CN114106411A - 一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法 - Google Patents
一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法 Download PDFInfo
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Abstract
本发明涉及节能环保、高分子及其复合材料领域。一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,将纤维素、海藻酸盐和蒙脱土在水中形成凝胶,对凝胶进行液氮冷冻干燥处理制成具有取向孔结构的气凝胶基体,将具有取向孔结构的气凝胶基体在聚乙二醇相变材料熔融液中浸泡,使聚乙二醇相变材料定向浸渗于气凝胶基体的取向孔道中,得到阻燃自熄型生物质气凝胶相变复合蓄热材料。本发明制备的生物质气凝胶相变复合蓄热材料,兼具良好的阻燃自熄功能、力学性能及热稳定性。
Description
技术领域
本发明涉及节能环保、高分子及其复合材料领域,具体涉及用于电采暖的电热式相变蓄热器的气凝胶相变复合蓄热材料领域。
背景技术
传统采暖方式为燃煤、燃气锅炉集中供暖,串联控制供热面积100%,造成严重的能源浪费和环境污染。近年来,随着节能环保蓄热技术的快速发展,对低温相变蓄热材料的需要日益迫切。急需环保型低温相变蓄热材料替代不可降解的高分子蓄热材料,以满足新一代节能环保蓄热技术的需求。
结合中低温相变蓄热材料的熔融温度、焓值及结构特征,聚乙二醇的相变温度(37- 67 ℃)随分子量(1000-20000)增加而提高,是适用于低温相变蓄热器的相变蓄热材料。聚乙二醇作为固-液相变材料的重要分支,其自身相变潜热高,热滞后效应低,无毒、无刺激性、不水解性、性能稳定,可以通过调整分子链的长短来调节相变温度和相变潜热,分子可设计性强,其作为相变材料存在以下缺点:在固-液相变或加工过程中,易渗漏,在相变过程中,主要依靠链节、基团等导热,热导率较低,致使其热交换性能差,影响储能和释能的效率。近几年来,微胶囊封装相变材料和定形相变材料成为研究的热点,然而微胶囊封装制备复合相变材料技术复杂,成本较高,不利于相变复合材料的实际应用;定形相变材料一般是用多孔支撑材料来吸附相变材料以保持相变材料形状稳定,常见的多孔支撑材料有膨润土、硅藻土、高聚物、气凝胶、泡沫金属等,其中,气凝胶具有较高的孔隙率、较低的密度及可调控的孔洞结构,适合用于聚乙二醇相变材料的封装定形骨架材料。生物质气凝胶具有高的比表面积和孔隙率、密度小及良好的力学性能、蓄热性能及可降解性能,是理想的节能环保型中低温相变蓄热材料的多孔骨架材料。
电热式相变蓄热器的应用环境对于相变材料的相变温度和相变焓要求有所不同,民用电采暖领域尤其对于相变材料的力学强度、稳定性、安全性及节能环保等综合性能要求较高,亟待开发适用于电采暖的电热式相变蓄热器的新型相变复合蓄热材料。生物质气凝胶相变复合蓄热材料能够利用相变组分的相转变(固-液)过程吸收或释放热量,实现蓄热功能,成为当今节能环保领域蓄热材料研究和应用的发展趋势。
发明内容
本发明所要解决的技术问题是:如何提供一种用于电热式相变蓄热器的阻燃自熄型生物质气凝胶相变复合蓄热材料,达到节能环保、降低采暖***运行成本的目的。
本发明所采用的技术方案是:一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,将纤维素、海藻酸盐和蒙脱土在水中形成凝胶,对凝胶进行液氮冷冻干燥处理制成具有取向孔结构的气凝胶基体,将具有取向孔结构的气凝胶基体在聚乙二醇相变材料熔融液中浸泡,使聚乙二醇相变材料定向浸渗于气凝胶基体的取向孔道中,得到阻燃自熄型生物质气凝胶相变复合蓄热材料。
作为聚乙二醇相变材料的定形封装基体,气凝胶的力学性能是相变材料保持形状的重要影响因素,根据本申请的研究,采用纤维素、海藻酸盐作为气凝胶的制备原料,同时引入蒙脱土,使得到的纤维素/海藻酸盐/蒙脱土基气凝胶不仅具有低密度特性,还具有良好的力学性能(抗压、抗形变能力等)和阻燃自熄功能,从而能够保证气凝胶相变复合蓄热材料的低密度、力学强度及阻燃自熄等特性;将上述气凝胶与聚乙二醇相变材料定向浸渗复合为一体,利用聚乙二醇熔体对该气凝胶中的孔洞进行定向浸渗和附着,相当于在纤维素/海藻酸盐/蒙脱土基气凝胶体系中设计多个微尺度的定向相变孔用于热传导,显著提高气凝胶相变复合蓄热材料的蓄热和传热性能,保证电热式相变蓄热器的使用稳定性和安全性。
纤维素、海藻酸盐和蒙脱土的质量比为2~4:10:5~10,凝胶中,纤维素、海藻酸盐和蒙脱土之和为1 wt %~3 wt %。
聚乙二醇相变材料的分子量为1000 ~10000,气凝胶相变复合蓄热材料的相变温度和相变焓随着聚乙二醇相变材料的分子量的变化而变化,根据所需的相变温度和相变焓,选择合适的聚乙二醇相变材料的分子量。如可以采用PEG1500、PEG10000等。利用该高分子相变材料对纤维素/海藻酸盐/蒙脱土气凝胶进行定向相变处理,使阻燃自熄型气凝胶相变复合蓄热材料能够表现出更好的蓄热性能、力学强度等综合性能。
根据所需的相变温度和相变焓是指,阻燃自熄型生物质气凝胶相变复合蓄热材料用于电采暖的电热式相变蓄热器,根据电采暖的环境温度需求而确定的相变温度和相变焓。
在气凝胶基体浸泡前在气凝胶基体中添加无机盐交联剂。
无机盐交联剂为氯化钙。
本发明的有益效果是:本发明制备的阻燃自熄型生物质气凝胶相变复合蓄热材料,兼具良好的阻燃自熄功能、力学性能及热稳定性,并且制备工艺简单,条件温和,原料廉价易得,成本低,绿色环保。
本发明采用天然绿色、无毒、无污染、廉价易得的纤维素、海藻酸盐、蒙脱土作为气凝胶基体的原料,以该阻燃自熄型气凝胶基体定向浸渗复合聚乙二醇相变材料,不仅使气凝胶相变复合蓄热材料具有可降解、绿色环保、成本低等优点,还具有良好的防泄漏、蓄热性能、力学性能和热稳定性,同时具有气凝胶的低密度特性,使得该相变复合蓄热材料能够广泛应用于对蓄热性能、力学性能、稳定性及阻燃自熄等综合性能要求较高的电热式相变蓄热器,比如可以应用于电热式相变蓄热器用于民用电采暖领域等。
本发明提供的阻燃自熄型气凝胶相变复合蓄热材料的制备方法,能够得到兼具阻燃自熄功能、良好蓄热性能、力学性能、热稳定性等综合性能的气凝胶相变复合蓄热材料,并且该方法制备工艺简单、温和无污染、绿色环保、原料廉价易得,显著降低生产成本,利于工业化生产和应用。
本发明中,将上述阻燃自熄型气凝胶相变复合蓄热材料用于电热式相变蓄热器,可直接用于民用电采暖领域,不仅能够保证或提高采暖效果,而且与现有锅炉集中供暖相比,可避免大量的能源浪费和严重的环境污染,达到节能环保,助力煤改电的能源结构调整早日实现“碳达峰”和“碳中和”。
附图说明
图1为本发明实施例1的具有取向孔结构的气凝胶(CNAMMTCa)扫描电子显微镜(SEM)观察到的微观形貌图,其中,(a)为放大倍数为500的横截面微观形貌图,(b)为放大倍数为500的纵截面微观形貌图;
图2为本发明实施例1的阻燃自熄型气凝胶相变蓄热材料(CNAMMTCa /PEG1500)经扫描电子显微镜观察到的微观形貌图;
图3为本发明实施例1的取向孔结构的气凝胶(CNAMMTCa)的压缩曲线(应力为纵坐标,应变为横坐标);
图4为本发明实施例1的气凝胶相变蓄热材料(CNAMMTCa/PEG1500)和另一实施例的气凝胶相变蓄热材料(A5MMT5Ca/PEG10000)的热失重曲线;
图5 为本发明实施例1的气凝胶相变蓄热材料(CNAMMTCa/PEG1500)和另一实施例的气凝胶相变蓄热材料(CNAMMTCa /PEG10000)的差示扫描量热分析曲线;
图6为本发明实施例2的气凝胶相变蓄热材料(CNAMMTCa /PEG10000)经扫描电子显微镜观察到的微观形貌图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明的实施例对本发明中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
称取5g的钠基蒙脱土加入到70ml的1wt%的纤维素的水分散液中,14000r/min机械搅拌、缓慢加入5g海藻酸铵,继续恒温(55℃左右)机械搅拌2小时,得到均匀的纤维素/海藻酸铵/蒙脱土基复合凝胶;将上述凝胶倒入模具置于液氮快速冷冻,然后将冷冻样品置于冷冻干燥机中,-35℃左右实施冷冻干燥72小时,移入40℃的真空烘箱中进一步干燥5h,得到未交联的纤维素/海藻酸铵/蒙脱土杂化气凝胶CNAMMT;将CNAMMT浸泡于饱和氯化钙的乙醇溶液进行交联反应,时间6小时左右,温度55℃左右,随后将交联产物移入40℃真空烘箱中干燥24小时除去乙醇,得到交联的纤维素/海藻酸铵/蒙脱土杂化气凝胶CNAMMTCa(其微观形貌见图1);称取适量聚乙二醇(PEG1500)于烧杯中,加热至80℃完全熔融,将CNAMMTCa沿取向孔轴向浸入PEG1500熔体中,放置于80℃真空烘箱中,抽真空24小时,辅助PEG1500充分浸渗到气凝胶取向孔道中,得到气凝胶相变复合蓄热材料CNAMMTCa/PEG1500(其微观形貌见图2)。
燃烧实验显示气凝胶CNAMMTCa不易点燃,仅有轻微的阴然现象,远离火焰1秒内熄灭,说明该气凝胶具有良好的阻燃自熄功能。经测定,CNAMMTCa的压缩模量达11.07 MPa、压缩强度(70%)4.89MPa(图3),表明本实施例制备的气凝胶具有良好的抗形变、抗压能力,从而保证了气凝胶相变复合蓄热材料CNAMMTCa/PEG1500具有良好的力学强度和形状稳定性;CNAMMTCa/PEG1500室温至200℃热稳定性良好,约400℃达到失重峰值(图4中的实线),表明本实施例制备的气凝胶相变复合蓄热材料具有良好的热稳定性;图5示出CNAMMTCa/PEG1500的DSC曲线中发生相变的吸热峰和放热峰(图5中的实线),其潜热值分别为157.80J/g和 147.65 J/g,表明本实施例制备的气凝胶相变复合蓄热材料具有良好的蓄热性能。
本实施例提供的气凝胶相变复合蓄热材料,不仅具有可降解、绿色环保、成本低等优点,还具有较高的抗形变、抗压能力,表现出良好的力学性能和热稳定性,同时兼具气凝胶的低密度特性,可广泛应用于对蓄热材料的阻燃自熄功能、蓄热能力、力学性能、热稳定性等综合性能要求较高的场所,比如可以应用于电热式相变蓄热器,解决民用电采暖的灵活性、安全性、节能环保及低成本等问题。
纤维素、海藻酸盐、蒙脱土为自然界储备非常丰富的天然材料,且纤维素、海藻酸盐具有可降解、无毒、无污染、易于改性等特点。本发明提供的制备方法,以纤维素、海藻酸盐、蒙脱土作为气凝胶的生产原料,并进一步通过交联反应、液氮冷冻干燥处理等各步骤控制工艺,调控气凝胶的孔隙率、孔洞结构、力学强度及密度等特性,配合聚乙二醇熔体定向浸渗步骤,对气凝胶进行相变处理,引入多个材料两相界面,通过多级结构调控其蓄热和力学性能,从而制备得到具有上述优异性能的气凝胶相变复合蓄热材料。
本实施例提供的气凝胶相变复合蓄热材料,其气凝胶基体的杨氏模量达9.48MPa、压缩强度(70%)为1.41MPa,具有良好的抗形变、抗压能力,使得气凝胶相变复合蓄热材料具有良好的力学性能;该气凝胶相变复合蓄热材料在室温至200℃热稳定性良好。经试验,该气凝胶相变复合蓄热材料能够作为电热式相变蓄热器的蓄热材料,相对于现有的蓄热材料,具有蓄热性好、可降解、绿色环保、成本低及不腐蚀等优点。
实施例2
本实施例与实施例1不同之处在于:采用聚乙二醇(PEG10000)替换聚乙二醇(PEG1500),得到气凝胶相变复合蓄热材料CNAMMTCa/PEG10000(其微观形貌参见图6)。经测试,CNAMMTCa/PEG10000室温至200 ℃的热稳定性良好,约400℃达到失重峰值(图4中的虚线),表明本实施例制备的气凝胶相变复合蓄热材料具有良好的热稳定性;图5示出CNAMMTCa/PEG10000的DSC曲线中发生相变的吸热峰和放热峰(图5中的虚线),其潜热值分别为217.04 J/g和196.46 J/g,表明本实施例制备的气凝胶相变复合蓄热材料具有良好的蓄热能力和热稳定性。
实施例提供的气凝胶相变复合蓄热材料,不仅具有可降解、绿色环保、成本低等优点,还具有较高的抗形变、抗压能力,表现出良好的力学性能和热稳定性,同时兼具气凝胶的低密度特性,可广泛应用于对蓄热材料的阻燃自熄功能、蓄热能力、力学性能、热稳定性等综合性能要求较高的场所,比如可以应用于电热式相变蓄热器,解决民用电采暖的灵活性、安全性、节能环保及低成本等问题。
Claims (6)
1.一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:将纤维素、海藻酸盐和蒙脱土在水中形成凝胶,对凝胶进行液氮冷冻干燥处理制成具有取向孔结构的气凝胶基体,将具有取向孔结构的气凝胶基体在聚乙二醇相变材料熔融液中浸泡,使聚乙二醇相变材料定向浸渗于气凝胶基体的取向孔道中,得到阻燃自熄型生物质气凝胶相变复合蓄热材料。
2.根据权利要求1所述的一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:纤维素、海藻酸盐和蒙脱土的质量比为2~4:10:5~10,凝胶中,纤维素、海藻酸盐和蒙脱土之和为1 wt %~3 wt %。
3.根据权利要求1所述的一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:聚乙二醇相变材料的分子量为1000 ~10000,气凝胶相变复合蓄热材料的相变温度和相变焓随着聚乙二醇相变材料的分子量的变化而变化,根据所需的相变温度和相变焓,选择合适的聚乙二醇相变材料的分子量。
4.根据权利要求3所述的一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:根据所需的相变温度和相变焓是指,阻燃自熄型生物质气凝胶相变复合蓄热材料适用于电采暖的电热式相变蓄热器,根据电采暖的环境温度需求而确定的相变温度和相变焓。
5.根据权利要求1所述的一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:在气凝胶基体浸泡前在气凝胶基体中添加无机盐交联剂。
6.根据权利要求5所述的一种阻燃自熄型生物质气凝胶相变复合蓄热材料制备方法,其特征在于:无机盐交联剂为氯化钙。
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