化学氧化聚合法下的聚苯胺复合纳米Al_2O_3的电磁参数
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摘要
为改善聚苯胺(PANI)的电磁性能,在PANI中掺杂纳米氧化铝,并以过硫酸铵为氧化剂,盐酸为质子酸,采用化学氧化聚合法制备聚苯胺/纳米氧化铝复合材料。固定苯胺浓度为0.5 mol/L,以过硫酸铵浓度、盐酸浓度、纳米氧化铝质量和反应时间为因素设计4因素4水平正交试验,并制备出16组聚苯胺/纳米氧化铝复合材料。分析聚苯胺/纳米氧化铝复合材料的聚合机理,计算各组试样阻抗值,得出聚苯胺/纳米氧化铝复合材料的最佳制备条件,利用扫描电镜及红外光谱分析表征复合材料表面形貌及结构,计算最佳制备条件下复合材料的反射损耗。结果表明:所制备出的聚苯胺/纳米氧化铝复合材料呈核-壳结构,合成过程中有类似氢键的相互作用;当过硫酸铵浓度为0.025 mol/L,盐酸浓度为2 mol/L,纳米氧化铝为2.5 g,反应时间为6 h时,制备的聚苯胺/纳米氧化铝阻抗最小,且反射损耗值增加。
In order to improve the electromagnetic properties of polyaniline(PANI), nano-alumina was doped in PANI, and with ammonium persulfate as oxidant and hydrochloric acid as proton acid, the polyaniline/nano-alumina composites were prepared by chemical oxidation polymerization. The concentration of fixed aniline was 0.5 mol/L;with ammonium persulfate concentration, hydrochloric acid concentration, nano-alumina quality and reaction time as factors,four factors and four levels orthogonal experiments were designed, and sixteen groups of composites were prepared. The polymerization mechanism was analyzed, and the impedance values of each group of samples were calculated. The optimum preparation conditions were obtained. The surface morphology and structure of the composites were characterized by scanning electron microscopy and infrared spectroscopy, and the reflection loss of the composites under the optimum preparation conditions was calculated. The results show that the prepared composites have core-shell structure and hydrogen bond-like interaction during the synthesis process. When ammonium persulfate concentration is 0.025 mol/L, hydrochloric acid concentration is 2 mol/L, nano-alumina concentration is 2.5 g and reaction time is 6 h, the impedance of the composites is the smallest, and the reflection loss value increases.
In order to improve the electromagnetic properties of polyaniline(PANI), nano-alumina was doped in PANI, and with ammonium persulfate as oxidant and hydrochloric acid as proton acid, the polyaniline/nano-alumina composites were prepared by chemical oxidation polymerization. The concentration of fixed aniline was 0.5 mol/L;with ammonium persulfate concentration, hydrochloric acid concentration, nano-alumina quality and reaction time as factors,four factors and four levels orthogonal experiments were designed, and sixteen groups of composites were prepared. The polymerization mechanism was analyzed, and the impedance values of each group of samples were calculated. The optimum preparation conditions were obtained. The surface morphology and structure of the composites were characterized by scanning electron microscopy and infrared spectroscopy, and the reflection loss of the composites under the optimum preparation conditions was calculated. The results show that the prepared composites have core-shell structure and hydrogen bond-like interaction during the synthesis process. When ammonium persulfate concentration is 0.025 mol/L, hydrochloric acid concentration is 2 mol/L, nano-alumina concentration is 2.5 g and reaction time is 6 h, the impedance of the composites is the smallest, and the reflection loss value increases.
引文
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[22] 王攀,刘羽熙,王永贵,等.PPy/MWNTs/GO复合材料的制备与电化学性能研究[J].材料科学与工艺,2016,24(3):92-96.WANG P,LIU Y X,WANG Y G,et al.Preparation and electrochemical performance of PPy/MWNTs/GO composites[J].Materials Science and Technology,2016,24(3):92-96.(in Chinese)
[23] 胡捷,卢英林.聚苯胺反应配比条件选择的研究[J].纺织基础科学学报,1992(1):16-20.HU J,LU Y L.A study on selection of mixture ratio for polyaniline reaction[J].1992(1):16-20.(in Chinese)
[24] 马硕.导电聚苯胺对金属/酸反应体系影响作用的研究[D].天津:天津工业大学,2016.MA S.Effect of conductive polyaniline on metal/acid reaction system [D].Tianjin:Tianjin University of Technology,2016.(in Chinese)
[25] 彭勇刚,纪俊玲,杨利霞,等.聚苯胺/涤纶导电织物的制备及其性能研究[J].印染助剂,2016,33(5):41-43.PENG Y G,JI J L,YANG L X,et al.Preparation of polyaniline/polyester conductive fabric and their properties[J].Textile Auxiliaries,2016,33(5):41-43.(in Chinese)
[26] 张捷,刘伟,张婷,等.导电聚合物基复合吸波材料的研究进展[J].微纳电子技术,2018,55(2):91-97.ZHANG J,LIU W,ZHANG T,et al.Research progress of conductive polymer composites for microwave absorption[J].Micronanoelectronic Technology,2018,55(2):91-97.(in Chinese)
[27] HU C B,ZHENG Y S,QING Y Q,et al.Preparation of poly(o-toluidine)/nano-ZrO2/epoxy composite coating and its application for corrosion protection of steel[J].Journal of Wuhan University of Technology(Materials Science Edition),2016,31(4):937-944.
[28] 张玉富.铁氧体/聚苯胺(石墨烯)复合材料的制备及微波吸收性能研究[D].淮南:安徽理工大学,2016.ZHANG Y F.Preparation and microwave absorption properties evaluation of Ferrite/Polyaniline(RGO)Nanocomposites[D].Huainan:Anhui University of Science & Technology,2016.(in Chinese)
[29] 李琳,姚正军,周金堂,等.聚苯胺纳米纤维/锂锌铁氧体复合吸波材料的制备与性能[J].复合材料学报,2016,33(4):814-820.LI L,YAO Z J,ZHOU J T,et al.Preparation and property of polyaniline nanofibers/lithium zinc ferrite composite absorbents[J].Acta Materiae Compositae Sinica,2016,33(4):814-820.(in Chinese)
[30] 高磊,何大伟,王永生.聚苯胺与还原石墨烯复合材料的微波吸收性能[J].发光学报,2018,39(10):1347-1351.GAO L,HE D W,WANG Y S.Microwave absorption property of Polyaniline/Reduced grapheme[J].Chinese Journal of Luminescence,2018,39(10):1347-1351.(in Chinese)
[2] CHAFAI H,LAABD M,ELAMINE M,et al.Chemical synthesis and characterization of polyaniline:Water depollution efficiency and effectiveness[J].Desalination & Water Treatment,2017:314-320.
[3] REKA D M,SARANYA A,PANDIARAJAN J,et al.Electro chemical and optical performance of organic acids doped polyaniline (PANI) [J].Journal of Applied Science and Engineering Methodologies,2016,3(2):317-321.
[4] LIU P,ZHU Y,TORRES J,et al.Facile and template-free method toward chemical synthesis of polyaniline film/nanotube structures[J].Journal of Polymer Science A Polymer Chemistry,2017,55(24):3973-3979.
[5] 郭亚军,张龙,后洁琼,等.中空结构聚苯胺/Fe3 O4/炭黑复合材料的制备及吸波性能[J].高等学校化学学报,2016,37(6):1202-1207.GUO Y J,ZHANG L,HOU J Q,et al.Preparation and wave-absorbing performance of PANI/Fe3 O4/CB hollow structured composites[J].Chemical Journal of Chinese Universities,2016,37(6):1202-1207.(in Chinese)
[6] 张保宏,薛涛,孟家光.聚苯胺基涤纶复合导电纱线的制备及表征[J].西安工程大学学报,2013,27(2):140-143.ZHANG B H,XUE T,MENG J G.Preparation and characterization on polyaniline/polyester[J].Journal of Xi’an Polytechnic University,2013,27(2):140-143.(in Chinese)
[7] FAN M,HE Z F,PANG H.Microwave absorption enhancement of CIP/PANI composites[J].Synthetic Metals,2013,166(1):1-6.
[8] 王海花,罗璐,李小瑞,等.聚苯胺/四氧化三铁吸波材料的制备与性能[J].精细化工,2017,34(9):988-995.WANG H H,LUO L,LI X R,et al.Preparation and properties of polyaniline/Fe3O4 absorbing materials[J].Fine Chemicals,2017,34(9):988-995.(in Chinese)
[9] WANG Y,WU X M,ZHANG W Z,et al.Fabrication and enhanced electromagnetic wave absorption properties of sandwich-like graphene@NiO@PANI decorated with Ag particles[J].Synthetic Metals,2017,229(7):82-88.
[10] YAO X C,KOU X C,QIU J.Generation mechanism of negative dielectric properties of nano-Fe3O4/PANI composites[J].Materials Chemistry and Physics,2018,208:177-182.
[11] LI B Z,WENG X D,WU G J,et al.Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties[J].Journal of Saudi Chemical Society,2017,21(4):466-472.
[12] 魏灿,尹德强,杨刚,等.合金元素Cu对α-Al2O3体结构拉伸强度和断裂性能影响的第一性原理研究[J].工程科学与技术,2017,49(S1):207-212.WEI C,YIN D Q,YANG G,et al.Investigation of the tensile strength and fracture property of α-Al2O3 doped by Cu ion bulk-materials from first principles[J].Advanced Engineering Sciences,2017,49(S1):207-212.(in Chinese)
[13] 牛海超,王为.由铝-空气电池放电产物制备单分散纳米α-Al2O3[J].化学工业与工程,2017,34(4):39-43.NIU H C,WANG W.Preparation of monodispersed Nano-Al2O3[J].Chemical Industry and Engineering,2017,34 (4):39-43.(in Chinese)
[14] ZHANG B,SUN F,ZHOU Q L,et al.First-principles investigation on stability and mobility of hydrogen in α-Al2O3 (0001)/α-Cr2O3 (0001) interface[J].Fusion Engineering and Design,2017,125:577-581.
[15] 黄媛媛,巢磊,李工,等.Cu-ZrO2-CeO2/γ-Al2O3催化甲醇水蒸气重整制氢反应的性能[J].化工进展,2017,36(1):216-223.HUANG Y Y,CHAO L,LI G,et al.Performance of Cu-ZrO-CeO/γ-Al2O3catalysts for hydrogen production from steam reforming of methanol[J].Chemical Industry & Engineering Progress,2017,36(1):216-223.(in Chinese)
[16] 陈焕章,李宏,李花.负载型Mn-Fe/γ-Al2O3低温脱硝催化剂的性能[J].化工进展,2016,35(4):1107-1112.CHEN H Z,LI H,L H.Denitration performance of supported Mn-Fe/γ-Al2O3 catalyst at low temperature[J].Chemical Industry and Engineering Progress,2016,35(4):1107-1112.(in Chinese)
[17] 张李锋,石悠,赵斌元,等.γ-Al2O3载体研究进展[J].材料导报,2007,21(2):67-71.ZHANG L F,SHI Y,ZHAO B Y,et al.Progress in research on γ-alumina catalyst carrier[J].Materials Review,2007,21(2):67-71.(in Chinese)
[18] 曾威,邓春明,刘敏,等.等离子喷涂Al2O3涂层的介电性能[J].材料研究与应用,2011,5(4):275-278.ZENG W,DENG C M,LIU M,et al.Dielectric properties for plasma sprayed alumina coating[J].Materials Research and Application,2011,5(4):275-278.(in Chinese)
[19] TSAI M L.Preparation and characterization of Ppy/Al2O3/Al used as solid-state capacitors for microsystems:Effect of amount of electricity passed[J].Journal of Power Sources,2007,173(1):613-620.
[20] QI Y N,XU F,MA H J,et al.Thermal stability and glass transition behavior of PANI/γ-Al2O3 composites[J].Journal of Thermal Analysis & Calorimetry,2008,91(1):219-223.
[21] 王芸,汤滢,谢长生,等.电化学阻抗谱在材料研究中的应用[J].材料导报,2011,25(13):5-9.WANG Y,TANG Y,XIE C S,et al.The applications of the electrochemical impedance spectroscopy in the materials researches[J].Materials Review,2011,25(13):5-9.(in Chinese)
[22] 王攀,刘羽熙,王永贵,等.PPy/MWNTs/GO复合材料的制备与电化学性能研究[J].材料科学与工艺,2016,24(3):92-96.WANG P,LIU Y X,WANG Y G,et al.Preparation and electrochemical performance of PPy/MWNTs/GO composites[J].Materials Science and Technology,2016,24(3):92-96.(in Chinese)
[23] 胡捷,卢英林.聚苯胺反应配比条件选择的研究[J].纺织基础科学学报,1992(1):16-20.HU J,LU Y L.A study on selection of mixture ratio for polyaniline reaction[J].1992(1):16-20.(in Chinese)
[24] 马硕.导电聚苯胺对金属/酸反应体系影响作用的研究[D].天津:天津工业大学,2016.MA S.Effect of conductive polyaniline on metal/acid reaction system [D].Tianjin:Tianjin University of Technology,2016.(in Chinese)
[25] 彭勇刚,纪俊玲,杨利霞,等.聚苯胺/涤纶导电织物的制备及其性能研究[J].印染助剂,2016,33(5):41-43.PENG Y G,JI J L,YANG L X,et al.Preparation of polyaniline/polyester conductive fabric and their properties[J].Textile Auxiliaries,2016,33(5):41-43.(in Chinese)
[26] 张捷,刘伟,张婷,等.导电聚合物基复合吸波材料的研究进展[J].微纳电子技术,2018,55(2):91-97.ZHANG J,LIU W,ZHANG T,et al.Research progress of conductive polymer composites for microwave absorption[J].Micronanoelectronic Technology,2018,55(2):91-97.(in Chinese)
[27] HU C B,ZHENG Y S,QING Y Q,et al.Preparation of poly(o-toluidine)/nano-ZrO2/epoxy composite coating and its application for corrosion protection of steel[J].Journal of Wuhan University of Technology(Materials Science Edition),2016,31(4):937-944.
[28] 张玉富.铁氧体/聚苯胺(石墨烯)复合材料的制备及微波吸收性能研究[D].淮南:安徽理工大学,2016.ZHANG Y F.Preparation and microwave absorption properties evaluation of Ferrite/Polyaniline(RGO)Nanocomposites[D].Huainan:Anhui University of Science & Technology,2016.(in Chinese)
[29] 李琳,姚正军,周金堂,等.聚苯胺纳米纤维/锂锌铁氧体复合吸波材料的制备与性能[J].复合材料学报,2016,33(4):814-820.LI L,YAO Z J,ZHOU J T,et al.Preparation and property of polyaniline nanofibers/lithium zinc ferrite composite absorbents[J].Acta Materiae Compositae Sinica,2016,33(4):814-820.(in Chinese)
[30] 高磊,何大伟,王永生.聚苯胺与还原石墨烯复合材料的微波吸收性能[J].发光学报,2018,39(10):1347-1351.GAO L,HE D W,WANG Y S.Microwave absorption property of Polyaniline/Reduced grapheme[J].Chinese Journal of Luminescence,2018,39(10):1347-1351.(in Chinese)