纳米红外(Nano IR)研究纤维素基炭纤维在制备过程中基团的变化
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摘要
从纤维截面微区化学基团变化的角度,深入地解析了纤维素基炭纤维制备过程中微观结构的演变。首先利用超薄切片技术获得低温热解各阶段(室温～600℃)纤维的横截面,通过纳米红外技术(Nano IR)获得了纤维的形貌、红外光谱图以及截面微区基团分布的mapping图。结果发现—OH、CO基团在纤维截面上分布不均匀,裂解过程中基团变化显著,皮层和芯层反应不同步;拉曼光谱分析了I_D/I_G的变化,进一步证实了截面微区结构的不均质导致的性能变化。
The evolution of functional groups during the preparation of cellulose-based carbon fibers(CFs) was investigated by nanoscale infrared spectroscopy(Nano IR) of the fiber cross-section and surface. The cross-sections of cellulose-based fibers at different stages of low-temperature pyrolysis from room temperature to 600 ℃ were obtained by an ultra-thin sectioning technique. The infrared spectra and maps of the functional groups at different locations on the cross-section and the surface of a fiber were obtained by the Nano IR. Results showed that C—O and CO groups were distributed evenly on the fiber surface, but —OH groups were unevenly distributed. The —OH group concentration was higher near the surface than in the inner area, but CO groups were distributed evenly on the fiber cross-section. The number of both —OH and CO groups started decreasing at 150 ℃ and levelled off at 300 and 600 ℃, respectively. Pyrolysis reactions proceeded from the outer to the inner part of the fiber, indicating that the skin and core were not pyrolyzed simultaneously. I_D/I_G values from Raman spectroscopy also confirmed the structural heterogeneity in the cross-section at the different pyrolysis temperatures examined. This study is useful to effectively optimize the preparation parameters of CFs with improved properties.
The evolution of functional groups during the preparation of cellulose-based carbon fibers(CFs) was investigated by nanoscale infrared spectroscopy(Nano IR) of the fiber cross-section and surface. The cross-sections of cellulose-based fibers at different stages of low-temperature pyrolysis from room temperature to 600 ℃ were obtained by an ultra-thin sectioning technique. The infrared spectra and maps of the functional groups at different locations on the cross-section and the surface of a fiber were obtained by the Nano IR. Results showed that C—O and CO groups were distributed evenly on the fiber surface, but —OH groups were unevenly distributed. The —OH group concentration was higher near the surface than in the inner area, but CO groups were distributed evenly on the fiber cross-section. The number of both —OH and CO groups started decreasing at 150 ℃ and levelled off at 300 and 600 ℃, respectively. Pyrolysis reactions proceeded from the outer to the inner part of the fiber, indicating that the skin and core were not pyrolyzed simultaneously. I_D/I_G values from Raman spectroscopy also confirmed the structural heterogeneity in the cross-section at the different pyrolysis temperatures examined. This study is useful to effectively optimize the preparation parameters of CFs with improved properties.
引文
[1]孙祝林,奚立华,李红,等.中间相沥青纤维的预氧化和应力应变行为研究[J].新型炭材料,2017,32(3):284-288.(Sun Z L,Xi L H,Li H,et al.Fourier transform infrared and dynamic thermomechanical analyses of mesophase pitch fibers during oxidative stabilization[J].NewCarbon Materials,2017,32(3):284-288.)
[2]Viana S T,Scariot V K,Provensi A,et al.Fabrication and thermal analysis of epoxy resin-carbon fiber fabric composite platecoil heat exchangers[J].Applied Thermal Engineering,2017,127:1451-1460.
[3]Thunga M,Chen K,Grewell D,et al.Bio-renewable precursor fibers from lignin/polylactide blends for conversion to carbon fibers[J].Carbon,2014,68(2):159-166.
[4]段春婷,郑冬芳,刘均庆,等.中间相沥青表征研究进展[J].新型炭材料,2018,33(03):193-202.(Duan C T,Zheng D F,Liu J Q,et al.Research progress on the characterization of mesophase pitch[J].NewCarbon Materials,2018,33(03):193-202.)
[5]Dazzi A,Prater C B.AFM-IR:Technology and applications in nanoscale infrared spectroscopy and chemical imaging[J].Chemical Reviews,2017,117(7):5146-5173.
[6]Rice J H.Nanoscale optical imaging by atomic force infrared microscopy[J].Nanoscale,2010,2(5):660-667.
[7]Mcleod A S,Kelly P,Goldflam MD,et al.Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants[J].Physical ReviewB,2014,90(8):085136.
[8]Ryu M,Kobayashi H,Balcytis A,et al.Nanoscale chemical mapping of laser-solubilized silk[J],Materials Research Express,2017,4(11):1-6.
[9]Baldassarre L,Giliberti V,Rosa A,et al.Mapping the amide Iabsorption in single bacteria and mammalian cells with resonant infrared nanospectroscopy[J].Nanotechnology,2016,27(7):075101.
[10]Ruggeri F S,Vieweg S,Cendrowska U,et al.Nanoscale studies link amyloid maturity with polyglutamine diseases onset[J].Scientific Reports,2016,6:31155.
[11]Tang F,Bao P,Su Z.Analysis of nanodomain composition in high-Impact polypropylene by atomic force microscopy-infrared[J].Analytical Chemistry,2016,88(9):4926-4930.
[12]Li N,Taylor L S.Nanoscale infrared,thermal,and mechanical characterization of telaprevir-polymer miscibility in amorphous solid dispersions prepared by solvent evaporation[J].Molecular Pharmaceutics,2016,13(3):1123-1136.
[13]Lo MK F,Dazzi A,Marcott C A,et al.Nanoscale chemicalmechanical characterization of nanoelectronic low-k dielectric/Cu interconnects[J].ECS Journal of Solid State Science and Technology,2016,5(4):P3018-P3024.
[14]Liu Z,Nrgaard K,Overgaard MH,et al.Direct observation of oxygen configuration on individual graphene oxide sheets[J].Carbon,2018,127:141-148.
[15]邓李慧,陈淙洁,陈振阳,等.一种制备纤维横截面切片的包埋板[P].ZL201320844419.6[P],2013,12.(Deng L H,Chen C J,Chen Z Y,et al.Embedded plate for preparing fiber cross section,ZL201320844419.6[P],2013,12.)
[16]Dazzi A,Prater C B,Hu Q,et al.AFM-IR:Combining atomic force microscopy and infrared spectroscopy for nanoscale chemical characterization[J].Applied Spectroscopy,2012,66(12):1365.
[17]杨序纲,吴琪琳.材料表征的近代物理方法[M].北京:科学出版社,2013:235-303.(Yang X G,et al.Modern Physics Method for Material Characterization[M].Beijing:Science Press,2013:235-303.)
[18]任桂知,陈淙洁,邓李慧,等.拉曼光谱分析炭纤维表面的微观结构(英文)[J].新型炭材料,2015,30(5):476-480.(Ren G Z,Chen C J,Deng L H,et al.Microstructural heterogeneity on the cylindrical surface of carbon fibers analyzed by Raman spectroscopy[J].NewCarbon Materials,2015,30(5):476-480.)
[19]苏灿军,高爱君,罗莎,等.PAN基炭纤维皮芯结构的高温演变规律[J].新型炭材料,2012,27(4):288-293.(Shu C J,Gao A J,Luo S,et al.High temperature evolution of PAN-based carbon fiber sheath core structure[J].NewCarbon Materials,2018,33(03):193-202.
[20]陈淙洁,邓李慧,吴琪琳.碳纤维微观结构研究进展[J].材料导报,2014(s1):21-25.(Chen C J,Deng L H,Wu Q L,et al.Research progress on microstructures of carbon fibers[J].Materials Review,2014(s1):21-25.)
[21]陈淙洁,邓李慧,陈师,等.黏胶纤维在热解过程中微孔结构的演变[J].宇航材料工艺,2015,45(03):24-27.(Chen C J,Deng L H,Chen S,et al.Evolution of microporosities in rayon fibers during pyrolysis[J].Aerospace Materials and Technology,2015,45(03):24-27.)
[2]Viana S T,Scariot V K,Provensi A,et al.Fabrication and thermal analysis of epoxy resin-carbon fiber fabric composite platecoil heat exchangers[J].Applied Thermal Engineering,2017,127:1451-1460.
[3]Thunga M,Chen K,Grewell D,et al.Bio-renewable precursor fibers from lignin/polylactide blends for conversion to carbon fibers[J].Carbon,2014,68(2):159-166.
[4]段春婷,郑冬芳,刘均庆,等.中间相沥青表征研究进展[J].新型炭材料,2018,33(03):193-202.(Duan C T,Zheng D F,Liu J Q,et al.Research progress on the characterization of mesophase pitch[J].NewCarbon Materials,2018,33(03):193-202.)
[5]Dazzi A,Prater C B.AFM-IR:Technology and applications in nanoscale infrared spectroscopy and chemical imaging[J].Chemical Reviews,2017,117(7):5146-5173.
[6]Rice J H.Nanoscale optical imaging by atomic force infrared microscopy[J].Nanoscale,2010,2(5):660-667.
[7]Mcleod A S,Kelly P,Goldflam MD,et al.Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants[J].Physical ReviewB,2014,90(8):085136.
[8]Ryu M,Kobayashi H,Balcytis A,et al.Nanoscale chemical mapping of laser-solubilized silk[J],Materials Research Express,2017,4(11):1-6.
[9]Baldassarre L,Giliberti V,Rosa A,et al.Mapping the amide Iabsorption in single bacteria and mammalian cells with resonant infrared nanospectroscopy[J].Nanotechnology,2016,27(7):075101.
[10]Ruggeri F S,Vieweg S,Cendrowska U,et al.Nanoscale studies link amyloid maturity with polyglutamine diseases onset[J].Scientific Reports,2016,6:31155.
[11]Tang F,Bao P,Su Z.Analysis of nanodomain composition in high-Impact polypropylene by atomic force microscopy-infrared[J].Analytical Chemistry,2016,88(9):4926-4930.
[12]Li N,Taylor L S.Nanoscale infrared,thermal,and mechanical characterization of telaprevir-polymer miscibility in amorphous solid dispersions prepared by solvent evaporation[J].Molecular Pharmaceutics,2016,13(3):1123-1136.
[13]Lo MK F,Dazzi A,Marcott C A,et al.Nanoscale chemicalmechanical characterization of nanoelectronic low-k dielectric/Cu interconnects[J].ECS Journal of Solid State Science and Technology,2016,5(4):P3018-P3024.
[14]Liu Z,Nrgaard K,Overgaard MH,et al.Direct observation of oxygen configuration on individual graphene oxide sheets[J].Carbon,2018,127:141-148.
[15]邓李慧,陈淙洁,陈振阳,等.一种制备纤维横截面切片的包埋板[P].ZL201320844419.6[P],2013,12.(Deng L H,Chen C J,Chen Z Y,et al.Embedded plate for preparing fiber cross section,ZL201320844419.6[P],2013,12.)
[16]Dazzi A,Prater C B,Hu Q,et al.AFM-IR:Combining atomic force microscopy and infrared spectroscopy for nanoscale chemical characterization[J].Applied Spectroscopy,2012,66(12):1365.
[17]杨序纲,吴琪琳.材料表征的近代物理方法[M].北京:科学出版社,2013:235-303.(Yang X G,et al.Modern Physics Method for Material Characterization[M].Beijing:Science Press,2013:235-303.)
[18]任桂知,陈淙洁,邓李慧,等.拉曼光谱分析炭纤维表面的微观结构(英文)[J].新型炭材料,2015,30(5):476-480.(Ren G Z,Chen C J,Deng L H,et al.Microstructural heterogeneity on the cylindrical surface of carbon fibers analyzed by Raman spectroscopy[J].NewCarbon Materials,2015,30(5):476-480.)
[19]苏灿军,高爱君,罗莎,等.PAN基炭纤维皮芯结构的高温演变规律[J].新型炭材料,2012,27(4):288-293.(Shu C J,Gao A J,Luo S,et al.High temperature evolution of PAN-based carbon fiber sheath core structure[J].NewCarbon Materials,2018,33(03):193-202.
[20]陈淙洁,邓李慧,吴琪琳.碳纤维微观结构研究进展[J].材料导报,2014(s1):21-25.(Chen C J,Deng L H,Wu Q L,et al.Research progress on microstructures of carbon fibers[J].Materials Review,2014(s1):21-25.)
[21]陈淙洁,邓李慧,陈师,等.黏胶纤维在热解过程中微孔结构的演变[J].宇航材料工艺,2015,45(03):24-27.(Chen C J,Deng L H,Chen S,et al.Evolution of microporosities in rayon fibers during pyrolysis[J].Aerospace Materials and Technology,2015,45(03):24-27.)