技术领域Technical Field
本发明属于地下能源存储技术领域，具体涉及一种二元纳米材料改性环氧树脂基材料及其在内衬式岩洞密封层中的应用。The present invention belongs to the technical field of underground energy storage, and in particular relates to a binary nanomaterial-modified epoxy resin-based material and an application thereof in a lining-type rock cave sealing layer.
背景技术Background Art
氢能是未来能源体系的组成部分，是用能终端高耗能、高排放行业实现绿色低碳转型的重要载体。储氢是氢能安全、高效、规模化和低成本运用的基础，也是解决氢能技术路线应用环节的关键。内衬式岩洞(Lined Rock Caves，简称LRC)储量大、安全性高、成本低，是较为理想的大规模氢气存储体系。Hydrogen energy is an integral part of the future energy system and an important carrier for high-energy-consuming and high-emission industries to achieve green and low-carbon transformation. Hydrogen storage is the basis for the safe, efficient, large-scale and low-cost use of hydrogen energy, and is also the key to solving the application link of hydrogen energy technology routes. Lined Rock Caves (LRC) have large reserves, high safety and low cost, and are an ideal large-scale hydrogen storage system.
传统内衬式岩洞由钢内衬、混凝土衬砌、围岩、排水系统等组成，但当钢内衬材料长期暴露在氢气中，特别是在高温高压环境下时，将会发生氢致气泡、氢致开裂和氢蚀脆化等现象，大大降低其耐久性能。此外，密封层必须具有较好的导热性能，以便及时将压缩氢气产生的热量传递出去，降低洞室内部气压，保障洞室受力安全。因此，亟需开发一种新型密封材料代替钢内衬，为高压氢气提供密封保障。Traditional lined caverns are composed of steel lining, concrete lining, surrounding rock, drainage system, etc. However, when the steel lining material is exposed to hydrogen for a long time, especially under high temperature and high pressure environment, hydrogen-induced bubbles, hydrogen-induced cracking and hydrogen embrittlement will occur, greatly reducing its durability. In addition, the sealing layer must have good thermal conductivity so that the heat generated by the compressed hydrogen can be transferred out in time, the internal air pressure of the cavern can be reduced, and the force safety of the cavern can be ensured. Therefore, it is urgent to develop a new type of sealing material to replace the steel lining to provide sealing protection for high-pressure hydrogen.
发明内容Summary of the invention
本发明的目的在于提供一种二元纳米材料改性环氧树脂基材料及其在内衬式岩洞密封层中的应用。The purpose of the present invention is to provide a binary nano material modified epoxy resin-based material and its application in a lining type cave sealing layer.
为实现上述目的，本发明提供了如下技术方案：To achieve the above object, the present invention provides the following technical solutions:
本发明技术方案之一：提供一种二元纳米材料改性环氧树脂基材料的制备方法，包括以下步骤：One of the technical solutions of the present invention is to provide a method for preparing a binary nanomaterial-modified epoxy resin-based material, comprising the following steps:
将氧化石墨烯(GO)分散液与4,4'-二苯基甲烷二异氰酸酯(MDI)混合，反应所得产物继续与氧化铝(AO)分散液反应，得到三维二元纳米填料，将所述三维二元纳米填料制成三维二元纳米填料分散液，利用环氧树脂排空所述三维二元纳米填料分散液中的溶剂，即得二元纳米材料改性环氧树脂基材料。A graphene oxide (GO) dispersion is mixed with 4,4'-diphenylmethane diisocyanate (MDI), and the reaction product is further reacted with an aluminum oxide (AO) dispersion to obtain a three-dimensional binary nanofiller. The three-dimensional binary nanofiller is made into a three-dimensional binary nanofiller dispersion, and the solvent in the three-dimensional binary nanofiller dispersion is emptied by epoxy resin to obtain a binary nanomaterial-modified epoxy resin-based material.
优选地，所述氧化石墨烯分散液中氧化石墨烯与所述4,4'-二苯基甲烷二异氰酸酯的质量比为1:1。Preferably, the mass ratio of graphene oxide to 4,4'-diphenylmethane diisocyanate in the graphene oxide dispersion is 1:1.
优选地，所述氧化石墨烯分散液和所述4,4'-二苯基甲烷二异氰酸酯的反应产物与所述氧化铝分散液中氧化铝的质量比为3:2。Preferably, the mass ratio of the reaction product of the graphene oxide dispersion and the 4,4'-diphenylmethane diisocyanate to the aluminum oxide in the aluminum oxide dispersion is 3:2.
优选地，所述氧化石墨烯分散液与所述4,4'-二苯基甲烷二异氰酸酯的反应温度为60℃。Preferably, the reaction temperature of the graphene oxide dispersion and the 4,4'-diphenylmethane diisocyanate is 60°C.
优选地，所述氧化石墨烯分散液和所述4,4'-二苯基甲烷二异氰酸酯的反应产物与所述氧化铝分散液的反应温度为60℃。Preferably, the reaction temperature of the reaction product of the graphene oxide dispersion and the 4,4'-diphenylmethane diisocyanate with the aluminum oxide dispersion is 60°C.
本发明技术方案之二：提供一种根据上述二元纳米材料改性环氧树脂基材料的制备方法制得的二元纳米材料改性环氧树脂基材料。The second technical solution of the present invention is to provide a binary nanomaterial-modified epoxy resin-based material prepared according to the preparation method of the above-mentioned binary nanomaterial-modified epoxy resin-based material.
本发明技术方案之三：提供一种上述二元纳米材料改性环氧树脂基材料在制备内衬式岩洞密封层中的应用。The third technical solution of the present invention is to provide an application of the above binary nanomaterial modified epoxy resin-based material in the preparation of a lining-type cave sealing layer.
利用上述二元纳米材料改性环氧树脂基材料制备内衬式岩洞密封层时，只需要向所述二元纳米材料改性环氧树脂基材料中加入固化剂，固化后即为内衬式岩洞密封层。When the lining-type cave sealing layer is prepared by using the above binary nanomaterial-modified epoxy resin-based material, it is only necessary to add a curing agent to the binary nanomaterial-modified epoxy resin-based material, and the lining-type cave sealing layer is obtained after curing.
本发明的有益技术效果如下：The beneficial technical effects of the present invention are as follows:
通过本发明提供的二元纳米材料改性环氧树脂基材料制备的内衬岩洞密封层，是以环氧树脂作为基体，并由氧化铝(AO)和氧化石墨烯(GO)组成二元纳米体系对其进行改性。其中，片状氧化石墨烯和球状氧化铝形成“豌豆荚”式网状结构，提供氢气密封网络和高效导热通路。The inner lining cave sealing layer prepared by the binary nanomaterial modified epoxy resin-based material provided by the present invention uses epoxy resin as the matrix and is modified by a binary nanosystem composed of aluminum oxide (AO) and graphene oxide (GO). Among them, the flake graphene oxide and the spherical aluminum oxide form a "pea pod" network structure, providing a hydrogen sealing network and an efficient heat conduction path.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为内衬式岩洞的结构示意图。Figure 1 is a schematic diagram of the structure of a lined cave.
图2为实施例1制备的内衬式岩洞密封层材料的结构示意图。FIG. 2 is a schematic diagram of the structure of the lining type cave sealing layer material prepared in Example 1.
图3为实施例1中内衬式岩洞密封层材料的反应流程图。FIG3 is a reaction flow chart of the lining type cave sealing layer material in Example 1.
图4为实施例1中内衬式岩洞密封层材料的制备流程图。FIG. 4 is a flow chart of the preparation of the lining type cave sealing layer material in Example 1.
图5为实施例1中各原料与最终制备的内衬式岩洞密封层材料的SEM图，其中，(a)为AO的SEM图，(b)为GO的SEM图，(c)为GO-MDI-AO掺量5％的内衬式岩洞密封层材料的SEM图，(d)为GO-MDI-AO掺量10％的内衬式岩洞密封层材料的SEM图，(e)为GO-MDI-AO掺量15％的内衬式岩洞密封层材料的SEM图，(f)为GO-MDI-AO掺量20％的内衬式岩洞密封层材料的SEM图。Figure 5 is the SEM images of the raw materials in Example 1 and the finally prepared lined cave sealing layer material, wherein (a) is the SEM image of AO, (b) is the SEM image of GO, (c) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 5%, (d) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 10%, (e) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 15%, and (f) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 20%.
图6为内衬式岩洞密封层材料提高氢气密封能力的机理图。FIG. 6 is a diagram showing the mechanism by which the lining-type cave sealing layer material improves the hydrogen sealing capability.
图7为内衬式岩洞密封层材料提高导热性能的机理图。FIG. 7 is a diagram showing the mechanism of improving thermal conductivity of lining-type cave sealing layer materials.
具体实施方式DETAILED DESCRIPTION
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。Now, various exemplary embodiments of the present invention are described in detail, which should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.
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。In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.
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。Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the invention.
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。The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
内衬式岩洞的结构示意图见图1。The structural diagram of the lined cave is shown in Figure 1.
实施例1Example 1
一种内衬式岩洞密封层材料的制备：Preparation of a lining type cave sealing layer material:
(1)将GO混入N,N-二甲基甲酰胺(DMF)溶液中；然后，使用VCX-500W超声波仪对GO悬浮液进行超声处理；加入与GO等质量的MDI粉末，然后，将悬浮液在60℃下加热并磁力搅拌24小时；GO表面和边缘的羟基(-OH)和羧基(-COOH)与MDI中的异氰酸酯(-NCO)发生反应，将MDI接枝到GO表面，随后过滤混合物并用乙酸乙酯洗涤，除去残留的MDI，产物在60℃的真空中干燥12小时，命名为GO-MDI。(1) GO was mixed into N,N-dimethylformamide (DMF) solution; the GO suspension was then sonicated using a VCX-500W sonicator; MDI powder of equal mass to GO was added, and then the suspension was heated at 60°C and magnetically stirred for 24 h; the hydroxyl (-OH) and carboxyl (-COOH) groups on the surface and edge of GO reacted with the isocyanate (-NCO) in MDI to graft MDI onto the GO surface, and then the mixture was filtered and washed with ethyl acetate to remove residual MDI. The product was dried in a vacuum at 60°C for 12 h and was named GO-MDI.
(2)将质量比为6:4的GO-MDI和AO的粉末分散在DMF中，超声20分钟；然后将悬浮液在60℃下加热并磁力搅拌24小时，AO表面的羟基(-OH)与MDI中的异氰酸酯(-NCO)发生反应，导致AO通过MDI与GO连接，形成三维二元纳米填料，命名为GO-MDI-AO；(2) GO-MDI and AO powders with a mass ratio of 6:4 were dispersed in DMF and ultrasonicated for 20 min. The suspension was then heated at 60 °C and magnetically stirred for 24 h. The hydroxyl groups (-OH) on the surface of AO reacted with the isocyanate (-NCO) in MDI, resulting in the connection of AO with GO through MDI to form a three-dimensional binary nanofiller named GO-MDI-AO.
(3)将所需质量比例的GO-MDI-AO以50％的恒定振幅在乙酸乙酯溶液中超声30分钟，以获得纳米填料在溶剂中的均匀分散液；然后，将分散液加入环氧树脂中，在60℃下持续搅拌，直到溶剂全部排空，得到环氧树脂与GO-MDI-AO的粘稠悬浮液，即为二元纳米材料改性环氧树脂基材料。(3) The GO-MDI-AO with the required mass ratio is ultrasonically treated in an ethyl acetate solution at a constant amplitude of 50% for 30 minutes to obtain a uniform dispersion of the nanofiller in the solvent; then, the dispersion is added to the epoxy resin and stirred continuously at 60°C until the solvent is completely drained to obtain a viscous suspension of the epoxy resin and GO-MDI-AO, i.e., the binary nanomaterial-modified epoxy resin-based material.
本步骤制备了四个质量占比的材料，其中GO-MDI-AO在二元纳米材料改性环氧树脂基材料中的质量占比分别为5％、10％、15％和20％；制备的二元纳米材料改性环氧树脂基材料的储存温度不高于25℃，以免其预固化。In this step, four materials with different mass ratios were prepared, in which the mass ratios of GO-MDI-AO in the binary nanomaterial-modified epoxy resin-based material were 5%, 10%, 15% and 20% respectively; the storage temperature of the prepared binary nanomaterial-modified epoxy resin-based material was not higher than 25°C to prevent pre-curing.
(4)将步骤(3)得到的各二元纳米材料改性环氧树脂基材料分别用于制备内衬式岩洞密封层：(4) Using each binary nanomaterial-modified epoxy resin-based material obtained in step (3) to prepare a lining-type cave sealing layer:
向二元纳米材料改性环氧树脂基材料中加入固化剂，混合5分钟，混合物用真空泵脱气10分钟，以除去气泡，在室温下初步固化24小时后，继续在70℃下固化5小时，得到内衬式岩洞密封层材料。A curing agent was added to the binary nanomaterial modified epoxy resin-based material and mixed for 5 minutes. The mixture was degassed with a vacuum pump for 10 minutes to remove bubbles. After preliminary curing at room temperature for 24 hours, it was further cured at 70°C for 5 hours to obtain a lining-type cave sealing layer material.
图2为实施例1制备的内衬式岩洞密封层材料的结构示意图。FIG. 2 is a schematic diagram of the structure of the lining type cave sealing layer material prepared in Example 1.
图3为实施例1中内衬式岩洞密封层材料的反应流程图。FIG3 is a reaction flow chart of the lining type cave sealing layer material in Example 1.
图4为实施例1中内衬式岩洞密封层材料的制备流程图。FIG. 4 is a flow chart of the preparation of the lining type cave sealing layer material in Example 1.
图5为实施例1中各原料与最终制备的内衬式岩洞密封层材料的SEM图，其中，(a)为AO的SEM图，(b)为GO的SEM图，(c)为GO-MDI-AO掺量5％的内衬式岩洞密封层材料的SEM图，(d)为GO-MDI-AO掺量10％的内衬式岩洞密封层材料的SEM图，(e)为GO-MDI-AO掺量15％的内衬式岩洞密封层材料的SEM图，(f)为GO-MDI-AO掺量20％的内衬式岩洞密封层材料的SEM图。Figure 5 is the SEM images of the raw materials in Example 1 and the finally prepared lined cave sealing layer material, wherein (a) is the SEM image of AO, (b) is the SEM image of GO, (c) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 5%, (d) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 10%, (e) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 15%, and (f) is the SEM image of the lined cave sealing layer material with a GO-MDI-AO dosage of 20%.
从图5中能够看出，氧化铝和氧化石墨烯分别呈现典型的球状结构和片状结构。复合材料中，可见环氧树脂基体中嵌入了二元纳米材料，其中片状氧化石墨烯与球状氧化铝形成了网状结构。如图3所示的化学反应流程图，MDI的加入有效加强了氧化铝与氧化石墨烯之间的链接作用，形成了高性能二元纳米填料。As can be seen from Figure 5, aluminum oxide and graphene oxide present typical spherical structures and lamellar structures, respectively. In the composite material, it can be seen that binary nanomaterials are embedded in the epoxy resin matrix, in which the lamellar graphene oxide and the spherical aluminum oxide form a network structure. As shown in the chemical reaction flow chart in Figure 3, the addition of MDI effectively strengthens the link between aluminum oxide and graphene oxide, forming a high-performance binary nanofiller.
图6为内衬式岩洞密封层材料提高氢气密封能力的机理图。其中，氢分子根据浓度梯度以垂直方向通过传统密封层材料，而不可穿透的二元纳米填料在固化反应后提供了物理屏蔽效果，使氢分子沿着曲折路径通过，从而降低了氢气渗透率。Figure 6 is a diagram showing the mechanism of improving the hydrogen sealing ability of the lining cave sealing layer material. In it, hydrogen molecules pass through the traditional sealing layer material in a vertical direction according to the concentration gradient, while the impenetrable binary nanofiller provides a physical shielding effect after the curing reaction, allowing hydrogen molecules to pass along a tortuous path, thereby reducing the hydrogen permeability.
图7为内衬式岩洞密封层材料提高导热性能的机理图。其中，氧化石墨烯的二维结构形成了相互连接的桥梁和渗流网络，促进了声子传输；同时，具有合理粒度级配的氧化铝填充在氧化石墨烯片之间的空隙中，共同形成了更致密的热传导网络。Figure 7 is a diagram showing the mechanism of improving thermal conductivity of the lining cave sealing layer material. The two-dimensional structure of graphene oxide forms interconnected bridges and percolation networks, promoting phonon transmission; at the same time, alumina with a reasonable particle size distribution fills the gaps between graphene oxide sheets, forming a denser heat conduction network.
为了验证本发明提出的采用MDI接枝AO与GO后形成的网状结构改性作用的优越性，以AO与GO按质量比1:1简单共混后(不采用MDI接枝，不采用本发明的制备方式)的环氧树脂基复合材料为对照组，测试二者的密封性和导热性并进行比较。In order to verify the superiority of the network structure modification effect formed by MDI grafting AO and GO proposed in the present invention, an epoxy resin-based composite material in which AO and GO were simply blended in a mass ratio of 1:1 (without MDI grafting and without the preparation method of the present invention) was used as a control group, and the sealing and thermal conductivity of the two were tested and compared.
其中，实施例1制备的不同掺量的内衬式岩洞密封层材料的氢气渗透率见表1，导热系数见表2；对照组制备的内衬式岩洞密封层材料的氢气渗透率见表3，导热系数见表4。Among them, the hydrogen permeability of the lining type cave sealing layer material with different dosages prepared in Example 1 is shown in Table 1, and the thermal conductivity is shown in Table 2; the hydrogen permeability of the lining type cave sealing layer material prepared in the control group is shown in Table 3, and the thermal conductivity is shown in Table 4.
表1不同掺量下内衬式岩洞密封层材料的氢气渗透率(cm3m-2d-1atm-1)Table 1 Hydrogen permeability of lining type cave sealing layer materials at different dosages (cm3 m-2 d-1 atm-1 )
表2不同掺量下内衬式岩洞密封层材料的导热系数(Wm-1k-1)Table 2 Thermal conductivity of lining type cave sealing layer materials at different dosages (Wm-1 k-1 )
表3AO与GO共混的内衬式岩洞密封层材料的氢气渗透率(cm3m-2d-1atm-1)Table 3 Hydrogen permeability of lining cave sealing layer materials blended with AO and GO (cm3 m-2 d-1 atm-1 )
表4AO与GO共混的内衬式岩洞密封层材料的导热系数(Wm-1k-1)Table 4 Thermal conductivity of lining cave sealing layer materials blended with AO and GO (Wm-1 k-1 )
表1～表4的测试结果表明，简单共混制备的复合材料与本发明材料相比，氢气渗透率增大、导热系数降低，证明了MDI的加入在降低氢气渗透率和提高导热性能方面均展现出积极效果。The test results in Tables 1 to 4 show that the composite materials prepared by simple blending have increased hydrogen permeability and reduced thermal conductivity compared with the materials of the present invention, proving that the addition of MDI has a positive effect in reducing hydrogen permeability and improving thermal conductivity.
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。The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410761269.5ACN118515952A (en) | 2024-06-13 | 2024-06-13 | A binary nanomaterial modified epoxy resin-based material and its application in lining-type cave sealing layer |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410761269.5ACN118515952A (en) | 2024-06-13 | 2024-06-13 | A binary nanomaterial modified epoxy resin-based material and its application in lining-type cave sealing layer |
| Publication Number | Publication Date |
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| CN118515952Atrue CN118515952A (en) | 2024-08-20 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410761269.5APendingCN118515952A (en) | 2024-06-13 | 2024-06-13 | A binary nanomaterial modified epoxy resin-based material and its application in lining-type cave sealing layer |
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| CN (1) | CN118515952A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627139A (en)* | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105255111A (en)* | 2015-10-27 | 2016-01-20 | 广州新莱福磁电有限公司 | Preparation method and application of improved high thermal conductivity coefficient thermistor epoxy resin potting material |
| CN106987112A (en)* | 2017-04-11 | 2017-07-28 | 上海交通大学 | Electric drive resin base shape memory composite and preparation method thereof |
| CN107880538A (en)* | 2017-10-11 | 2018-04-06 | 上海阿莱德实业股份有限公司 | A kind of high heat conduction graphene modified nylon composite material and preparation method thereof |
| US20200071487A1 (en)* | 2016-12-15 | 2020-03-05 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-d) graphene polymer composite materials, methods of making, and uses thereof |
| CN115651342A (en)* | 2022-11-04 | 2023-01-31 | 谭鹏 | High thermal conductivity composition and use thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627139A (en)* | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105255111A (en)* | 2015-10-27 | 2016-01-20 | 广州新莱福磁电有限公司 | Preparation method and application of improved high thermal conductivity coefficient thermistor epoxy resin potting material |
| US20200071487A1 (en)* | 2016-12-15 | 2020-03-05 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-d) graphene polymer composite materials, methods of making, and uses thereof |
| CN106987112A (en)* | 2017-04-11 | 2017-07-28 | 上海交通大学 | Electric drive resin base shape memory composite and preparation method thereof |
| CN107880538A (en)* | 2017-10-11 | 2018-04-06 | 上海阿莱德实业股份有限公司 | A kind of high heat conduction graphene modified nylon composite material and preparation method thereof |
| CN115651342A (en)* | 2022-11-04 | 2023-01-31 | 谭鹏 | High thermal conductivity composition and use thereof |
| Title |
|---|
| KAI QIU ET AL.: "《Enhancing comprehensive performance of epoxy-based sealing layer with a binary nanofiller for underground hydrogen energy storage》", 《JOURNAL OF ENERGY STORAGE》, vol. 80, 1 March 2024 (2024-03-01), pages 110261* |
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