CN103781624A - 具有水分及气体吸附吸收材料的真空绝热材料及其制备方法 - Google Patents

具有水分及气体吸附吸收材料的真空绝热材料及其制备方法 Download PDF

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CN103781624A
CN103781624A CN201280040860.7A CN201280040860A CN103781624A CN 103781624 A CN103781624 A CN 103781624A CN 201280040860 A CN201280040860 A CN 201280040860A CN 103781624 A CN103781624 A CN 103781624A
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heat insulation
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insulation materials
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CN103781624B (zh
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闵丙勋
黄承锡
全胜敏
韩程弼
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Ace Global Ltd.
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    • E04B1/00Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62Insulation or other protection; Elements or use of specified material therefor
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    • E04B1/62Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
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    • E04B1/78Heat insulating elements
    • E04B1/80Heat insulating elements slab-shaped
    • E04B1/803Heat insulating elements slab-shaped with vacuum spaces included in the slab
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00Thermal insulation in general
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Abstract

本发明涉及具有吸附水分及气体的吸收材料,从而能够提高长期耐久性,并降低费用的真空绝热材料及其制备方法。本发明的真空绝热材料,其特征在于,包括:芯材部,被减压密封的,吸收部,设在上述芯材部的中间一侧,以及外皮材料部,包围上述芯材部并密封;上述吸收部是用无纺布将混合了吸湿剂和吸气剂的吸收剂包装而成的。在本发明的真空绝热材料中,上述吸湿剂为氧化钙、氯化钙、沸石、硅胶、氧化铝、活性炭中的某一种,上述吸气剂为由Fe类化合物构成的吸氧剂,并且,以20:1~200:1的比例混合上述吸湿剂和吸气剂。

Description

具有水分及气体吸附吸收材料的真空绝热材料及其制备方法
技术领域
本发明涉及具有水分及气体吸附用吸收材料的真空绝热材料及其制备方法,尤其涉及具有吸附水分及气体的吸收材料,从而能够提高长期耐久性,并降低费用的真空绝热材料及其制备方法。
背景技术
如韩国国内公开专利公报第2011-0077860号(2011年07月07日)中所记载,以往常用的真空绝热材料通常包括:芯材,用于保持与内部和外部之间的大气压的压力差,并维持绝热材料的形态;气体阻隔性的外皮材料,用于包围芯材的同时,维持绝热材料的内部的真空状态;以及吸收材料,用于吸附绝热材料的内部的残留气体及汽体,从而维持长时间的真空。
即,如图1所示,以往的真空绝热材料10可具有包括:芯部11,包括芯材12,以及外皮材料14,用于覆盖上述芯部11;并将棒形吸收材料13直接插入于芯材12的内部的结构。
就这种真空绝热材料10而言,为了确保长期的耐久性,最重要的是吸收材料13的作用,而以往的吸收材料13可以吸附作为大气气体的主要成分的N2、O2和H2气体以及除了CO/CO2及烃(Hydrocarbon)气体等非活性气体之外的可产生的气体。
但是,以往的吸收材料由于原材料的费用高,在使用前为了活性化而需要经过300℃以上的高的热处理过程,并且还需要具有用于吸附水分的吸湿剂,因而会产生生产费用增加的问题。
发明内容
技术问题
本发明的目的在于,提供能够提高耐久性,并降低生产费用的具有水分及气体吸附用吸收材料的真空绝热材料。
本发明的另一目的在于,提供能够达成上述目的的真空绝热材料的制备方法。
解决问题的手段
用于达成上述目的的本发明的真空绝热材料,其特征在于,包括:芯材部,被减压密封的,吸收部,设在上述芯材部的中间一侧,以及外皮材料部,包围上述芯材部并密封;上述吸收部是用无纺布将混合了吸湿剂和吸气剂的吸收剂包装(packing)而成的。
本发明的真空绝热材料,其特征在于,上述吸湿剂为氧化钙、氯化钙、沸石、硅胶、氧化铝、活性炭中的某一种;上述吸气剂为由Fe类化合物构成的吸氧剂。
本发明的真空绝热材料,其特征在于,以20:1~200:1的比例混合上述吸湿剂和吸气剂。
本发明的真空绝热材料的制备方法,其特征在于,包括:设置包括上部芯材、下部芯材以及吸收部的结构要素的步骤,上述上部芯材设置于上部外皮材料与下部外皮材料之间,分别具有吸收剂插入部,上述吸收部与上述吸收剂插入部相对应,以及向真空状态的腔室内装入上述结构要素并进行热压接的步骤;上述吸收部是用无纺布将混合了吸湿剂和吸气剂的吸收剂包装而成的。
本发明的真空绝热材料的制备方法,其特征在于,在进行上述热压接的步骤中,利用与上述上部外皮材料的上部相对应的上部热压接夹具和与上述下部外皮材料的下部相对应的下部热压接夹具,从上下朝向上述吸收部方向进行热压接。
发明的效果
本发明的真空绝热材料能够利用混合了吸湿剂和少量的吸气剂的吸收剂,容易地吸附从内部产生的气体,从而维持内部的减压状态,并提高耐久性。
本发明的真空绝热材料的制备方法由于利用混合了少量的吸气剂和吸湿剂的吸收剂,因而具有能够提供可降低制备费用,并维持内部的减压状态,来提高耐久性的真空绝热材料的效果。
附图说明
图1为用于说明以往的真空绝热材料的剖视图。
图2为本发明的实施例的真空绝热材料的剖视图。
图3a至图3c为用于说明本发明的实施例的真空绝热材料的制备方法的工序剖视图。
图4为用于说明本发明的实施例的真空绝热材料的效果的图表。
具体实施方式
以下,参照附图,对本发明的实施例进行详细说明。在这里,本发明的实施方式能够以多种不同的方式变形,本发明的范围并不局限于以下说明的实施方式。
如图2所示,本发明的实施例的真空绝热材料100包括:芯材部120,被减压密封的;吸收部130,安装在形成于芯材部120的中间部分的吸收剂插入部123;以及外皮材料部110、110',以包围芯材部120的方式密封。
外皮材料部110、110'由包围芯材部120且上下密封的上部外皮材料110和下部外皮材料110'构成。这种上部外皮材料110和下部外皮材料110'包括共同以与芯材部120相接触的方式包围的热压接层111、气体阻隔层112、第一保护层113及第二保护层114。
热压接层111为分别设在上部外皮材料110和下部外皮材料110',从而在制备真空绝热材料100的过程中,包围芯材部120并沿着边缘相互进行热压接的层。这种热压接层111可由线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、超低密度聚乙烯(VLDPE)、高密度聚乙烯(HDPE)等聚乙烯类的树脂,除上述树脂之外的聚丙烯(PP)等可进行热压接的树脂或它们的混合物构成。
气体阻隔层112为覆盖热压接层111的外部面的层,而为了防止透气,上述气体阻隔层112可由在表面蒸镀铝箔等金属箔或金属、金属氧化物、类金刚石碳等的塑料膜形成。
第一保护层113及第二保护层114为依次覆盖气体阻隔层112的外部面,从而用于确保机械强度的层。这种第一保护层113及第二保护层114可分别由选自由聚酰胺、聚丙烯、聚对苯二甲酸乙二醇酯、聚丙烯腈、聚乙烯醇、尼龙、PET、K-PET及乙烯乙烯醇构成的组中的一种以上的树脂构成。
芯材部120为由上部外皮材料110和下部外皮材料110'包围并被减压密封的部件,可由玻璃棉(glass wool)的无机纤维、聚酯纤维等有机纤维、聚氨基甲醇乙酯、聚苯乙烯、聚乙烯、聚丙烯等树脂发泡体、气相二氧化硅、珍珠岩、炭黑等无机粉末、或合成树脂粉末的有机粉末中的某一种或一种以上的合成物形成。在这里,当芯材120由上述合成物形成的情况下,也可以形成为由上述合成物的各个层的多个层层叠而成的结构。
吸收部130作为安装在形成于芯材部120的中间部分的吸收剂插入部123的包含水分及气体吸附用吸收剂131和无纺布132的部件,是用无纺布132包装吸收剂131的部件,上述吸收剂131以20:1~200:1的比例混合吸附水分的吸湿剂和吸气剂。
在这里,吸湿剂使用氧化钙、氯化钙、沸石、硅胶、氧化铝、活性炭中的一种纳米细孔物质以及上述物质的混合物或化合物的纳米细孔物质,而作为选择性的吸气剂,可使用沸石、活性炭、氧化铝中的一种或一种以上的合成物纳米细孔物质或Ta、Cb、Zr、Th、Mg、Ba、Ti、Al、Nb、Fe、Li、Pd、Pt、Au等金属及这种金属的氧化物等。
这种吸收剂131可根据从芯材部120放出的气体和从外皮材料部110、110'放出的气体,选择性地使用吸气剂。例如,从芯材部120放出二氧化碳或被捕集的氧、氢、氮等大气气体或从外皮材料部110、110'放出烃或水分的情况下,可根据各个的气体,将上述金属或金属氧化物用作吸气剂。
尤其,吸收剂131作为选择性的吸气剂包含吸氧剂的情况下,吸氧剂可利用Fe3O4、Zn2[Fe(CN)6]、Zn3[Fe(CN)6]2、Ce[Fe(CN)6]等Fe类化合物。
并且,为了防止可能为粉末形态的吸收剂131的脱离,无纺布132可利用聚丙烯(PP)无纺布、聚乙烯(PE)无纺布等。
在这种真空绝热材料100中,利用混合吸湿剂和少量的吸气剂的吸收剂131,来容易地吸附从芯材部120和外皮材料部110、110'放出的气体,从而维持内部的减压状态,并提高耐久性。
以下,参照图3a至图3c,对本发明的实施例的真空绝热材料100的制备方法进行说明。图3a至图3c为用于说明本发明的实施例的真空绝热材料的制备方法的工序剖视图。
如图3a所示,本发明的实施例的真空绝热材料100的制备方法首先在上部外皮材料110与下部外皮材料110'之间设置上部芯材121和下部芯材122,上述上部芯材121和下部芯材122分别具有与吸收部130相对应的吸收剂插入部123。
在这里,分别形成于上部芯材121和下部芯材122的吸收剂插入部123为分别对上部芯材121和下部芯材122的相应部分进行切割的同时进行冲压,来以槽形态预先形成的部分。这种吸收剂插入部123可设置成适于吸收部130的大小或者大于吸收部130的大小。
此时,可在450℃以上的温度下,对以20:1~200:1的比例混合吸湿剂与吸气剂的吸收剂131进行加热,并在活性化之后,以用无纺布132包装的形态预先设置吸收部130。在这里,吸气剂能够以小容量充分执行气体吸附,因而吸气剂能够在0.05~1g的容量范围内按上述比例进行混合,优选地,能够混合0.5g。
像这样设置真空绝热材料100的结构要素之后,如图3b所示,向真空状态的腔室200内装入真空绝热材料100的结构要素并进行热压接。
具体地,腔室200内的真空状态与真空绝热材料100的内部所需的真空状态相同,以1~20Pa的减压状态维持,而在这种状态下设置真空绝热材料100的结构要素。在这里,为了防止吸气剂的改性,减压状态的腔室200的内部可选择性地形成为He、Ar等非活性气体气氛。
对于如此设置的真空绝热材料100的结构要素,上部外皮材料110和下部外皮材料110'将通过热压接夹具(jig)相对应并进行热压接。即,利用与上部外皮材料110的上部相对应的上部热压接夹具(未图示)和与下部外皮材料110'的下部相对应的下部热压接夹具(未图示),从上下进行热压接,使得分别构成上部外皮材料110和下部外皮材料110'的热压接层111沿着边缘相互以一体的方式粘结。
由此,上部外皮材料110与下部外皮材料110'之间的上部芯材121和下部芯材122以一体的方式融合,同时吸收部130可分别与上部芯材121和下部芯材122的吸收剂插入部123相对应地进行安装。
像这样,若执行利用热压接夹具的热压接,则如图3c所示,结束真空绝热材料100的制备。
此时,解除腔室200的内部的真空,腔室200的内部压力从1~20Pa上升至1×105Pa左右的大气压。但是,由外皮材料110、110'密封的真空绝热材料100的内部可始终维持1~20Pa左右的真空。
这种本发明的实施例的真空绝热材料100的制备方法由于利用混合了小容量的吸气剂和吸湿剂的吸收剂131,来制备容易地吸附从芯材部120和外皮材料部110、110'放出的气体的真空绝热材料100,因而能够降低制备费用,并维持内部的减压状态,从而提高耐久性。
以下,将本发明的实施例的真空绝热材料100的特性和效果与使用混合多种吸气剂的吸收剂的比较例进行比较,并进行详细说明。在这里,以下说明只是本发明的优选例示,无论从任何意义也不能解释本发明局限于此。对于未在此记载的内容,只要是本发明所属技术领域的普通技术人员就能够充分以技术性的方式进行类推,因而省略其说明。
实施例
实施例适用本发明的真空绝热材料100,并将用聚丙烯(PP)无纺布132包装吸收剂131的吸收部130安装于层叠有玻璃棉的芯材部120的中间,上述吸收剂131以40:1的比例混合氧化钙(CaO)的吸湿剂及由Fe3O4、Zn2[Fe(CN)6]、Zn3[Fe(CN)6]2及Ce[Fe(CN)6]中的某一种Fe类化合物构成的吸氧剂。
外皮材料部110、110'适用厚度约为50μm的线性低密度聚乙烯(LLDPE)的热压接层111、厚度约为6μm的铝的气体阻隔层112、厚度约为25μm的尼龙的第一保护层113以及具有厚度约为12μm的涂敷有聚偏二氯乙烯(PVDC)的K-PET树脂层的第二保护层114。
测定这种真空绝热材料100的初始热传导率之后,在90℃温度下进行6周的热处理,从而用热传导率测定仪测定了真空绝热材料100的热传导率。
比较例1
比较例1适用于实施例的真空绝热材料100,并具有吸收剂以40:1的比例混合氧化钙(CaO)的吸湿剂及Zr/Ti成分的氢吸气剂的区别。
测定像这样包含由氧化钙(CaO)的吸湿剂及Zr/Ti成分的氢吸气剂构成的吸收剂的比较例1的真空绝热材料的初始热传导率之后,在90℃温度下对比较例1的真空绝热材料进行6周的热处理,并用热传导率测定仪测定了比较例1的真空绝热材料的热传导率。
比较例2
比较例2适用于实施例的真空绝热材料100,并具有吸收剂以40:1的比例混合氧化钙(CaO)的吸湿剂及Zr/Ba成分的氮吸气剂的区别。
测定像这样包含由氧化钙(CaO)的吸湿剂及Zr/Ba成分的氮吸气剂构成的吸收剂的比较例2的真空绝热材料的初始热传导率之后,在90℃温度下对比较例2的真空绝热材料进行6周的热处理,并用热传导率测定仪测定了比较例2的真空绝热材料的热传导率。
比较例3
比较例3适用于实施例的真空绝热材料100,并具有吸收剂不包含吸气剂,而仅由氧化钙(CaO)的吸湿剂构成的区别。
测定像这样包含仅由氧化钙(CaO)的吸湿剂构成的吸收剂的比较例3的真空绝热材料的初始热传导率之后,在90℃温度下对比较例3的真空绝热材料进行6周的热处理,并用热传导率测定仪测定了比较例3的真空绝热材料的热传导率。
如图4所示,这种实施例和比较例的测定结果分别具有明显的区别,实施例的真空绝热材料的热传导率测定为0.0040Kcal/mhr℃,比较例1的真空绝热材料的热传导率测定为0.0045Kcal/mhr℃,比较例2的真空绝热材料的热传导率测定为0.0048Kcal/mhr℃。并且,比较例3的真空绝热材料的热传导率测定为0.0055Kcal/mhr℃。
通过这种结果,可知,优选地,相比于混合其他吸气剂,应以混合由Fe类化合物构成的吸氧剂和吸湿剂的形态制备吸收剂131,因此,即使随着时间的经过,也能够减少真空泄露引起的热传导率的性能的下降。
因此,优选地,本发明的真空绝热材料100应适用用无纺布132包装吸收剂131的吸收部130,上述吸收剂131混合氧化钙成分的吸湿剂及由Fe类化合物构成的吸氧剂。
本发明的技术思想根据优选的上述实施例进行了详细说明,但应当注意的是,上述实施例仅用于说明,而并非用于限制。
并且,只要是本发明所属技术领域的普通技术人员,就能够理解在本发明的技术思想的范围内能够进行各种实施。

Claims (15)

1.一种真空绝热材料,其特征在于,
包括:
被减压密封的芯材部,
吸收部,设在上述芯材部的中间一侧,以及
外皮材料部,包围上述芯材部并密封;
上述吸收部是用无纺布将混合了吸湿剂和吸气剂的吸收剂包装而成的。
2.根据权利要求1所述的真空绝热材料,其特征在于,
上述吸湿剂为氧化钙、氯化钙、沸石、硅胶、氧化铝、活性炭中的一种;
上述吸气剂为由Fe类化合物构成的吸氧剂。
3.根据权利要求2所述的真空绝热材料,其特征在于,上述吸氧剂为Fe3O4、Zn2[Fe(CN)6]、Zn3[Fe(CN)6]2及Ce[Fe(CN)6]中的一种。
4.根据权利要求1所述的真空绝热材料,其特征在于,以20:1~200:1的比例混合上述吸湿剂和吸气剂。
5.根据权利要求1所述的真空绝热材料,其特征在于,上述无纺布为聚丙烯无纺布或聚乙烯无纺布。
6.根据权利要求1所述的真空绝热材料,其特征在于,上述芯材部由无机纤维、有机纤维、树脂发泡体、无机粉末及有机粉末中的一种或一种以上的合成物形成。
7.根据权利要求6所述的真空绝热材料,其特征在于,上述无机纤维为玻璃棉,上述有机纤维为聚酯纤维,上述树脂发泡体由聚氨基甲醇乙酯、聚苯乙烯、聚乙烯、聚丙烯中的一种形成,上述无机粉末由气相二氧化硅、珍珠岩及炭黑中的一种形成,上述有机粉末为合成树脂粉末。
8.一种真空绝热材料的制备方法,其特征在于,
包括:
设置包括上部芯材、下部芯材以及吸收部的结构要素的步骤,上述上部芯材和下部芯材设置于上部外皮材料与下部外皮材料之间,分别具有吸收剂插入部,上述吸收部与上述吸收剂插入部相对应,以及
向真空状态的腔室内装入上述结构要素并进行热压接的步骤;
上述吸收部是用无纺布将混合了吸湿剂和吸气剂的吸收剂包装而成的。
9.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,
上述吸湿剂为氧化钙、氯化钙、沸石、硅胶、氧化铝、活性炭中的一种;
上述吸气剂为由Fe类化合物构成的吸氧剂。
10.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,上述吸氧剂为Fe3O4、Zn2[Fe(CN)6]、Zn3[Fe(CN)6]2及Ce[Fe(CN)6]中的一种。
11.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,以20:1~200:1的比例混合上述吸湿剂和吸气剂。
12.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,
上述无纺布为聚丙烯无纺布或聚乙烯无纺布;
上述芯材部由无机纤维、有机纤维、树脂发泡体、无机粉末及有机粉末中的一种或一种以上的合成物形成。
13.根据权利要求12所述的真空绝热材料的制备方法,其特征在于,上述无机纤维为玻璃棉,上述有机纤维为聚酯纤维,上述树脂发泡体由聚氨基甲醇乙酯、聚苯乙烯、聚乙烯、聚丙烯中的一种形成,上述无机粉末由气相二氧化硅、珍珠岩及炭黑中的一种形成,上述有机粉末为合成树脂粉末。
14.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,设置上述结构要素的步骤还包括以下步骤:分别对上述上部芯材和下部芯材的相应部分进行切割并冲压,来以槽形态形成上述吸收剂插入部。
15.根据权利要求8所述的真空绝热材料的制备方法,其特征在于,在进行上述热压接的步骤中,利用与上述上部外皮材料的上部相对应的上部热压接夹具和与上述下部外皮材料的下部相对应的下部热压接夹具,从上下朝向上述吸收部方向进行热压接。
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