Taking the Lower Silurian Longmaxi Formation shale in the Sichuan Basin as an example,this study employs atomic force microscopy-based infrared(AFM-IR)spectroscopy to analyze the submicron-scale molecular functional g...Taking the Lower Silurian Longmaxi Formation shale in the Sichuan Basin as an example,this study employs atomic force microscopy-based infrared(AFM-IR)spectroscopy to analyze the submicron-scale molecular functional groups of different types and occurrences of organic matter.Combined with the quantitative evaluation of pore development via scanning electron microscopy(SEM),the response of organic pore formation and evolution mechanisms to chemical composition and structural evolution of organic matter in overmature marine shale is investigated.The results indicate that the AFM-IR spectra of graptolite periderms and pyrobitumen in shale are dominated by the stretching vibrations of conjugated C=C bonds in aromatic compounds at approximately 1600 cm-1,with weak absorption peaks near 1375,1450 and 1720 cm-1,corresponding to aliphatic chains and carbonyl/carboxyl functional groups.Overall,the AFM-IR structural indices(A and C factors)of organic matter show a strong correlation with visible porosity in shales of equivalent maturity.Lower A and C factor values correlate with enhanced development of organic pores,which is associated with the detachment of more aliphatic chains and oxygen-containing functional groups during thermal evolution.Pyrobitumen-clay mineral composites generally exhibit superior pore development,likely attributable to clay mineral dehydration participating in hydrocarbon generation reactions that promote the removal of more functional groups.Additionally,hydrocarbon generation within organic-clay composites during high-over mature stages may induce volumetric expansion,resulting in microfracturing and hydrocarbon expulsion.The associated higher hydrocarbon expulsion rates promote the formation of larger pores and fracture-shaped pores along the flake-shaped clay minerals.This study highlights that the research of submicron-scale molecular functional groups provides a deeper understanding of organic matter evolution and pores development mechanisms in overmature shales,thereby offering critical theoretical parameters for reservoir evaluation in shale oil and gas exploration.展开更多
综述了基于原子力显微镜的红外光谱(Atomic force microscopy-based infrared spectroscopy,AFM-IR)的特点,测量和检测原理及其技术优势。AFM-IR是能在纳米尺度对不同材料进行表征的新兴技术,该技术可以以远低于常规光学衍射极限的分辨...综述了基于原子力显微镜的红外光谱(Atomic force microscopy-based infrared spectroscopy,AFM-IR)的特点,测量和检测原理及其技术优势。AFM-IR是能在纳米尺度对不同材料进行表征的新兴技术,该技术可以以远低于常规光学衍射极限的分辨率检测材料的化学成分,同时提供不同组分的分布图谱。AFM-IR的原理是利用原子力显微镜(AFM)悬臂梁的振动检测样本因吸收红外辐射脉冲产生的热膨胀,因此AFM-IR在继承了AFM的纳米级分辨率的基础上结合了红外光谱的化学分析能力,克服了二者原有的缺点并实现了优势互补。这项新技术在过去十多年备受关注并获得了长足的发展,因其操作简便、系统稳定、样品制备要求相对较低,以及与红外光谱直接相关而无需数学建模或额外数据后续处理,已被广泛用于材料科学、生命科学等诸多领域。展开更多
Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanic...Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work,four IPCs were investigated by atomic force microscopy-infrared(AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer(EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.展开更多
基金Supported by the National Natural Science Foundation of China(42172148,42172142)。
文摘Taking the Lower Silurian Longmaxi Formation shale in the Sichuan Basin as an example,this study employs atomic force microscopy-based infrared(AFM-IR)spectroscopy to analyze the submicron-scale molecular functional groups of different types and occurrences of organic matter.Combined with the quantitative evaluation of pore development via scanning electron microscopy(SEM),the response of organic pore formation and evolution mechanisms to chemical composition and structural evolution of organic matter in overmature marine shale is investigated.The results indicate that the AFM-IR spectra of graptolite periderms and pyrobitumen in shale are dominated by the stretching vibrations of conjugated C=C bonds in aromatic compounds at approximately 1600 cm-1,with weak absorption peaks near 1375,1450 and 1720 cm-1,corresponding to aliphatic chains and carbonyl/carboxyl functional groups.Overall,the AFM-IR structural indices(A and C factors)of organic matter show a strong correlation with visible porosity in shales of equivalent maturity.Lower A and C factor values correlate with enhanced development of organic pores,which is associated with the detachment of more aliphatic chains and oxygen-containing functional groups during thermal evolution.Pyrobitumen-clay mineral composites generally exhibit superior pore development,likely attributable to clay mineral dehydration participating in hydrocarbon generation reactions that promote the removal of more functional groups.Additionally,hydrocarbon generation within organic-clay composites during high-over mature stages may induce volumetric expansion,resulting in microfracturing and hydrocarbon expulsion.The associated higher hydrocarbon expulsion rates promote the formation of larger pores and fracture-shaped pores along the flake-shaped clay minerals.This study highlights that the research of submicron-scale molecular functional groups provides a deeper understanding of organic matter evolution and pores development mechanisms in overmature shales,thereby offering critical theoretical parameters for reservoir evaluation in shale oil and gas exploration.
文摘综述了基于原子力显微镜的红外光谱(Atomic force microscopy-based infrared spectroscopy,AFM-IR)的特点,测量和检测原理及其技术优势。AFM-IR是能在纳米尺度对不同材料进行表征的新兴技术,该技术可以以远低于常规光学衍射极限的分辨率检测材料的化学成分,同时提供不同组分的分布图谱。AFM-IR的原理是利用原子力显微镜(AFM)悬臂梁的振动检测样本因吸收红外辐射脉冲产生的热膨胀,因此AFM-IR在继承了AFM的纳米级分辨率的基础上结合了红外光谱的化学分析能力,克服了二者原有的缺点并实现了优势互补。这项新技术在过去十多年备受关注并获得了长足的发展,因其操作简便、系统稳定、样品制备要求相对较低,以及与红外光谱直接相关而无需数学建模或额外数据后续处理,已被广泛用于材料科学、生命科学等诸多领域。
基金financially supported by the National Natural Science Foundation of China (No.52073277)the Science and Technology Department of Fujian Province (No.2020HZ06019)。
文摘Ethylene-propylene block copolymer(EbP) is a vital component in impact polypropylene copolymer(IPC), yet its distribution in the multiphase composite material and how it influences the phase structure and the mechanical properties are not well understood. In this work,four IPCs were investigated by atomic force microscopy-infrared(AFM-IR) to assess the phase compositions in situ, based on which in conjunction with the chain microstructure information obtained ex situ the distributions of the copolymer components were derived for each alloy. For the IPCs whose EbP comprises long P and long E segments, the EbP fraction was found to phase separate from the rubber and the PP matrix to form the cores of the disperse particles with the E-P segmented copolymer(EsP). In contrast, in the IPC with EbP composed of long P and short E segments, the EbP fraction formed an outer shell for the rubber particles with the cores comprising the EsP alone, and this IPC, containing a lower E comonomer content than its counterpart, exhibited both better impact resistance and higher flexural modulus. These results clarify how the chain structure of EbP governs the phase morphology in IPC, which in turn impacts the properties of the composite material.
