋可以为高模量聚乙烯薄膜袋、聚酯类薄膜袋；
④将烘干处理后的气凝胶毡放入薄膜袋中，用真空泵进行抽真空，使真空度达到-0.05MPa～-0.08MPa，即得薄膜-气凝胶毡真空块。
进一步地，所述低温隔热纸的常温下导热系数为0.01～0.02W/(m.K)，使用温度范围为-269℃～300℃；所述步骤f)中烘干的温度为100℃～110℃。
具体地，所述纤维可以按照使用环境条件选用玻璃纤维、碳纤维或者其他纤维；所述薄膜为某种含氟聚合物薄膜；所述热反射层3是双面镀铝的超薄聚酯膜；所述双面镀铝的超薄聚酯膜厚度为0.005mm～0.01mm，共30层，反射率为0.25；所述低温隔热纸4为阻燃型纤维隔热纸，共30层，厚度为0.02mm～0.05mm，常温下导热系数为0.01～0.02W/(m.K)，使用温度范围为-269℃～300℃；所述薄膜-气凝胶毡真空块5包括薄膜袋、气凝胶毡和吸附剂；所属薄膜袋为某种含氟聚合物薄膜，该薄膜抗透气性能优异，共30层，厚度为0.01mm～0.03mm；所述气凝胶毡厚度为3mm～5mm，密度为0.1～0.3g/cm3，导热系数为0.017～0.02W/(m.K)；所述吸附剂为氧化钯和5A分子筛。
本发明还提供了真空型柔性绝热夹层在制备低温液体贮箱或低温液体管道外表面隔热材料中的应用，所述低温为-200℃～-300℃。
发明有益效果
本发明采用的是多层绝热结构与薄膜-气凝胶毡真空块交替铺设的方式制成，其质轻高强、加工容易、绝热性能极佳，能在-200℃～-300℃温度环境范围内使用，能够用作柔性板材、柔性管材以及硬质轻质板材，具有很大的灵活使用性。
目前，许多低温液体(液化天然气、液氮、液氧等)容器的保温设备，复杂笨重，浪费材料，使得制造成本很高，而且后期维修麻烦。而真空型柔性绝热夹层制造成本低，制造工艺简单，绝热性能优异，使用温度范围宽泛，完全可以用于低温液体容器的保温隔热使用。
另外，真空型柔性绝热夹层，不但可以用于辅助保温隔热，还能直接用于低温液体(液化天然气、液氮、液氧等)柔性输送管道，现在很多低温液体管道为获得优异的低温韧性，开始使用非金属材料制备，而该发明完全可以用于这种管道的生产使用。
附图说明
图1为本发明所述真空型柔性绝热夹层的结构。
图中，1、纤维衬布；2、纤维增强薄膜；3、热反射层；4、低温隔热纸；5、薄膜-气凝胶毡真空块。
具体实施方式
本发明的真空型柔性绝热夹层及其制备方法，通过采用薄膜袋与气凝胶毡制得薄膜-气凝胶毡真空块5，然后在外表面紧密铺设双面镀铝超薄聚酯膜3与低温隔热纸4的交替层叠结构，最终形成隔热层，在隔热层外表面处铺设由纤维衬布1和纤维增强薄膜2结合的保护层。利用抗透气性薄膜以及在真空块中放入吸附剂很好的吸附剂来保证真空块的真空寿命，该真空型柔性绝热夹层能够在-200℃～300℃温度范围内使用，该真空型柔性绝热夹层可以根据需要改变形状能够分别用于直面和曲面结构进行隔热使用。该真空型柔性绝热夹层在-200℃仍具有一定的韧性，所以特能用于低温液体输送软管相关结构。
为了让本发明的形状、性能、优点能够更加的明显易懂，下面的实施例结合附图可以更加容易对本发明进行理解。但是此发明也可以通过许多下面描述不同的方式来实施，本领域的技术人员可以在不违背本发明内容的基础上进行类似改进，因此本发明不受下面公开的具体实施的限制。
下面结合具体实施例和附图对本发明进一步说明：
实施例1
一种低温真空型柔性绝热夹层及其制备方法，本实施例是一种对称结构的柔性绝热夹层，其结构如图1所示，主要有隔热层和保护层，其中隔热层由最中间的薄膜-气凝胶毡真空块5、低温隔热纸4、热反射层3构成；保护层由纤维增强薄膜2和纤维衬布1构成；
(1)制备隔热层
①将氧化钯与5A分子筛按照质量比1：3混合均匀，形成吸附剂；
②将混合均匀的吸附剂按质量比1：4分别塞填到气凝胶毡内部以及均匀涂撒到气凝胶毡表面，所用气凝胶毡厚度为3mm；
③将上述处理后的气凝胶毡与两个薄膜袋一起放入烘箱中50℃，保持40分钟，所用薄膜袋为BOPET薄膜袋，单层厚度为0.03mm；
④将烘干处理后的气凝胶毡放入薄膜袋中，用真空泵进行抽真空，使真空度达到-0.05MPa～-0.08MPa；
由此获得薄膜-气凝胶真空块，放入烘箱50℃恒温备用。
取导热系数0.01W/(m.K)的阻燃性低温隔热纸30层，每一层的厚度为0.02～0.05mm即可，放入烘箱50℃烘干，然后对称铺叠到薄膜-气凝胶真空块上下两面。
用表面镀铝500nm厚的超薄聚酯薄膜30层，每一层厚度为0.005mm～0.01mm即可，继续对称铺叠到上述块状物的上下两面。然后将整体用热压机处理后放入烘箱中70～80℃恒温备用。
由此获得隔热层。
(2)制备保护层
用碳纤维与聚三氟氯乙烯按照克重1：10的比例组合，把碳纤维编织铺放在单层厚度为0.01mm的两层聚三氟氯乙烯薄膜之间，利用热压机将他们热压成型一体，然后这种纤维增强薄膜组合体制得10层，每5层一组。用厚度为0.1mm的聚酯织物(这里采用聚对苯二甲酸按乙二醇酯含量为90％的涤纶)作为纤维衬布，将这种纤维衬布分别铺叠到两组纤维增强薄膜的一面，纤维衬布均为两层，放入烘箱70～80℃备用。
由此制得两块保护层。
最后将首先制得的隔热层取出来，把两块保护层对称铺设到隔热层上下两面，
然后用热压机180℃、500N、持续30分钟进行热压。
最终获得真空型柔性绝热夹层结构。该结构厚度为4.5mm，常温韧性优异，放在液氮中也能表现出很好的折弯性能。绝热性能优异，将液氮放入薄壁金属容器中，外面包覆一层该绝热夹层，夹层外表面温度长时间无变化。以上详细描述了本发明的具体实施例以及使用领域。应当理解，本领域的普通技术人员无需创造性劳动既能够根据本发明的设计方案作出一系列的变化。因此，凡是相关领域中的技术人员依据本发明的设计思路进行推出的技术方案，皆在本发明的权力保护范围之内。
将制得的真空柔性绝热夹层结构包覆在金属薄壁容器外，将购得的液氮输送软管材料包覆在薄壁金属容器外，然后将二者在盛放液氮介质的情况下进行对比得到以下数据：
Figure BDA0002712683080000071
Figure BDA0002712683080000081

Claims (10)

1.一种真空型柔性绝热夹层，其特征在于：所述真空型柔性绝热夹层的中间层为薄膜-气凝胶毡真空块(5)，由中间层向两侧的外层分别依次为低温隔热纸(4)、热反射层(3)、纤维增强薄膜(2)和纤维衬布(1)；
所述纤维衬布(1)和纤维增强薄膜(2)构成保护层，所述热反射层(3)、低温隔热纸(4)和薄膜-气凝胶毡真空块(5)构成隔热层，所述纤维衬布(1)至少为1层，所述纤维增强薄膜(2)为1～30层；所述热反射层(3)为1～30层；所述低温隔热纸(4)为1～30层；所述薄膜-气凝胶毡真空块(5)至少为1层。
2.根据权利要求1所述的真空型柔性绝热夹层，其特征在于：所述纤维衬布(1)的厚度为0.1～0.3mm，所述纤维衬布包括玻璃纤维衬布、碳纤维衬布、聚酯纤维衬布或尼龙纤维衬布。
3.根据权利要求1所述的真空型柔性绝热夹层，其特征在于：所述纤维增强薄膜(2)由薄膜和纤维编织物组成，所述纤维编织物包括玻璃纤维、碳纤维、尼龙纤维或聚酯纤维，所述纤维编织物的厚度为0.01～0.03mm；所述薄膜包括—聚四氟乙烯薄膜、聚三氟氯乙烯薄膜和聚偏氟乙烯薄膜中的一种或几种；所述薄膜的厚度为0.04～0.06mm。
4.根据权利要求1所述的真空型柔性绝热夹层，其特征在于：所述热反射层(3)是厚度为0.005～0.01mm的双面镀铝聚酯薄膜，所述双面镀铝聚酯薄膜的镀铝层厚度为450nm～500nm。
5.根据权利要求1所述的真空型柔性绝热夹层，其特征在于：所述低温隔热纸(4)厚度为0.02～0.05mm。
6.根据权利要求1所述的真空型柔性绝热夹层，其特征在于：所述薄膜-气凝胶毡真空块(5)由薄膜、气凝胶毡和吸附剂组成，所述薄膜包括高模量聚乙烯薄膜、聚酯类薄膜；所述薄膜厚度为0.01～0.03mm；所述气凝胶毡厚度为3～5mm，所述吸附剂为氧化钯和5A分子筛按照质量比1：2.8～3.4混合而成。
7.权利要求1-6中任一项所述的真空型柔性绝热夹层的制备方法，其特征在于：包括如下步骤：
a)制备包含有吸附剂的薄膜-气凝胶毡真空块；
b)将0.02mm～0.05mm厚的低温隔热纸1～30层，放入烘箱中，50℃～60℃，保持60～70分钟，然后对称铺叠到薄膜-气凝胶毡真空块的上、下表面；
c)将热反射层对称铺叠到低温隔热纸的上、下表面，所述热反射层为0.005mm～0.01mm厚的双面镀铝超薄聚酯薄膜1～30层；放入烘箱中，70℃～80℃，保持60～80分钟，制得隔热层；
d)按照纤维与含氟聚合物薄膜克重比1：9.7～10.3的比例，把纤维铺放在两层或多层含氟聚合物薄膜之间，利用热压机或挤塑机进行挤压成型，制成纤维增强薄膜；所述纤维包括玻璃纤维、碳纤维、尼龙纤维或聚酯纤维，所述含氟聚合包括聚四氟乙烯、聚三氟氯乙烯和聚偏氟乙烯中的一种或几种；
e)采用0.1mm～0.3mm厚的玻璃纤维、尼龙纤维或者聚酯纤维中的一种或两种作为纤维衬布，铺叠在纤维增强薄膜上、下表面，制得保护层；
f)将保护层对称铺在隔热层上、下两表面，进行烘干、热压处理，得到真空型柔性绝热夹层。
8.根据权利要求7所述的制备方法，其特征在于：所述薄膜-气凝胶毡真空块的制备方法包括如下步骤：
①将氧化钯与5A分子筛按照质量比1：2.8～3.4混合均匀，形成吸附剂；
②将吸附剂按质量比1：2～6分别塞填到气凝胶毡中以及均匀涂撒到气凝胶毡表面；所述气凝胶毡厚度为3mm～5mm，密度为0.1～0.3g/cm3，导热系数为0.017～0.02W/(m.K)；
③将上述处理后的气凝胶毡与薄膜袋一起放入烘箱中50℃～70℃，保持40～60分钟，所用薄膜袋包括高模量聚乙烯薄膜袋、聚酯类薄膜袋；
④将烘干处理后的气凝胶毡放入薄膜袋中，用真空泵进行抽真空，使真空度达到-0.05MPa～-0.08MPa，即得薄膜-气凝胶毡真空块。
9.根据权利要求7所述的制备方法，其特征在于：所述低温隔热纸的常温下导热系数为0.01～0.02W/(m.K)，使用温度范围为-269℃～300℃；所述步骤f)中烘干的温度为100℃～110℃。
10.权利要求1-6中任一项所述的真空型柔性绝热夹层在制备低温液体贮箱或低温液体管道外表面隔热材料中的应用，所述低温为-200℃～-300℃。
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