Technology of Iron Carbide Synthesis

Iron carbides are very promising metallurgical products and can be used for steelmaking process, where it plays as an alternative raw material with significant economic advantages. Also it has many other applications, e.g. catalysts, magnets, sensors. The present review investigates the different properties and uses of the iron carbides. The commercial production and the different varieties for the iron carbides synthesis （gaseous carburization, mechanochemical synthesis, laser pyrolysis, plasma pyrolysis, chemical vapor deposition and ion implantation） were reviewed. Also the effect of different factors on the carburization process like gas composition, raw material, temperature, reaction time, catalyst presence and sulfur addition was indicated.

Catalytic performance of iron carbide for carbon monoxide hydrogenation

Novel iron carbide and potassium-promoted iron carbide catalysts were prepared and investigated for CO hydrogenation. The iron carbide showed high activity for CO hydrogenation under high pressures; with the addition of potassium, activity and selectivity to C5＋ hydrocarbons were greatly enhanced, and the selectivity to methane was suppressed under high pressure.

Speeding up the prediction of C-O cleavage through bond valence and charge on iron carbides

The activation of CO on iron-based materials is a key elementary reaction for many chemical processes.We investigate CO adsorption and dissociation on a series of Fe,Fe_(3)C,Fe_(5)C_(2),and Fe_(2)C catalysts through density functional theory calculations.We detect dramatically different performances for CO adsorption and activation on diverse surfaces and sites.The activation of CO is dependent on the local coordination of the molecule to the surface and on the bulk phase of the underlying catalyst.The bulk properties and the different local bonding environments lead to varying interactions between the adsorbed CO and the surface and thus yielding different activation levels of the C-O bond.We also examine the prediction of CO adsorption on different types of Fe-based catalysts by machine learning through linear regression models.We combine the features originating from surfaces and bulk phases to enhance the prediction of the activation energies and perform eight different linear regressions utilizing the feature engineering of polynomial representations.Among them,a ridge linear regression model with2nd-degree polynomial feature generation predicted the best CO activation energy with a mean absolute error of 0.269 eV.

Mechanism of high temperature reduction on iron carbide preparation with low-grade siderite

The carburization roasting followed by magnetic separation is a feasible method to utilize low-grade siderite ore.In order to enhance the carburization efficiency and separation effciency,high temperature reduction was carried out,and its mechanism was demonstrated by measuring carburization index,phase change,and microstructure under a carbon-sulfur infrared analyzer,an X-ray diffractometer,and a metallurgical microscope.The results show that both the carburization effciency of siderite pellet and the separation efficiency of iron carbide from gangue are very low.However,high temperature reduction is a useful way to enhance the carburization efficiency,as it can accelerate the reduction reaction rate and carburization reaction rate.Furthermore,high temperature reduction can improve the growth of iron carbide particle,promote the carburization efficiency,and strengthen the sodium modification reactions,thereby greatly accelerating the separation efficiency of iron carbide and gangue.When the siderite pellets were reduced at 1050℃ for 90 min and carburized at 650℃ for 120 min,the carburization index of carburized pellets reached 36.06.After magnetic separation treatment,an electric furnace burden assaying 83.12 wt.%Fe and 6.96 wt.%C was prepared,and the corresponding iron recovery rate was 95.43%.The high temperature reduction is promisingly adopted to promote the utilization of low-grade siderite ores using carburization-magnetic separation technology.

Effect of vanadium and chromium on the microstructural features of V–Cr–Mn–Ni spheroidal carbide cast irons

The objective of this investigation is to study the influence of vanadium（5.0wt%–10.0wt%） and chromium（0–9.0wt%） on the microstructure and hardness of Cr-V-Mn-Ni white cast irons with spheroidal vanadium carbides. The alloys＇ microstructural features are presented and discussed with regard to the distribution of phase elements. The structural constituents of the alloys are spheroidal VC, proeutectoid cementite, ledeburite eutectic, rosette-shaped carbide eutectic（based on M7C3）, pearlite, martensite, and austenite. Their combinations and area fraction（AF） ratios are reported to be influenced by the alloys＇ chemical composition. Spheroidized VC particles are found to be sites for the nucleation of carbide eutectics. Cr and V are shown to substitute each other in the VC and M7C3 carbides, respectively. Chromium alloying leads to the formation of a eutectic（γ-Fe ＋ М7С3）, preventing the appearance of proeutectoid cementite in the structure. Vanadium and chromium are revealed to increase the total carbide fraction and the amount of austenite in the matrix. Cr is observed to play a key role in controlling the metallic matrix microstructure.

Abrasive resistance of metastable V–Cr–Mn–Ni spheroidal carbide cast irons using the factorial design method

Full factorial design was used to evaluate the two-body abrasive resistance of 3wt%C–4wt%Mn–1.5wt%Ni spheroidal carbide cast irons with varying vanadium（5.0wt%–10.0wt%） and chromium（up to 9.0wt%） contents. The alloys were quenched at 920℃. The regression equation of wear rate as a function of V and Cr contents was proposed. This regression equation shows that the wear rate decreases with increasing V content because of the growth of spheroidal VC carbide amount. Cr influences the overall response in a complex manner both by reducing the wear rate owing to eutectic carbides（M7C3） and by increasing the wear rate though stabilizing austenite to deformation-induced martensite transformation. This transformation is recognized as an important factor in increasing the abrasive response of the alloys. By analyzing the regression equation, the optimal content ranges are found to be 7.5wt%–10.0wt% for V and 2.5wt%–4.5wt% for Cr, which corresponds to the alloys containing 9vol%–15vol% spheroidal VC carbides, 8vol%–16vol% M7C3, and a metastable austenite/martensite matrix. The wear resistance is 1.9–2.3 times that of the traditional 12wt% V–13wt% Mn spheroidal carbide cast iron.

Application Research of Dense Sintered Alumina in Iron Runner Castables

Three different kinds of corundum aggregates-tabular sintered alumina, dense sintered alumina, and fused dense corundum-were introduced into the silica fume .free or silica fume containing Al2O3 -SiC - C iron runner castables to investigate their influences on the flow ability, linear change on heating, bulk density, apparent porosity, cold strength, hot modulus of rupture, therm, al shock resistance, slag resistance, oxidation resistance as well as wear resistance of Al2O3 - SiC - C iron runner castables. The results show that （ 1 ） compared with the specimens with fused dense corundum, the specimens with dense sintered alumina have equivalent installation property, slag resistance and oxidation resistance, equivalent or even higher cold modulus of rupture, cold crushing strength and hot modulus of rupture, exhibiting better thermal shock resistance and cold wear resistance ; （2） adopting bimodal alumina micropowder LISAL22RABL as well as water reducers ZX2 and ZD2 can well reduce the water requirement of silica fume free castables, solving the problem of deteriorated flow ability resulted from the lack of silica fume; since the lack of silica fume avoids the formation of low melting point liquid, the hot modulus of rupture and the thermal shock resistance of the silica fume free castables are both better than those of the silica fume containing castables ; （3） the density of the castable specimens with dense sintered alumina is 4% -6% lower than that of the castable specimens with Jhsed dense corundum so the refractories consumption of one iron runner reduces by 5% by using the tastable with dense sintered alumina, which obviously reduces the cost of refractories.

Hetero-Epitaxial Diamond Single Crystal Growth on Surface of cBN Single Crystals at High Pressure and High Temperature

We report a new diamond synthesis process in which cubic boron nitride single crystals are used as seeds, FesoNi20 alloy powder is used as catalyst/solvent and natural flake-like graphite is used as the carbon source. The samples are investigated using laser Raman spectra and x-ray diffraction （XRD）. Morphology of the sample is observed by a scanning electron microscope （SEM）. Based on the measurement results, we conclude that diamond single crystals have grown on the cBN crystal seeds under the conditions of high temperature 1230℃ and high pressure 4.8 GPa. This work provides an original method for synthesis of high quality hereto-semiconductor with cBN and diamond single crystals, and paves the way for future development.

Boosting CO_(2) hydrogenation to high-value olefins with highly stable performance over Ba and Na co-modified Fe catalyst

CO_(2)hydrogenation has been considered to be a highly promising route for the production of high-value olefins(HVOs)while also mitigating CO_(2)emissions.However,it is challenging to achieve high selectivity and maintain stable performance for HVOs(ethylene,propylene,and linear a-olefins)over a prolonged reaction time due to the difficulty in precise control of carbon coupling and rapid catalyst deactivation.Herein,we present a selective Ba and Na co-modified Fe catalyst enriched with Fe_(5)C_(2)and Fe_(3)C active sites that can boost HVO synthesis with up to 66.1%selectivity at an average CO_(2)conversion of 38%for over 500 h.Compared to traditional NaFe catalyst,the combined effect of Ba and Na additives in the NaBaFe-0.5 catalyst suppressed excess oxidation of FeCxsites by H_(2)O.The absence of Fe3O4phase in the spent NaBaFe-0.5 catalyst reflects the stabilization effect of the co-modifiers on the FeCxsites.This study provides a strategy to design Fe-based catalysts that can be scaled up for the stable synthesis of HVOs from CO_(2)hydrogenation.

Active Fischer-Tropsch synthesis Fe-Cu-K/SiO_2 catalysts prepared by autocombustion method without a reduction step

The purpose of this study was to prepare iron-based catalysts supported on silica by autocombustion method for directly using for Fischer-Tropsch synthesis（FTS） without a reduction step. The effect of different citric acid（CA）：iron nitrate（N） molar ratios and acid types on the FTS performance of catalysts were investigated. The CA：N molar ratios had an important influence on the formation of iron active phases and FTS activity. The iron carbide（FexC）, which is known to be one of the iron active phases, was demonstrated by the X-ray diffraction and X-ray photoelectron spectroscopy. Increasing the CA：N molar ratios up to 0.1 increased CO conversion of catalyst to 86.5%, which was then decreased markedly at higher CA：N molar ratios. An excess of CA resulted in carbon residues covering the catalyst surface and declined FTS activity. The optimal catalyst（CA：N molar ratio = 0.1） achieved the highest CO conversion when compared with other autocombustion catalysts as well as reference catalyst prepared by impregnation method, followed by a reduction step. The autocombustion method had the advantage to synthesize more efficient catalysts without a reduction step. More interestingly, iron-based FTS catalysts need induction duration at the initial stage of FTS reaction even after reduction, because metallic iron species need time to be transformed to FexC. But here, even if without reduction, FexC was formed directly by autocombustion and induction period was eliminated during FTS reaction.

Synthesis of Iron-Carbide Nanoparticles:Identification of the Active Phase and Mechanism of Fe-Based Fischer-Tropsch Synthesis

Despite the extensive study of the Fe-based Fischer-Tropsch synthesis(FTS)over the past 90 years,its active phases and reaction mechanisms are still unclear due to the coexistence of metals,oxides,and carbide phases presented under realistic FTS reaction conditions and the complex reaction network involving CO activation,C-C coupling,and methane formation.To address these issues,we successfully synthesized a range of pure-phase iron and iron-carbide nanoparticles(Fe,Fe_(5)C_(2),Fe_(3)C,and Fe_(7)C_(3))for the first time.By using them as the ideal model catalysts on high-pressure transient experiments,we identified unambiguously that all the iron carbides are catalytically active in the FTS reaction while Fe_(5)C_(2) is the most active yet stable carbide phase,consistent with density functional theory(DFT)calculation results.The reaction mechanism and kinetics of Fe-based FTS were further explored on the basis of those model catalysts by means of transient high-pressure stepwise temperature-programmed surface reaction(STPSR)experiments and DFT calculations.Our work provides new insights into the active phase of iron carbides and corresponding FTS reaction mechanism,which is essential for better iron-based catalyst design for FTS reactions.

Effect of hydrogen plasma treatment on the growth and microstructures of multiwalled carbon nanotubes

The effect of hydrogen plasma treatment of iron oxide films on the growth and microstructure of carbon nanotubes(CNTs)by microwave plasma enhanced chemical vapor deposition process has been investigated.Microwave plasma was characterized in-situ using optical emission spectrometer.Morphology of the films was examined by scanning electron microscopy.Structural analysis was carried out by high resolution transmission electron microscopy(HRTEM)equipped with energy dispersive X-ray spectroscopy(EDS)and micro-diffraction attachments.It is found that oxide films without H_2 plasma pretreatment or treated for lesser time resulted in CNT films with high percentage of carbonaceous particles and with embedded particles/nanorods distributed discontinuously in the cavity of the nanotubes.The embedded particles were found to be of iron carbide(Fe-C)as confirmed by HRTEM,EDS and micro-diffraction analysis.Experimental observations suggested that the iron oxide particles had poor catalytic action for CNT growth and in-situ reduction of oxide clusters to Fe by hydrogen plasma plays a key role in discontinuous filling of the nanotubes by the catalytic particles.

First-principles calculations of high pressure and temperature properties of Fe_(7)C_(3)

Eckstrom-adcock iron carbide(Fe_(7)C_(3))is considered to be the main constituent of the Earth’s inner core due to its low shear wave velocity.However,the crystal structure of Fe_(7)C_(3)remains controversial and its thermoelastic properties are not well constrained at high temperature and pressure.Based on the first-principles simulation method,we calculate the relative phase stability,equation of state,and sound velocity of Fe_(7)C_(3)under core condition.The results indicate that the orthorhombic phase of Fe_(7)C_(3)is stable under the core condition.While Fe_(7)C_(3)does reproduce the low shear wave velocity and high Poisson’s ratio of the inner core,its compressional wave velocity and density are 12%higher and 6%lower than those observed in seismic data,respectively.Therefore,we argue that carbon alone cannot completely explain the thermal properties of the inner core and the inclusion of other light elements may be required.

XRD Synchrotron Study of Carbide Precipitation in Martensitic Steels During Tempering

In order to improve the knowledge of the precipitation mechanism in martensitic steels containing carbon,XRD synchrotron experiments were performed. Firstly, the influence of Ni,Co and Al were studied and it was found that the precipitation of iron carbides occurs in same way as in Fe-C steel. However, with the addition of molybdenum and chromium in same steels, XRD synchrotron investigations clearly showed alloyed carbides directly precipitate, thereby preventing the iron carbides formation.

Theoretical study of the strain effects on CO activation by Fe_(2)C confined with graphene

The intrinsic strains at the confinement interface of iron carbide with graphene play important roles in the catalytic Fischer-Tropsch synthesis.In this study,we performed theoretical study of the biaxial strain effects on the CO adsorption and dissociation on the Fe_(2)C(121)surface covered by graphene(Fe_(2)C@graphene).By varying the lattice strains within a range of±5%,the apparent energy barriers(E_(a,app))correlate with the adsorption energies(E_(ad))in nonlinear scaling relations for the direct and H-assisted CO dissociation at the Fe_(2)C active sites,which is normal Br∅nsted-Evans-Polanyi relation for those at the graphene sites.The nonlinear scaling relations can be interpreted by the strain effects on the confinement distances in the adsorption and transition states.This study provides a deep understanding of the intrinsic strain effects of Fe_(2)C@graphene for CO activation.

Research Trends in Fischer-Tropsch Catalysis for Coal to Liquids Technology

Fischer–Tropsch Synthesis(FTS) constitutes catalytic technology that converts synthesis gas to synthetic liquid fuels and chemicals.While synthesis gas can be obtained from any carbonaceous feedstock,current industrial FTS operations are almost exclusively based on natural gas.Due to the energy structure of China where cheap coal is abundant,coal to liquids(CTL) technology involving coal gasification,FTS and syncrude upgrading is increasingly being considered as a viable option to convert coal to clean transportation fuels.In this brief paper,we review some pertinent issues about Fe-and Co-based FTS catalysts.Fe is better suited to convert synthesis gas derived from coal gasification into fuels.The authors limit themselves to noting some important trends in the research on Fe-based catalysts.They focus on the preparation of phase-pure carbides and innovative cheap synthesis methods for obtaining active and stable catalysts.These approaches should be augmented by(1) computational investigations that are increasingly able to predict not only mechanism,reaction rates and selectivity but also optimum catalyst composition,as well as(2) characterization of the catalytic materials under conditions close to the operation in real reactors.

A facile template approach for the synthesis of mesoporous Fe3C/Fe-N- doped carbon catalysts for efficient and durable oxygen reduction reaction

Facile synthetic approaches toward the development of efficient and durable nonprecious metal catalysts for the oxygen reduction reaction （ORR） are very important for commercializing advanced electrochemical devices such as fuel cells and metal-air batteries. Here we report a novel template approach to synthesize mesoporous Fe-N-doped carbon catalysts encapsulated with Fe3C nanoparticles. In this approach, the layer-structured FeOCI was first used as a template for the synthesis of a three- dimensional polypyrrole （PPy） structure. During the removal of the FeOCI template, the Fe^3＋ can be absorbed by PPy and then converted into Fe3C nanoparticles and Fe-N-C sites during the pyrolyzing process. As a result, the as-prepared catalysts could exhibit superior electrocatalytic ORR performance to the commercial Pt/C catalyst in alkaline solutions. Furthermore, the Zn-air battery assembled using the mesoporous carbon catalyst as the air electrode could surpass the commercial Pt/C catalyst in terms of the power density and energy density.