多壁碳纳米管/硬脂酸-十八醇@脲醛树脂微胶囊的制备及表征
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摘要
通过原位聚合法以硬脂酸-十八醇低共融复合相变材料(SA-OA,质量比为50.02%,相变温度为55℃)为芯材,三聚氰胺改性的脲醛树脂(UF)为壁材,氨基化多壁碳纳米管(MWCNTs-NH2)为高导热填料制备了MWCNTs/SA-OA@UF相变微胶囊。采用FTIR、SEM、DSC、TGA和导热系数仪,对MWCNTs/SA-OA@UF相变微胶囊的化学结构、表面形貌、相变性能和导热性能进行表征。讨论了不同的MWCNTs修饰方法、不同乳化剂种类和MWCNTs-NH2添加量对SA-OA@UF相变微胶囊的影响。结果表明:MWCNTs-NH2在溶液中分散性良好;十二烷基苯磺酸钠(SDBS)和曲拉通X-100复配乳化剂使SA-OA@UF相变微胶囊的表面形貌更加光滑平整;添加质量比为0.5%的MWCNTs-NH2,使MWCNTs/SA-OA@UF相变微胶囊的导热系数达到0.224W/(m·K),提高了38%(55℃),包覆率提高了6.9%,粒度更加均一,热稳定性有明显提高。
The multi-walled carbon nanotubes/stearic acid-octadecyl alcohol@urea formaldehyde resin(MWCNTs/SA-OA@UF)phase change microcapsules with SA-OA eutectic composite phase change materials(at the mass ratio of 50.02%,phase change temperature was 55℃)as core material,UF modified by melamine as wall material and amino multi-walled carbon nanotubes(MWCNTs-NH_2)as highly thermally conductive filler were prepared by using in-situ polymerization method.The chemical structure,morphology,thermal properties and thermal conductivity of the MWCNTs/SA-OA@UF phase change microcapsules were characterized by FTIR,SEM,DSC,TGA and thermal conductivity meter.The effects of different MWCNT modification methods,different types of emulsifiers and the amount of MWCNTs-NH_2 added in the SA-OA@UF phase change microcapsules were discussed.The results show that the MWCNTs-NH_2 have good dispersibility in the solution;The compounded emulsifiers of sodium dodecyl benzene sulfonate(SDBS)and Triton X-100 make the surface morphology of the SA-OA@UF phase change microcapsules smoother and smoother;The addition of MWCNTs-NH2 with the mass ratio of 0.5% make the MWCNTs/SA-OA@UF phase change microcapsule's thermal conductivity reaches 0.224 W/(m·K),which increases by38%(55℃),the coating rate increases by 6.9%,the particle size is more uniform and the thermal stability is significantly improved.
The multi-walled carbon nanotubes/stearic acid-octadecyl alcohol@urea formaldehyde resin(MWCNTs/SA-OA@UF)phase change microcapsules with SA-OA eutectic composite phase change materials(at the mass ratio of 50.02%,phase change temperature was 55℃)as core material,UF modified by melamine as wall material and amino multi-walled carbon nanotubes(MWCNTs-NH_2)as highly thermally conductive filler were prepared by using in-situ polymerization method.The chemical structure,morphology,thermal properties and thermal conductivity of the MWCNTs/SA-OA@UF phase change microcapsules were characterized by FTIR,SEM,DSC,TGA and thermal conductivity meter.The effects of different MWCNT modification methods,different types of emulsifiers and the amount of MWCNTs-NH_2 added in the SA-OA@UF phase change microcapsules were discussed.The results show that the MWCNTs-NH_2 have good dispersibility in the solution;The compounded emulsifiers of sodium dodecyl benzene sulfonate(SDBS)and Triton X-100 make the surface morphology of the SA-OA@UF phase change microcapsules smoother and smoother;The addition of MWCNTs-NH2 with the mass ratio of 0.5% make the MWCNTs/SA-OA@UF phase change microcapsule's thermal conductivity reaches 0.224 W/(m·K),which increases by38%(55℃),the coating rate increases by 6.9%,the particle size is more uniform and the thermal stability is significantly improved.
引文
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[2]童晓梅,闫子英,韩洋.石墨和纳米SiO2改性P(MMA-CoAA)/石蜡相变储热微胶囊的制备及性能研究[J].新型建筑材料,2015,42(11):58-61.TONG X M,YAN Z Y,HAN Y.Study on the preparation and the properties of P(MMA-co-AA)/paraffin phase change thermal storage microcapsules modified by graphite and nanoSiO2[J].New Building Materials,2015,42(11):58-61(in Chinese).
[3]VASANTHAN N,KOTEK R,JUNG D W,et al.Lewis acid-base complexation of polyamide 66to control hydrogen bonding,extensibility and crystallinity[J].Polymer,2004,45(12):4077-4085.
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[5]王瑞,孙艳丽,刘星,等.碳纳米管改性相变微胶囊的力学与热学性能[J].纺织学报,2018,39(2):119-125.WANG R,SUN Y L,LIU X,et al.Mechanical and thermal properties of phase change microcapsules modified with carbon nanotubes[J].Journal of Textile Research,2018,39(2):119-125(in Chinese).
[6]ZUO J,LI W,WENG L.Thermal performance of caprylic acid/1-dodecanol eutectic mixture as phase change material(PCM)[J].Energy and Building,2011,3(1):207-210.
[7]ZUO J,LI W,WENG L.Thermal performance of lauric acid/decanol binary system for energy storage[J].Applied Engineering,2011,31(6):1352-1355.
[8]黄雪.三元低共熔脂肪酸复合相变材料的制备及热性能研究[D].广州:广东工业大学,2015.HUANG X.The preparation and thermal properties of fatty acids ternary eutectic mixture composite phase change material[D].Guangzhou:Guangdong University of Technology,2015(in Chinese).
[9]SARI A,BIER A,KARAIPEKLI A.Synthesis,characterization,thermal properties of a series of stearic acid esters as novel solid-liquid phase change materials[J].Materials Letters,2009,63(13-14):1213-1216.
[10]吴梓敏.癸酸-棕榈酸/脲醛树脂微胶囊相变材料的制备及应用研究[D].广州:仲恺农业工程学院,2015.WU Z M.Preparation and application of capric acid-palmitic acid/urea-formaldehyde resin microcapsule phase change material[D].Guangzhou:Zhongkai University of Agriculture and Engineering,2015(in Chinese).
[11]曾少华,申明霞,段鹏鹏,等.碳纳米管微胶囊制备与应用进展[J].粘接,2016(5):39-42.ZENG S H,SHEN M X,DUAN P P,et al.Preparation and application of carbon nanotubes microcapsules[J].Adhesion,2016(5):39-42(in Chinese).
[12]周文英,丁小卫.导热高分子材料[M].北京:国防工业出版社,2014.ZHOU W Y,DING X W.Thermal conductive polymer materials[M].Beijing:National Defense Industry Press,2014(in Chinese).
[13]李军,黄际伟,李庆彪.壁材掺杂碳纳米管的相变微胶囊的制备及热性能研究[J].功能材料,2014,45(s2):110-114.LI J,HUANG J W,LI Q B.Preparation and thermal properties of phase change microcapsules doped with carbon nanotubes[J].Journal of Functional Materials,2014,45(s2):110-114(in Chinese).
[14]国家质量技术监督局.非金属固体材料导热系数的测定热线法:GB/T 10297-1998[S].北京:中国标准出版社,1998.State Bureau of Quality Technical Supervision.Test method for thermal conductivity of nonmetal solid materials by hotwire method:GB/T 10297-1998[S].Beijing:China Standards Press,1998(in Chinese).
[15]袁婕.碳纳米管在水中的分散性研究[D].南京:南京工业大学,2008.YUAN J.Dispersion of carbon nanOtubes in water[D].Nanjing:Nanjing Tech University,2008(in Chinese).
[16]KARAIPEKLI A,SARI A.Preparation,thermal properties and thermal reliability of eutectic mixtures of fatty acids/expanded vermiculite as novel form-stable composites for energy storage[J].Journal of Industrial&Engineering Chemistry,2010,16(5):767-773.
[17]SARI A,KAYGUSUZ K.Thermal energy storage system using some fatty acids as latent heat energy storage materials[J].Energy Sources,2001,23(3):275-285.
[18]LU S,SHEN T,XING J,et al.Preparation,characterization,and thermal stability of double-composition shell microencapsulated phase change material by interfacial polymerization[J].Colloid&Polymer Science,2017,295(10):2061-2067.
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[21]DAOU I,EL-KADDADI L,ZEGAOUI O,et al.Structural,morphological and thermal properties of novel hybrid-microencapsulated phase change materials based on Fe2O3,ZnOand TiO2,nanoparticles for latent heat thermal energy storage applications[J].Journal of Energy Storage,2018,17:84-92.