CN116639994A - 一种多层中空核壳纤维气凝胶 - Google Patents

一种多层中空核壳纤维气凝胶 Download PDF

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CN116639994A
CN116639994A CN202310666361.9A CN202310666361A CN116639994A CN 116639994 A CN116639994 A CN 116639994A CN 202310666361 A CN202310666361 A CN 202310666361A CN 116639994 A CN116639994 A CN 116639994A
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hollow core
shell
layer
fiber aerogel
shell fiber
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CN116639994B (zh
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唐桂华
彼得·埃武卡·奥卡福
贺晨波
胡洋
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Xian Jiaotong University
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Abstract

本发明涉及材料结构设计技术领域,特别是涉及一种多层中空核壳纤维气凝胶。本发明多层中空核壳纤维气凝胶由若干个空间随机分布的多层中空核壳纳米纤维(2)相互搭接组成;所述多层中空核壳纳米纤维(2)的结构组成从内到外依次为具有中空结构(3)的氧化物陶瓷纳米纤维(4)、抗氧化陶瓷防护层(5)以及遮光防护层(6)。本发明提供一种多层中空核壳纤维气凝胶,能够有效阻隔航天器外部环境热流,保证热防护系统具备使役可靠性,满足航天飞行器的热防护需求。

Description

一种多层中空核壳纤维气凝胶
技术领域
本发明涉及材料结构设计技术领域,特别是涉及一种多层中空核壳纤维气凝胶。
背景技术
随着航天飞行器的不断发展,其飞行速度不断提高、应用环境逐渐恶劣,因此,亟需发展一种轻质/高效隔热/高承载/高热稳定一体化的隔热材料以满足航天飞行器的热防护需求。
纳米多孔气凝胶因其重量轻、隔热性能好,在航天热防护领域受到了重要关注。然而,纳米多孔气凝胶在实际应用中还存在一定问题:(1)传统纳米颗粒多孔气凝胶的骨架结构中纳米颗粒的连接处易产生应力集中,发生脆性断裂,整体机械强度较低。同时,传统气凝胶的热稳定性较差,高温下骨架结构易发生烧结,导致颗粒融合、结构坍塌、体积收缩,致使材料的热、力性能退化,不利于航天飞行器的服役安全。(2)传统纳米颗粒多孔气凝胶不利于抑制高温辐射传热,热防护系统在高温环境下难以实现高效隔热的目标。(3)传统纳米颗粒多孔气凝胶通常掺杂高密度纤维以改善其高温隔热性能与力学性能,然而纤维掺杂气凝胶难以同时满足轻质与高效隔热的需求,严重制约了热防护系统的轻量化设计。
发明内容
基于上述内容,本发明提供一种多层中空核壳纤维气凝胶,能够有效阻隔航天器外部环境热流,保证热防护系统具备使役可靠性,满足航天飞行器的热防护需求。
为实现上述目的,本发明提供了如下方案:
本发明提供一种多层中空核壳纤维气凝胶,由若干个空间随机分布的多层中空核壳纳米纤维2相互搭接组成;所述多层中空核壳纳米纤维2的结构组成从内到外依次为具有中空结构3的氧化物陶瓷纳米纤维4、抗氧化陶瓷防护层5以及遮光防护层6。
进一步地,所述具有中空结构3的氧化物陶瓷纳米纤维4的空心度为0-1,且不为0,不为1。
空心度即中空结构3的直径和氧化物陶瓷纳米纤维4的直径(外径)之比为大于0小于1。
进一步地,所述氧化物陶瓷纳米纤维4的材料组成为三氧化二铝或莫来石。
进一步地,所述抗氧化陶瓷防护层5的材料组成为碳化硅、二氧化钛或二氧化锆中的一种。
进一步地,所述遮光防护层6的材料组成为热解碳、树脂碳、沥青碳中的一种或多种。
进一步地,所述多层中空核壳纳米纤维2的长径比为4-6。
本发明技术方案之二,上述的多层中空核壳纤维气凝胶在航天飞行器隔热材料中的应用。
本发明公开了以下技术效果:
本发明多层中空核壳纤维气凝胶具有轻质/高效隔热/高承载/高热稳定一体化的特点,其中多层中空核壳纳米纤维单元具有较大的长径比,有利于组装形成连续的三维多孔网络骨架结构,且纤维连接处接触比较大,可有效缓解纤维连接处产生应力集中,防止骨架结构发生脆性断裂,同时,氧化物陶瓷纳米纤维与抗氧化陶瓷防护层均具有优异的力学特性,提高了多层中空核壳纤维气凝胶的整体机械强度。
本发明多层中空核壳纤维气凝胶中,具有中空结构的氧化物陶瓷纳米纤维具有高耐温性,同时中空结构可有效降低纤维密度与本征固相热导率,并抑制辐射传热。
本发明多层中空核壳纤维气凝胶中,抗氧化陶瓷防护层与遮光防护层均具有高遮光性能,可降低纳米纤维气凝胶的高温辐射热导率;虽然遮光防护层具有更优异的遮光效果,但在高温环境下易发生氧化,抗氧化陶瓷防护层可保证遮光防护层发生氧化后纳米纤维气凝胶依然具有优异的遮光特性,有效抑制高温辐射传热。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明多层中空核壳纤维气凝胶的结构组成示意图;图中,1-多层中空核壳纤维气凝胶,2-多层中空核壳纳米纤维,3-中空结构,4-氧化物陶瓷纳米纤维,5-抗氧化陶瓷防护层,6-遮光防护层。
图2为本发明中空核壳纳米纤维2在不同长径比下的消光系数。
图3为本发明抗氧化陶瓷防护层5在不同厚度下的消光系数。
图4为本发明遮光防护层6在不同厚度下的消光系数。
图5为本发明实施例1中的多层中空核壳纤维气凝胶的等效热导率、气相热导率、固相热导率、辐射热导率。
图6为本发明实施例1中的多层中空核壳纤维气凝胶的等效弹性模量。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值,以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
实施例1
如图1所示,本实施例多层中空核壳纤维气凝胶1是由若干个空间随机分布的多层中空核壳纳米纤维2相互搭接组成的三维多孔纤维气凝胶材料,多层中空核壳纳米纤维2的结构从内到外依次为:具有中空结构3的氧化物陶瓷纳米纤维4、抗氧化陶瓷防护层5及遮光防护层6。
本实施例多层中空核壳纤维气凝胶1通过以下步骤制备得到:
通过静电纺丝制备得到具有中空结构3的氧化物陶瓷纳米纤维4包裹抗氧化陶瓷防护层5的中空核壳纤维。
通过在抗氧化陶瓷防护层5表面包覆具有粘合作用的间苯二酚-甲醛树脂材料,在氩气环境的高温管式炉里于1000℃碳化2小时(碳化的温度为800-1600℃均可),使得纤维外表面形成遮光防护层6(即间苯二酚-甲醛树脂经高温碳化形成遮光防护层),遮光防护层6可有效链接相邻的多层中空核壳纳米纤维2构成三维多孔纤维气凝胶材料(即多层中空核壳纤维气凝胶1)。
具有中空结构3的氧化物陶瓷纳米纤维4的内径即中空结构3的直径为15nm,外径即氧化物陶瓷纳米纤维4的直径为30nm。
氧化物陶瓷纳米纤维4的材料组成为三氧化二铝。
抗氧化陶瓷防护层5的材料组成为碳化硅;厚度为10nm。
遮光防护层6的组分材料为热解碳;厚度为30nm。
多层中空核壳纳米纤维2的长径比为5,即纤维直径为70nm,长度为350nm。
本实施例中多层中空核壳纤维气凝胶的密度为0.072g·cm-3,孔隙率为90%。
在实施例1的基础上,其他条件不变的情况下,测试多层中空核壳纳米纤维2的长径比对于消光系数的影响,结果如图2所示,当多层中空核壳纳米纤维2的长径比为5,即纤维直径为70nm,长度为350nm时,所制备的多层中空核壳纤维气凝胶1的消光系数最大,具有最佳的高温辐射抑制效果。
本发明还验证了当多层中空核壳纳米纤维2的长径比为6、7时多层中空核壳纤维气凝胶1的消光系数,结果表明,随着多层中空核壳纳米纤维2的长径比的进一步增大,多层中空核壳纤维气凝胶1的消光系数反而开始降低。当多层中空核壳纳米纤维2的长径比为5时,所制备的多层中空核壳纤维气凝胶1的消光系数最大。
在实施例1的基础上,其他条件不变的情况下,测试抗氧化陶瓷防护层5厚度(即碳化硅厚度)对于消光系数的影响,结果如图3所示,当碳化硅的厚度为10nm时,多层中空核壳纤维气凝胶1的消光系数最大,具有最佳的高温辐射抑制效果。
本发明还验证了当抗氧化陶瓷防护层5的厚度为5nm时多层中空核壳纤维气凝胶1的消光系数,结果表明,当碳化硅的厚度小于10nm时,多层中空核壳纤维气凝胶1的消光系数随着碳化硅厚度的增大而增大,当碳化硅的厚度大于10nm时,多层中空核壳纤维气凝胶1的消光系数随着碳化硅厚度的增大而减小,当碳化硅的厚度为10nm时,多层中空核壳纤维气凝胶1的消光系数最大。
在实施例1的基础上,其他条件不变的情况下,测试遮光防护层6厚度(即热解碳厚度)对于消光系数的影响,结果如图4所示,当热解碳的厚度为30nm时,多层中空核壳纤维气凝胶1的消光系数最大,具有最佳的高温辐射抑制效果。
本发明还验证了当遮光防护层6厚度(即热解碳厚度)为40nm时多层中空核壳纤维气凝胶1的消光系数,结果表明,随着遮光防护层6的厚度的进一步增大,多层中空核壳纤维气凝胶1的消光系数反而开始减小,当遮光防护层6的厚度为30nm时,多层中空核壳纤维气凝胶1的消光系数最大。
如图5所示,多层中空核壳纤维气凝胶1的等效热导率在常温环境下(300K)为0.012W·m-1·K-1,在高温环境下(1500K)为0.028W·m-1·K-1
如图6所示,多层中空核壳纤维气凝胶1的等效弹性模量在常温环境下(300K)为165.8GPa,在高温环境下(1500K)为155.6GPa。
本发明通过空间随机分布的多层中空核壳纳米纤维2组成的三维多孔纤维气凝胶材料(多层中空核壳纤维气凝胶1)的纤维连接处不易产生应力集中,防止骨架结构发生脆性断裂,提高纳米纤维气凝胶的整体机械强度;具有中空结构3的氧化物陶瓷纳米纤维4具有高耐温性,同时中空结构3可有效降低纤维密度与本征固相热导率,并抑制辐射传热;抗氧化陶瓷防护层5与遮光防护层6均具有高遮光性能,可降低纳米纤维气凝胶的高温辐射热导率,然而,遮光防护层6在高温环境下易发生氧化,抗氧化陶瓷防护层5可保证遮光防护层发生氧化后纳米纤维气凝胶依然具有优异的遮光特性,有效抑制高温辐射传热。
本发明采用若干个空间随机分布的多层中空核壳纳米纤维2组成的多层中空核壳纤维气凝胶1,兼具有低密度、低热导率、高机械强度及高热稳定性的优点,可有效阻隔航天器外部环境热流,保证热防护系统具备使役可靠性,满足航天飞行器的热防护需求。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。

Claims (7)

1.一种多层中空核壳纤维气凝胶,其特征在于,由若干个空间随机分布的多层中空核壳纳米纤维(2)相互搭接组成;所述多层中空核壳纳米纤维(2)的结构组成从内到外依次为具有中空结构(3)的氧化物陶瓷纳米纤维(4)、抗氧化陶瓷防护层(5)以及遮光防护层(6)。
2.根据权利要求1所述的多层中空核壳纤维气凝胶,其特征在于,所述具有中空结构(3)的氧化物陶瓷纳米纤维(4)的空心度为0-1,且不为0,不为1。
3.根据权利要求1所述的多层中空核壳纤维气凝胶,其特征在于,所述氧化物陶瓷纳米纤维(4)的材料组成为三氧化二铝或莫来石。
4.根据权利要求1所述的多层中空核壳纤维气凝胶,其特征在于,所述抗氧化陶瓷防护层(5)的材料组成为碳化硅、二氧化钛或二氧化锆中的一种。
5.根据权利要求1所述的多层中空核壳纤维气凝胶,其特征在于,所述遮光防护层(6)的材料组成为热解碳、树脂碳、沥青碳中的一种或多种。
6.根据权利要求1所述的多层中空核壳纤维气凝胶,其特征在于,所述多层中空核壳纳米纤维(2)的长径比为4-6。
7.根据权利要求1-6任一项所述的多层中空核壳纤维气凝胶在航天飞行器隔热材料中的应用。
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