Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor...Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.展开更多
Ni-Fe alloy was electrodeposited on the surface of polyacrylonitrile （PAN）-based carbon fibers, and catalytic graphitization effect of the heat-treated carbon fibers was investigated by X-ray diffractometry and Rama...Ni-Fe alloy was electrodeposited on the surface of polyacrylonitrile （PAN）-based carbon fibers, and catalytic graphitization effect of the heat-treated carbon fibers was investigated by X-ray diffractometry and Raman spectra. It is found that Ni-Fe alloy exhibits significant catalytic effect on the graphitization of the carbon fibers at low temperatures. The degree of graphitization of the carbon fibers coated with Ni-Fe alloy （57.91% Fe, mass fraction） reaches 69.0% through heat treatment at 1 250 °C. However, the degree of graphitization of the carbon fibers without Ni-Fe alloy is only 30.1% after being heat-treated at 2 800 °C. The catalytic effect of Ni-Fe alloy on graphitization of carbon fibers is better than that of Ni or Fe at the same temperature, indicating that Ni and Fe elements have synergic catalytic function. Furthermore, Fe content in the Ni-Fe alloy also influences catalytic effect. The catalytic graphitization of Ni-Fe alloy follows the dissolution-precipitation mechanism.展开更多
Graphite brasses were prepared by graphitizing annealing of cast brasses containing cementite particles,which were in-situ formed during the fasting process.The eutectic cast iron as carbon source was added into commo...Graphite brasses were prepared by graphitizing annealing of cast brasses containing cementite particles,which were in-situ formed during the fasting process.The eutectic cast iron as carbon source was added into common brasses by casting.SEM and EDS were used to analyze the microstructure of graphite brasses,and the relationship between the microstructure and machinability was investigated.The results show that graphite particles are formed by the decomposition of cementite particles in cast brasses.The graphite particles are uniformly dispersed in the brass matrix with the average size of 5.0 μm and the volume fraction of ~1.1%.The machinability in the graphite brass is dramatically increased relative to the common brass,because of the lubricating properties of graphite particles and its role in chip breaking.The workpiece surface of the graphite brasses chips is smooth and burr-free,and the chips of graphite brasses are short（C-shape） and discontinuous,which is much better than that of the long spiral chips of common brasses.展开更多
To improve the oxidation and graphitization resistances of the polycrystalline diamond(PCD), Ti coating was deposited on the diamond powders via magnetic sputtering method, which achieved a uniform Ti C protection bar...To improve the oxidation and graphitization resistances of the polycrystalline diamond(PCD), Ti coating was deposited on the diamond powders via magnetic sputtering method, which achieved a uniform Ti C protection barrier in PCD during the sintering process. The phase compositions, microstructures and thermal stability of Ti-PCD were characterized by X-ray diffraction(XRD), Auger electron spectroscopy(AES),scanning electron microscopy(SEM) and thermal gravimetric-differential scanning calorimetry(TG-DSC).The results demonstrate that the oxidation and graphitization resistances of PCD are strengthened due to the existence of Ti C phase, which acts as an effective inhibitor. The as-received inhibitor delays the oxidation and graphitization of PCD, elevating their initial temperature by ~50°C and ~100°C, respectively. During the annealing treatment of Ti-PCD, the priory oxidation of Ti C, which produces Ti O2 as an oxygen barrier, postpones the diamond oxide. Moreover, the Ti C barrier also protects diamond grains from direct contact with cobalt, thus a lower cobalt-catalytic graphitization, and yields to an improved graphitization resistance of PCD. The enhanced oxidation and graphitization resistances of PCD are of significant importance for practical applications to elevated temperatures.展开更多
The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium...The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.展开更多
Pore structure is an important factor influencing coke strength,while the property of coke is essential to maintaining gas and liquid permeability in a blast furnace.Therefore,an in-depth understanding of the pore str...Pore structure is an important factor influencing coke strength,while the property of coke is essential to maintaining gas and liquid permeability in a blast furnace.Therefore,an in-depth understanding of the pore structure evolution during the graphitization process can reveal the coke size degradation behavior during its descent in a blast furnace.Coke graphitization was simulated at different heating temperatures from 1100 to 1600℃ at intervals of 100℃.The quantitative evaluation of the coke pore structure with different graphitization degree was determined by vacuum drainage method and nitrogen adsorption method.Results show that the adsorption and desorption curves of graphitized coke have intersection points,and the two curves did not coincide,instead forming a“hysteresis loop.”Based on the hysteresis loop analysis,the porous structure of the graphitized coke mostly appeared in the shape of a“hair follicle.”Furthermore,with an increase in heating temperature,the apparent porosity,specific surface area,total pore volume,and amount of micropores showed good correlation and can divided into three stages:1100-1200,1200-1400,and 1400-1600℃.When the temperature was less than 1400℃,ash migration from the inner part mainly led to changes in the coke pore structure.When the temperature was greater than 1400℃,the pore structure evolution was mainly affected by the coke graphitization degree.The results of scanning electron microscopy,energy dispersive spectrometry,and ash content analyses also confirmed that the migration of the internal ash to the surface of the matrix during the graphitization process up to 1400℃ contributed to these changes.展开更多
Materialization of coal is one of effective and clean pathways for its utilization. The microstructures of coal-based carbon materials have an important influence on their functional applications. Herein, the microstr...Materialization of coal is one of effective and clean pathways for its utilization. The microstructures of coal-based carbon materials have an important influence on their functional applications. Herein, the microstructural evolution of anthracite in the temperature range of 1000–2800 ℃ was systematically investigated to provide a guidance for the microstructural regulation of coal-based carbon materials.The results indicate that the microstructure of anthracite undergoes an important change during carbonization-graphitization process. As the temperature increases, aromatic layers in anthracite gradually transform into disordered graphite microcrystals and further grow into ordered graphite microcrystals, and then ordered graphite microcrystals are laterally linked to form pseudo-graphite phase and eventually transformed into highly ordered graphite-like sheets. In particular, 2000–2200 ℃ is a critical temperature region for the qualitative change of ordered graphite crystallites to pseudo-graphite phase,in which the relevant structural parameters including stacking height, crystallite lateral size and graphitization degree show a rapid increase. Moreover, both aromaticity and graphitization degree have a linear positive correlation with carbonization-graphitization temperature in a specific temperature range.Besides, after initial carbonization, some defect structures in anthracite such as aliphatic carbon and oxygen-containing functional groups are released in the form of gaseous low-molecular volatiles along with an increased pore structure, and the intermediates derived from minerals could facilitate the conversion of sp^(3) amorphous carbon to sp^(2) graphitic carbon. This work provides a valuable reference for the rational design of microstructure of coal-based carbon materials.展开更多
Serving as gas diffusion layers(GDLs),the thermal conductivity of carbon paper(CP)plays a significant role in the heat transfer management in fuel cells.In the present study,the effect of graphitization degree of CP o...Serving as gas diffusion layers(GDLs),the thermal conductivity of carbon paper(CP)plays a significant role in the heat transfer management in fuel cells.In the present study,the effect of graphitization degree of CP on its through plane thermal conductivity and in-plane thermal conductivity is investigated.The relationship between heat treatment temperatures(1800,2000,2200,2400 and 2500℃)and graphitization degree is also investigated by SEM,XRD and Raman measurements.A model for CP under different graphitization degree is suggested considering the thermal conductivity difference of carbon fiber and matrix carbon.The experimental and simulation results are compared.The results show that the graphitization degree has a significant impact on the through-plane thermal conductivity and in plane thermal conductivity.展开更多
Graphitized carbon/carbon composites were prepared by the process of catalytic graphitization with the rare-earth catalyst, lantha-num oxide （La2O3）, in order to increase the degree of graphitization and reduce the ...Graphitized carbon/carbon composites were prepared by the process of catalytic graphitization with the rare-earth catalyst, lantha-num oxide （La2O3）, in order to increase the degree of graphitization and reduce the electrical resistivity. The modified coal tar pitch and coal-based needle coke were used as carbon source, and a small amount of La2O3 was added to catalyze the graphitization of the disordered carbon materials. The effects of La2O3 catalyst on the graphitization degree and microstructure of the carbon/carbon composites were investi-gated by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. The results showed that La2O3 promoted the formation of more perfect and larger crystallites, and improved the electrical/mechanical properties of carbon/carbon composites. Carbon/carbon compos-ites with a lower electrical resistivity （7.0 ？？？m） could be prepared when adding 5 wt.% La2O3 powder with heating treatment at 2800 oC. The catalytic effect of La2O3 for the graphitization of carbon/carbon composites was analyzed.展开更多
We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman sp...We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman spectroscopy.The morphology of furan resin carbon was characterized by scanning electron microscopy.The effects of the praseodymium content and the heat-treatment temperature on the catalytic graphitization of furan resin carbon were also investigated.The results indicated that the praseodymium c...展开更多
From the points of both molten cast iron structure and the appearing ratio of electrons in outer-layer of different atoms, analysis on enhancement mechanism of graphitization ability after processing of the iron by pu...From the points of both molten cast iron structure and the appearing ratio of electrons in outer-layer of different atoms, analysis on enhancement mechanism of graphitization ability after processing of the iron by pulse electric discharge has been made, and the theory has been proofed by corresponding experiments. The results show that when the molten cast iron is being processed by pulse electric discharge, both the size of crystal embryos that composed by Fe and C atoms as well as the number of clusters can be reduced, even be separated by such discharging; consequently results in the segre- gation of C atoms in the molten cast iron near the cathode of discharging. The nucleation of graphite in these areas of the iron has been promoted at the discharging temperature; even though such degree has not been reached, the most favorable nucleation conditions of graphite can be at least created. Under the preconditions of not breaking up the graphite crystal embryos, with proper adjustment of discharging frequency, the stronger of the electric field and the longer of the pulsation treatment time are, the more graphitization ability of the molten cast iron is. The theoretical analysis on the above rules consists well with experimental results.展开更多
The shrinkage and chilling tendency of spheroidal graphite (abbreviated SG) cast iron is much greater than that of the flake graphite cast iron in spite of its higher amount of C and Si contents. Why? The main reason ...The shrinkage and chilling tendency of spheroidal graphite (abbreviated SG) cast iron is much greater than that of the flake graphite cast iron in spite of its higher amount of C and Si contents. Why? The main reason should be the difference in their graphitization during the eutectic solidification. In this paper, we discuss the difference in the solidification mechanism of both cast irons for solving these problems using unidirectional solidification and the cooling curves of the spheroidal graphite cast iron. The eutectic solidification rate of the SG cast iron is controlled by the diffusion of carbon through the austenite shell, and the final thickness is 1.4 times the radius of the SG, therefore, the reduction of the SG size, namely, the increase in the number, is the main solution of these problems.展开更多
A novel carbon fiber pretreatment was proposed.Polyacrylonitrile(PAN)-based carbon fibers were first anodized in H3PO4 electrolyte to achieve an active surface,and then coated with Mo-B catalysts by immersed the carbo...A novel carbon fiber pretreatment was proposed.Polyacrylonitrile(PAN)-based carbon fibers were first anodized in H3PO4 electrolyte to achieve an active surface,and then coated with Mo-B catalysts by immersed the carbon fibers in a uniformly dispersed Mo-B sol.The as-treated carbon fibers were then graphitized at 2 400 ℃ for 2 h.The structural changes were characterized by X-ray diffractometry(XRD),Raman spectroscopy,scanning electron microscopy(SEM) and high-resolution transmission electronic microscopy(HRTEM).The results show that much better graphitization can be achieved in the presence of Mo-B,with an interlayer spacing(d002) of 0.335 8 nm and a crystalline size(Lc) of 28 nm.展开更多
The process of electrodepositing Fe-Cr2O3 composite coating on polyacrylonitrile （PAN）-based carbon fibers and its catalytic graphitization were studied. Carbon fibers with and without electrodeposited Fe-Cr2O3 comp...The process of electrodepositing Fe-Cr2O3 composite coating on polyacrylonitrile （PAN）-based carbon fibers and its catalytic graphitization were studied. Carbon fibers with and without electrodeposited Fe-Cr2O3 composite coating were heat treated at different temperatures and the structural changes were characterized by XRD, Raman spectroscopy and SEM. The results indicate that Fe-Cr2O3 composite coating exhibits a significant catalytic effect on graphitization of carbon fibers at low temperatures. When the Fe-Cr2O3-coated carbon fibers were heat treated at 1 300℃ the interlayer spacing （doo2） and ratio of relative peak area （AD/AG） reach 3.364/k and 0.34, respectively. Whereas, the extent of graphitization of pristine carbon fibers is comparatively low even after heat treatment at 2 800℃ and the values of doo2 and AD/AG are 3.414 A and 0.68, respectively. The extent of graphitization of carbon fibers increases not only with the increase of the catalyst gross but also the Cr2O3 content in Fe-Cr2O3 coating. The catalytic effect of Fe-Cr2O3 composite coating accords with the dissolution-precipitation mechanism.展开更多
Cu-Fe based diamond composites used for saw-blade segments are directly fabricated by vacuum and pressureassisted sintering. The carbide forming elements Cr and Ti are added to improve interfacial bonding between diam...Cu-Fe based diamond composites used for saw-blade segments are directly fabricated by vacuum and pressureassisted sintering. The carbide forming elements Cr and Ti are added to improve interfacial bonding between diamond and the Cu-Fe matrix. The interfacial reactions between diamond/graphite and Cr or Ti, and diamond graphitization are investigated by thermodynamics/kinetics analyses and experimental methods. The results show that interfacial reactions and graphitization of diamond can automatically proceed thermodynamically. The Cr3C2, Cr7C3, Cr23C6, and TiC are formed at the interfaces of composites by reactions between diamond and Cr or Ti; diamond graphitization does not occur because of the kinetic difficulty at 1093 K under the pressure of 13 MPa.展开更多
The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functio...The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functional groups,carbon chemical state,and graphitization degree during thermal treatment in an inert gas environment at intermediate temperatures of 600℃,800℃,and 1000℃ and explore the chemical species that were desorbed from the diesel soot surface during thermal treatment using a thermogravimetric analyser coupled with a gas-chromatograph mass spectrometer(TGA-GC/MS).The surface functional groups and carbon chemical statewere characterized using Fourier transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopy(XPS).The graphitization degree was evaluated by means of Raman spectroscopy(RS).The concentrations of aliphatic C–H,C–OH,C=O,and O–C=O groups are reduced for diesel soot and carbon black when increasing the thermal treatment temperature,while the sp^(2)/sp^(3) hybridized ratio and graphitization degree enhance.These results provide comprehensive evidence of the decreased reactivity of soot samples.Among oxygenated functional groups,the percentage reduction during thermal treatment is the largest for the O–C=O groups owing to its worst thermodynamic stability.TGA-GC/MS results show that the aliphatic and aromatic chains and oxygenated species would be desorbed from the soot surface during 1000℃ thermal treatment of diesel soot.展开更多
The graphitization behavior of ultrahigh carbon steels containing Si in hot rolling processes was investigated. The graphite stringers went mostly through the small pores and generally paralleled to the rolling direct...The graphitization behavior of ultrahigh carbon steels containing Si in hot rolling processes was investigated. The graphite stringers went mostly through the small pores and generally paralleled to the rolling direction. The influence of alloy elements on graphitization was estimated based on thermodynamics, which showed that Si content was important for graphitization. Graphite stringers nucleated at small pores and grew with carbon diffusion during hot rolling. Alloy contents, pores and hot deformation at γ+Fe3C phase range were the key factors for the formation of graphite. The probable effect of deformation on graphite formation during hot rolling was discussed in this paper.展开更多
Common strategies for catalytic graphitization of biochar into graphitic porous carbon(GPC)still face great challenges,such as the realization of simple procedures,energy conservation,and green processes.Controlling o...Common strategies for catalytic graphitization of biochar into graphitic porous carbon(GPC)still face great challenges,such as the realization of simple procedures,energy conservation,and green processes.Controlling over the graphitization degree and pore structure of biochar is the key to its structural diversification.Herein,a clean and energy-efficient method is developed to synthesize adjustable graphitic degree and structure porosity GPC from rice husk-based carbon(RHC)at a relatively low temperature of 800–1000°C with environment-benign organometallic catalyst ethylenediaminetetraacetic acid ferric sodium salt(EDTA-iron)and the recovery ratio of catalyst is as high as 97%.The formed by the organic ligands of EDTA-iron facilitates the etching of RHC surface and pore by iron,resulting in highly graphitized and developed porous GPCs.The pore structure and graphitization degree of GPCs can be adjusted by altering the catalyst loading,temperature,and holding time.The catalyst EDTA-iron with a lower concentration mainly plays the role of etching,which promotes the formation of porous carbon with larger surface area(SBET=1187.2 m^(2)·g^(-1)).The catalyst with higher concentration mainly plays the role of catalyzing graphitization and promotes the obtaining of graphitic carbon with high graphitization degree(ID/IG=0.19).The mechanism of EDTA-iron catalyzed graphitization of RHC is explored by the comprehensive analysis of BET,XRD,Raman,TEM and TGA.This research not only provides an efficient method for the preparation of high-quality biomass-based graphite carbon,but also provides a feasible method for the preparation of biomass-based porous carbon.展开更多
To inhibit the graphitization of diamond under high temperature and low pressure, diamond/SiC composites were firstly fabricated by a rapid gaseous Si vacuum reactive infiltration process. The microstructure and graph...To inhibit the graphitization of diamond under high temperature and low pressure, diamond/SiC composites were firstly fabricated by a rapid gaseous Si vacuum reactive infiltration process. The microstructure and graphitization behavior of diamond in the composites under various infiltration temperatures and holding time were investigated. The thermal conductivity of the resul- tant materials was discussed. The results show that the diamond-to-graphite transition is effectively inhibited at temperature of as high as 1600 ℃ under vacuum, and the substantial graphitization starts at 1700 ℃. The microstructure of those ungraphitized samples is uniform and fully densified. The inhibition mechanisms of graphitization include the isolation of the catalysts from diamond by a series of protective layers, high pressure stress applied on diamond by the reaction-bonded SiC, and the moderate gas-solid reaction. For the graphitized samples, the boundary between diamond and SiC is coarse and loose. The graphitization mechanism is considered to be an initial detachment of the bilayers from the diamond surfaces, and subsequently flattening to form graphite. The ungraphitized samples present higher thermal conductivity of about 410 W.m-1.K-1 due to the fine interfacial structure. For the graphitized samples, the thermal conductivity decreases significantly to 285 W.m-1.K-1 as a result of high interfacial thermal resistance.展开更多
The etching technique using Ce is a convenient and fast method for polishing and shaping diamond films. In this study, the influence of polishing parameters such as polishing temperature and time on the surface crysta...The etching technique using Ce is a convenient and fast method for polishing and shaping diamond films. In this study, the influence of polishing parameters such as polishing temperature and time on the surface crystallinity and phase composition of diamond films was thoroughly investigated via the analysis of Raman spectra such as FWHM and ID/IG. Moreover, the issue on the graphitization of diamond after polishing with Ce was further researched through the detailed study of the depth distribution of Raman data including FWHM and ID/IG, and a result completely different from the hot-iron metal polished ones was obtained. The results showed that polished diamond films had considerably higher diamond content than those before polishing, and not a bit of graphitization was found in the polished ones, owing to a higher solubility of carbon in rare earth metal Ce than that in transition metals, and the original crystallinity of the films polished with Ce did not deteriorate.展开更多
基金supported by the National Natural Science Foundation of China(22209103)Science and Technology Commission of Shanghai Municipality(22010500400)Australian Research Council(FT180100705)。
文摘Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.
基金Project (2006CB600903) supported by the National Basic Research Program of ChinaProject (2010GK3208) supported by Science and Technology Program of Hunan Province, China
文摘Ni-Fe alloy was electrodeposited on the surface of polyacrylonitrile （PAN）-based carbon fibers, and catalytic graphitization effect of the heat-treated carbon fibers was investigated by X-ray diffractometry and Raman spectra. It is found that Ni-Fe alloy exhibits significant catalytic effect on the graphitization of the carbon fibers at low temperatures. The degree of graphitization of the carbon fibers coated with Ni-Fe alloy （57.91% Fe, mass fraction） reaches 69.0% through heat treatment at 1 250 °C. However, the degree of graphitization of the carbon fibers without Ni-Fe alloy is only 30.1% after being heat-treated at 2 800 °C. The catalytic effect of Ni-Fe alloy on graphitization of carbon fibers is better than that of Ni or Fe at the same temperature, indicating that Ni and Fe elements have synergic catalytic function. Furthermore, Fe content in the Ni-Fe alloy also influences catalytic effect. The catalytic graphitization of Ni-Fe alloy follows the dissolution-precipitation mechanism.
基金Projects(51271090,51364036,51471083)supported by the National Natural Science Foundation of ChinaProject(IRT0730)supported by the Program for Changjiang Scholars and Innovative Research Team in University,China+1 种基金Project(NCET-10-0184)supported by the Program for New Century Excellent Talents in University,ChinaProject(20103601110001)supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China
文摘Graphite brasses were prepared by graphitizing annealing of cast brasses containing cementite particles,which were in-situ formed during the fasting process.The eutectic cast iron as carbon source was added into common brasses by casting.SEM and EDS were used to analyze the microstructure of graphite brasses,and the relationship between the microstructure and machinability was investigated.The results show that graphite particles are formed by the decomposition of cementite particles in cast brasses.The graphite particles are uniformly dispersed in the brass matrix with the average size of 5.0 μm and the volume fraction of ~1.1%.The machinability in the graphite brass is dramatically increased relative to the common brass,because of the lubricating properties of graphite particles and its role in chip breaking.The workpiece surface of the graphite brasses chips is smooth and burr-free,and the chips of graphite brasses are short（C-shape） and discontinuous,which is much better than that of the long spiral chips of common brasses.
基金financially supported by the National Natural Science Foundation of China(Nos.51875537,41572359 and 51375466)the Beijing Natural Science Foundation(No.3172026)+2 种基金the Beijing Nova program(No.Z171100001117059)the Fundamental Research Funds for the Central University(No.2652018094)the Natural Science Foundation of Ningxia Province(No.2018AAC03200)。
文摘To improve the oxidation and graphitization resistances of the polycrystalline diamond(PCD), Ti coating was deposited on the diamond powders via magnetic sputtering method, which achieved a uniform Ti C protection barrier in PCD during the sintering process. The phase compositions, microstructures and thermal stability of Ti-PCD were characterized by X-ray diffraction(XRD), Auger electron spectroscopy(AES),scanning electron microscopy(SEM) and thermal gravimetric-differential scanning calorimetry(TG-DSC).The results demonstrate that the oxidation and graphitization resistances of PCD are strengthened due to the existence of Ti C phase, which acts as an effective inhibitor. The as-received inhibitor delays the oxidation and graphitization of PCD, elevating their initial temperature by ~50°C and ~100°C, respectively. During the annealing treatment of Ti-PCD, the priory oxidation of Ti C, which produces Ti O2 as an oxygen barrier, postpones the diamond oxide. Moreover, the Ti C barrier also protects diamond grains from direct contact with cobalt, thus a lower cobalt-catalytic graphitization, and yields to an improved graphitization resistance of PCD. The enhanced oxidation and graphitization resistances of PCD are of significant importance for practical applications to elevated temperatures.
基金financially supported by National Key Research and Development Program of China(2018YFC1901605)the National Postdoctoral Program for Innovative Talents(BX201600192)+1 种基金Hunan Provincial Science and Technology Plan(2017TP1001)Innovation Mover Program of Central South University(GCX20190893Y)。
文摘The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51604148,51874171,and 51974154)the Science Foundation for the Talents by University of Science and Technology Liaoning(USTL),China(2019RC11).
文摘Pore structure is an important factor influencing coke strength,while the property of coke is essential to maintaining gas and liquid permeability in a blast furnace.Therefore,an in-depth understanding of the pore structure evolution during the graphitization process can reveal the coke size degradation behavior during its descent in a blast furnace.Coke graphitization was simulated at different heating temperatures from 1100 to 1600℃ at intervals of 100℃.The quantitative evaluation of the coke pore structure with different graphitization degree was determined by vacuum drainage method and nitrogen adsorption method.Results show that the adsorption and desorption curves of graphitized coke have intersection points,and the two curves did not coincide,instead forming a“hysteresis loop.”Based on the hysteresis loop analysis,the porous structure of the graphitized coke mostly appeared in the shape of a“hair follicle.”Furthermore,with an increase in heating temperature,the apparent porosity,specific surface area,total pore volume,and amount of micropores showed good correlation and can divided into three stages:1100-1200,1200-1400,and 1400-1600℃.When the temperature was less than 1400℃,ash migration from the inner part mainly led to changes in the coke pore structure.When the temperature was greater than 1400℃,the pore structure evolution was mainly affected by the coke graphitization degree.The results of scanning electron microscopy,energy dispersive spectrometry,and ash content analyses also confirmed that the migration of the internal ash to the surface of the matrix during the graphitization process up to 1400℃ contributed to these changes.
基金supported by the National Natural Science Foundation of China(Nos.51974110,52074109 and 52274261)the Key Scientific and Technological Project of Henan Province(No.202102210183)the Coal Green Conversion Outstanding Foreign Scientists Foundation of Henan Province(No.GZS2020012).
文摘Materialization of coal is one of effective and clean pathways for its utilization. The microstructures of coal-based carbon materials have an important influence on their functional applications. Herein, the microstructural evolution of anthracite in the temperature range of 1000–2800 ℃ was systematically investigated to provide a guidance for the microstructural regulation of coal-based carbon materials.The results indicate that the microstructure of anthracite undergoes an important change during carbonization-graphitization process. As the temperature increases, aromatic layers in anthracite gradually transform into disordered graphite microcrystals and further grow into ordered graphite microcrystals, and then ordered graphite microcrystals are laterally linked to form pseudo-graphite phase and eventually transformed into highly ordered graphite-like sheets. In particular, 2000–2200 ℃ is a critical temperature region for the qualitative change of ordered graphite crystallites to pseudo-graphite phase,in which the relevant structural parameters including stacking height, crystallite lateral size and graphitization degree show a rapid increase. Moreover, both aromaticity and graphitization degree have a linear positive correlation with carbonization-graphitization temperature in a specific temperature range.Besides, after initial carbonization, some defect structures in anthracite such as aliphatic carbon and oxygen-containing functional groups are released in the form of gaseous low-molecular volatiles along with an increased pore structure, and the intermediates derived from minerals could facilitate the conversion of sp^(3) amorphous carbon to sp^(2) graphitic carbon. This work provides a valuable reference for the rational design of microstructure of coal-based carbon materials.
基金Projects(2020 JJ 5142,2019 RS 2067)supported by the Science and Technology Planning Project of Hunan Province,ChinaProject(19 C 0581)supported by the Research Foundation of Education Bureau of Hunan Province,China。
文摘Serving as gas diffusion layers(GDLs),the thermal conductivity of carbon paper(CP)plays a significant role in the heat transfer management in fuel cells.In the present study,the effect of graphitization degree of CP on its through plane thermal conductivity and in-plane thermal conductivity is investigated.The relationship between heat treatment temperatures(1800,2000,2200,2400 and 2500℃)and graphitization degree is also investigated by SEM,XRD and Raman measurements.A model for CP under different graphitization degree is suggested considering the thermal conductivity difference of carbon fiber and matrix carbon.The experimental and simulation results are compared.The results show that the graphitization degree has a significant impact on the through-plane thermal conductivity and in plane thermal conductivity.
基金Project supported by the National High-Tech R&D Program (863 Program) of China (2009AA06Z102)the Fundamental Research Fund for the Central Universities and State Key Laboratory of Exploration Fund of China
文摘Graphitized carbon/carbon composites were prepared by the process of catalytic graphitization with the rare-earth catalyst, lantha-num oxide （La2O3）, in order to increase the degree of graphitization and reduce the electrical resistivity. The modified coal tar pitch and coal-based needle coke were used as carbon source, and a small amount of La2O3 was added to catalyze the graphitization of the disordered carbon materials. The effects of La2O3 catalyst on the graphitization degree and microstructure of the carbon/carbon composites were investi-gated by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. The results showed that La2O3 promoted the formation of more perfect and larger crystallites, and improved the electrical/mechanical properties of carbon/carbon composites. Carbon/carbon compos-ites with a lower electrical resistivity （7.0 ？？？m） could be prepared when adding 5 wt.% La2O3 powder with heating treatment at 2800 oC. The catalytic effect of La2O3 for the graphitization of carbon/carbon composites was analyzed.
基金supported by the National Basic Research Program of China (2006CB600903)
文摘We introduced a new catalyst,rare earth element praseodymium,for the catalytic graphitization of furan resin carbon.The extent of graphitization of the furan resin carbon was examined by X-ray diffraction and Raman spectroscopy.The morphology of furan resin carbon was characterized by scanning electron microscopy.The effects of the praseodymium content and the heat-treatment temperature on the catalytic graphitization of furan resin carbon were also investigated.The results indicated that the praseodymium c...
文摘From the points of both molten cast iron structure and the appearing ratio of electrons in outer-layer of different atoms, analysis on enhancement mechanism of graphitization ability after processing of the iron by pulse electric discharge has been made, and the theory has been proofed by corresponding experiments. The results show that when the molten cast iron is being processed by pulse electric discharge, both the size of crystal embryos that composed by Fe and C atoms as well as the number of clusters can be reduced, even be separated by such discharging; consequently results in the segre- gation of C atoms in the molten cast iron near the cathode of discharging. The nucleation of graphite in these areas of the iron has been promoted at the discharging temperature; even though such degree has not been reached, the most favorable nucleation conditions of graphite can be at least created. Under the preconditions of not breaking up the graphite crystal embryos, with proper adjustment of discharging frequency, the stronger of the electric field and the longer of the pulsation treatment time are, the more graphitization ability of the molten cast iron is. The theoretical analysis on the above rules consists well with experimental results.
文摘The shrinkage and chilling tendency of spheroidal graphite (abbreviated SG) cast iron is much greater than that of the flake graphite cast iron in spite of its higher amount of C and Si contents. Why? The main reason should be the difference in their graphitization during the eutectic solidification. In this paper, we discuss the difference in the solidification mechanism of both cast irons for solving these problems using unidirectional solidification and the cooling curves of the spheroidal graphite cast iron. The eutectic solidification rate of the SG cast iron is controlled by the diffusion of carbon through the austenite shell, and the final thickness is 1.4 times the radius of the SG, therefore, the reduction of the SG size, namely, the increase in the number, is the main solution of these problems.
基金Project(2006CB600903) supported by the National Basic Research Program of China
文摘A novel carbon fiber pretreatment was proposed.Polyacrylonitrile(PAN)-based carbon fibers were first anodized in H3PO4 electrolyte to achieve an active surface,and then coated with Mo-B catalysts by immersed the carbon fibers in a uniformly dispersed Mo-B sol.The as-treated carbon fibers were then graphitized at 2 400 ℃ for 2 h.The structural changes were characterized by X-ray diffractometry(XRD),Raman spectroscopy,scanning electron microscopy(SEM) and high-resolution transmission electronic microscopy(HRTEM).The results show that much better graphitization can be achieved in the presence of Mo-B,with an interlayer spacing(d002) of 0.335 8 nm and a crystalline size(Lc) of 28 nm.
基金Project(2006CB600903) supported by the National Basic Research Program of China
文摘The process of electrodepositing Fe-Cr2O3 composite coating on polyacrylonitrile （PAN）-based carbon fibers and its catalytic graphitization were studied. Carbon fibers with and without electrodeposited Fe-Cr2O3 composite coating were heat treated at different temperatures and the structural changes were characterized by XRD, Raman spectroscopy and SEM. The results indicate that Fe-Cr2O3 composite coating exhibits a significant catalytic effect on graphitization of carbon fibers at low temperatures. When the Fe-Cr2O3-coated carbon fibers were heat treated at 1 300℃ the interlayer spacing （doo2） and ratio of relative peak area （AD/AG） reach 3.364/k and 0.34, respectively. Whereas, the extent of graphitization of pristine carbon fibers is comparatively low even after heat treatment at 2 800℃ and the values of doo2 and AD/AG are 3.414 A and 0.68, respectively. The extent of graphitization of carbon fibers increases not only with the increase of the catalyst gross but also the Cr2O3 content in Fe-Cr2O3 coating. The catalytic effect of Fe-Cr2O3 composite coating accords with the dissolution-precipitation mechanism.
基金Project supported by the National Natural Science Foundation of China (Grant No. 51165021)the Science Fund for Distinguished Young Scholars of Gansu Province, China (Grant No. 111RJDA0103)
文摘Cu-Fe based diamond composites used for saw-blade segments are directly fabricated by vacuum and pressureassisted sintering. The carbide forming elements Cr and Ti are added to improve interfacial bonding between diamond and the Cu-Fe matrix. The interfacial reactions between diamond/graphite and Cr or Ti, and diamond graphitization are investigated by thermodynamics/kinetics analyses and experimental methods. The results show that interfacial reactions and graphitization of diamond can automatically proceed thermodynamically. The Cr3C2, Cr7C3, Cr23C6, and TiC are formed at the interfaces of composites by reactions between diamond and Cr or Ti; diamond graphitization does not occur because of the kinetic difficulty at 1093 K under the pressure of 13 MPa.
基金supported by the National Natural Science Foundation of China (No.52006054)the State Key Laboratory of Engines at Tianjin University (No.K2021-05)+1 种基金the European Union’s projects MODALES (No.815189)nPETS (No.954377)
文摘The thermal deactivation of diesel soot particles exerts a significant influence on the control strategy for the regeneration of diesel particulate filters(DPFs).This work focused on the changes in the surface functional groups,carbon chemical state,and graphitization degree during thermal treatment in an inert gas environment at intermediate temperatures of 600℃,800℃,and 1000℃ and explore the chemical species that were desorbed from the diesel soot surface during thermal treatment using a thermogravimetric analyser coupled with a gas-chromatograph mass spectrometer(TGA-GC/MS).The surface functional groups and carbon chemical statewere characterized using Fourier transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopy(XPS).The graphitization degree was evaluated by means of Raman spectroscopy(RS).The concentrations of aliphatic C–H,C–OH,C=O,and O–C=O groups are reduced for diesel soot and carbon black when increasing the thermal treatment temperature,while the sp^(2)/sp^(3) hybridized ratio and graphitization degree enhance.These results provide comprehensive evidence of the decreased reactivity of soot samples.Among oxygenated functional groups,the percentage reduction during thermal treatment is the largest for the O–C=O groups owing to its worst thermodynamic stability.TGA-GC/MS results show that the aliphatic and aromatic chains and oxygenated species would be desorbed from the soot surface during 1000℃ thermal treatment of diesel soot.
文摘The graphitization behavior of ultrahigh carbon steels containing Si in hot rolling processes was investigated. The graphite stringers went mostly through the small pores and generally paralleled to the rolling direction. The influence of alloy elements on graphitization was estimated based on thermodynamics, which showed that Si content was important for graphitization. Graphite stringers nucleated at small pores and grew with carbon diffusion during hot rolling. Alloy contents, pores and hot deformation at γ+Fe3C phase range were the key factors for the formation of graphite. The probable effect of deformation on graphite formation during hot rolling was discussed in this paper.
基金the Science and Technology Research Project of Education Department of Jilin Province(JJKH20220683KJ)Natural Science Foundation of Jilin Province(20220101093JC).
文摘Common strategies for catalytic graphitization of biochar into graphitic porous carbon(GPC)still face great challenges,such as the realization of simple procedures,energy conservation,and green processes.Controlling over the graphitization degree and pore structure of biochar is the key to its structural diversification.Herein,a clean and energy-efficient method is developed to synthesize adjustable graphitic degree and structure porosity GPC from rice husk-based carbon(RHC)at a relatively low temperature of 800–1000°C with environment-benign organometallic catalyst ethylenediaminetetraacetic acid ferric sodium salt(EDTA-iron)and the recovery ratio of catalyst is as high as 97%.The formed by the organic ligands of EDTA-iron facilitates the etching of RHC surface and pore by iron,resulting in highly graphitized and developed porous GPCs.The pore structure and graphitization degree of GPCs can be adjusted by altering the catalyst loading,temperature,and holding time.The catalyst EDTA-iron with a lower concentration mainly plays the role of etching,which promotes the formation of porous carbon with larger surface area(SBET=1187.2 m^(2)·g^(-1)).The catalyst with higher concentration mainly plays the role of catalyzing graphitization and promotes the obtaining of graphitic carbon with high graphitization degree(ID/IG=0.19).The mechanism of EDTA-iron catalyzed graphitization of RHC is explored by the comprehensive analysis of BET,XRD,Raman,TEM and TGA.This research not only provides an efficient method for the preparation of high-quality biomass-based graphite carbon,but also provides a feasible method for the preparation of biomass-based porous carbon.
基金financially supported by the National Natural Science Foundation of China(No.51274040)the State Basic Research Development Program of China(No.2011CB606306)the Fundamental Research Funds for the Central Universities(No.FRF-TP-10-003B)
文摘To inhibit the graphitization of diamond under high temperature and low pressure, diamond/SiC composites were firstly fabricated by a rapid gaseous Si vacuum reactive infiltration process. The microstructure and graphitization behavior of diamond in the composites under various infiltration temperatures and holding time were investigated. The thermal conductivity of the resul- tant materials was discussed. The results show that the diamond-to-graphite transition is effectively inhibited at temperature of as high as 1600 ℃ under vacuum, and the substantial graphitization starts at 1700 ℃. The microstructure of those ungraphitized samples is uniform and fully densified. The inhibition mechanisms of graphitization include the isolation of the catalysts from diamond by a series of protective layers, high pressure stress applied on diamond by the reaction-bonded SiC, and the moderate gas-solid reaction. For the graphitized samples, the boundary between diamond and SiC is coarse and loose. The graphitization mechanism is considered to be an initial detachment of the bilayers from the diamond surfaces, and subsequently flattening to form graphite. The ungraphitized samples present higher thermal conductivity of about 410 W.m-1.K-1 due to the fine interfacial structure. For the graphitized samples, the thermal conductivity decreases significantly to 285 W.m-1.K-1 as a result of high interfacial thermal resistance.
文摘The etching technique using Ce is a convenient and fast method for polishing and shaping diamond films. In this study, the influence of polishing parameters such as polishing temperature and time on the surface crystallinity and phase composition of diamond films was thoroughly investigated via the analysis of Raman spectra such as FWHM and ID/IG. Moreover, the issue on the graphitization of diamond after polishing with Ce was further researched through the detailed study of the depth distribution of Raman data including FWHM and ID/IG, and a result completely different from the hot-iron metal polished ones was obtained. The results showed that polished diamond films had considerably higher diamond content than those before polishing, and not a bit of graphitization was found in the polished ones, owing to a higher solubility of carbon in rare earth metal Ce than that in transition metals, and the original crystallinity of the films polished with Ce did not deteriorate.
