Towards carbon neutrality of calcium carbide-based acetylene production with sustainable biomass resources

Acetylene is produced from the reaction between calcium carbide(CaC_(2))and water,while the production of CaC_(2) generates significant amount of carbon dioxide not only because it is an energy-intensive process but also the raw material for CaC_(2) synthesis is from coal.Here,a comprehensive biomass-to-acetylene process was constructed that integrated several units including biomass pyrolysis,oxygen-thermal CaC_(2) fabrication and calcium looping.For comparison,a coal-to-acetylene process was also established by using coal as feedstock.The carbon efficiency,energy efficiency and environmental impacts of the bio-based calcium carbide acetylene(BCCA)and coal-based calcium carbide acetylene(CCCA)processes were systematically analyzed.Moreover,the environmental impacts were further evaluated by applying thermal integration at system level and energy substitution in CaC_(2) furnace.Even though the BCCA process showed lower carbon efficiency and energy efficiency than that of the CCCA process,life cycle assessment demonstrated the BCCA(1.873 kgCO_(2eq) kg-prod^(-1))a lower carbon footprint process which is 0.366 kgCO_(2eq) kg-prod^(-1) lower compared to the CCCA process.With sustainable energy(biomass power)substitution in CaC_(2) furnace,an even lower GWP value of 1.377 kgCO_(2eq) kg-prod^(-1) can be achieved in BCCA process.This work performed a systematic analysis on integrating biomass into industrial acetylene production,and revealed the positive role of biomass as raw material(carbon)and energy supplier.

Growth kinetics of titanium carbide coating by molten salt synthesis process on graphite sheet surface

The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kinetics involved in MSS,shedding light on key aspects of the process.The involvement of Ti powder through liquid-phase mass transfer is revealed,where the diffusion distance and quantity of Ti powder play a crucial role in determining the reaction rate by influencing the C content gradient on both sides of the carbide.Furthermore,the growth kinetics of the carbide coating are predominantly governed by the diffusion behavior of C within the carbide layer,rather than the chemical reaction rate.To analyze the kinetics,the thickness of the carbide layer is measured with respect to heat treatment time and temperature,unveiling a parabolic relationship within the temperature range of 700-1300℃.The estimated activation energy for the reaction is determined to be 179283 J·mol^(-1).These findings offer valuable insights into the synthesis of carbide coatings via MSS,facilitating their optimization and enhancing our understanding of their growth mechanisms and properties for various applications.

Spark Plasma Sintering of Boron Carbide Using Ti_(3)SiC_(2) as a Sintering Additive

Boron carbide has unique properties for wide application possibilities;however,poor sinterability limits its applications.One approach to overcome this limitation is the addition of secondary phases into boron carbide.Boron carbide based composite ceramics are produced by the direct addition of secondary phases into the structure or via reactive sintering using a sintering additive.The present study investigated the effect of Ti_(3)SiC_(2) addition to boron carbide by reactive spark plasma sintering in the range of 1700-1900℃.Ti_(3)SiC_(2) phase decomposed at high temperatures and reacted with B4C to form secondary phases of TiB2 and SiC.The results demonstrated that the increase of Ti_(3)SiC_(2) addition(up to 15 vol%)effectively promoted the densification of B4C and yielded higher hardness.However,as the amount of Ti_(3)SiC_(2) increased further,the formation of microstructural inhomogeneity and agglomeration of secondary phases caused a decrease in hardness.

Synthesis methods and powder quality of titanium monocarbide

Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.

Research Progress of High Entropy Carbides

High entropy carbides (HECds) are multi-component carbides consisting of transition metal carbides.HECds are generally composed of five or more metal cations of the equal or near-equal substances,obtaining a single crystal structure.HECds have great potentials for future applications due to excellent mechanical,antioxidant and thermal properties.Due to their complex crystal structures and lattice distortion,computer simulations are widely used to efficiently associate the properties of HECds with the corresponding microstructures.In response to the development of HECds,this article provides an overview of the basic design,preparation process and properties of HECds.

Effect of Sintering Temperature on the Microstructure and Mechanical Properties of Nanocrystalline Cemented Carbide

WC-Co nanocrystalline nitrogen-containing cemented carbides were prepared by vacuum sintering and low pressure sintering.The sintering processes of Cr_(2)(C,N)doped nano WC-Co powders were studied by using thermogravimetric analysis(TGA)and differential scanning calorimetry(DSC).The effect of sintering temperature on the microstructure and mechanical properties of nanocrystalline cemented carbide was studied by scanning electron microscope(SEM),high resolution transmission electron microscope(HRTEM)and mechanical property test.The results showed that the nano WC grains began to grow in the solid phase sintering stage.A high-performance nano-nitrogen-containing cemented carbide with uniform microstructure and good interfacial bonding can be obtained by increasing the sintering temperature to 1380℃.It has a transverse rupture strength(TRS)of 5057 MPa and a hardness of 1956 HV30.

Recent Advances in Interface Modification of Cu/graphite Composites and Layered Ternary Carbides of Modified Layer Candidate

We review the fundamental properties and significant issues related to Cu/graphite composites.In particular,recent research on the interfacial modification of Cu/graphite composites is addressed,including the metal-modified layer,carbide-modified layer,and combined modified layer.Additionally,we propose the use of ternary layered carbide as an interface modification layer for Cu/graphite composites.

“Blocking and rebalance”mechanism-guided design strategies of bimetallic doped 2D a-phosphorus carbide as efficient catalysts for N_(2) electroreduction

Compared to single atom catalysts(SACs),the introduction of dual atom catalysts(DACs)has a significantly positive effect on improving the efficiency in the electrocatalytic nitrogen reduction reaction(NRR)which provides an environmental alternative to the Haber-Bosch process.However,the research on the mechanism and strategy of designing bimetallic combinations for better performance is still in its early stages.Herein,based on"blocking and rebalance"mechanism,45 combinations of bimetallic pair dopedα-phosphorus carbide(TM_(A)TM_(B)@PC)are investigated as efficient NRR catalysts through density functional theory and machine learning method.After a multi-step screening,the combinations of TiV,TiFe,MnMo,and FeW exhibit highly efficient catalytic performance with significantly lower limiting potentials(-0.17,-0.18,-0.14,and-0.30 V,respectively).Excitingly,the limiting potential for CrMo and CrW combinations is 0 V,which are considered to be extremely suitable for the NRR process.The mechanism of"blocking and rebalance"is revealed by the exploration of charge transfer for phosphorus atoms in electron blocking areas.Moreover,the descriptorφis proposed with machine learning,which provides design strategies and accurate prediction for finding efficient DACs.This work not only offers promising catalysts TM_(A)TM_(B)@PC for NRR process but also provides design strategies by presenting the descriptorφ.

Multiscale confinement nitridation in molybdenum carbide for efficient hydrogen production

The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.

Quasi-plastic deformation mechanisms and inverse Hall-Petch relationship in nanocrystalline boron carbide under compression

Grain boundaries(GBs)play a significant role in the deformation behaviors of nanocrystalline ceramics.Here,we investigate the compression behaviors of nanocrystalline boron carbide(nB_(4)C)with varying grain sizes using molecular dynamics simulations with a machine-learning force field.The results reveal quasi-plastic deformation mechanisms in nB_(4)C:GB sliding,intergranular amorphization and intragranular amorphization.GB sliding arises from the presence of soft GBs,leading to intergranular amorphization.Intragranular amorphization arises from the interaction between grains with unfavorable orientations and the softened amorphous GBs,and finally causes structural failure.Furthermore,nB_(4)C models with varying grain sizes from 4.07 nm to 10.86 nm display an inverse Hall-Petch relationship due to the GB sliding mechanism.A higher strain rate in nB_(4)C often leads to a higher yield strength,following a 2/3 power relationship.These deformation mechanisms are critical for the design of ceramics with superior mechanical properties.

Preparation and Analysis of Carbon Fiber-Silicon Carbide Thermally Conductive Asphalt Concrete

An experimental investigation into the thermal conductivity of CF-SiC two-phase composite asphalt concrete is presented.The main objective of this study was to verify the possibility of using SiC powder instead of mineral powder as the thermal conductive filler to prepare a new type of asphalt concrete and improve the efficiency of electrothermal snow and ice melting systems accordingly.The thermal conductivity of asphalt concrete prepared with different thermally conductive fillers was tested by a transient plane source method,and the related performances were measured.Then the temperature rise rate and surface temperature were studied through field heating tests.Finally,the actual ice melting efficiency of the thermally conductive asphalt concrete was evaluated using an effective electrothermal system.As shown by the experimental results,the composite made of SiC powder and carbon fiber has a high thermal conductivity.When SiC replaces mineral powder,the thermal conductivity of the asphalt mixture increases first and then decreases with the increase of carbon fiber content.In the present study,in particular,the thermal conductivity attained a peak when the carbon fiber content was 0.2%of the aggregate mass.

Comparative Study on Microstructure and Mechanical Properties of Coarse-grained WC-based Cemented Carbides Sintered with Ultrafine WC or (W+C) as Additives

The effects of ultrafine WC(WC_(UF),0.5μm) or W(1μm) and C(0.3μm)(W+C)_(UF) additives on the densification,microstructure and mechanical properties of coarse-grained cemented carbides were compared systematically.Overall,the cemented carbides with WC_(UF)/(W+C)_(UF) additives are almost fully densification to be higher than 99%,and the average grain size is kept above 2.8μm.The WC_(UF) additive assists grains to(truncated)trigonal prism shape by two dimensional(2D) growth,whereas the(W+C)_(UF) additive assists grains to rounded shape by three dimensional(3D) growth,lowers WC contiguity and increases face-centered-cubic Co.The hardness and bending strength of(75WC_(C)-15WC_(UF))-10Co are 86.6 HRA and 2 272 MPa,respectively,both higher than those of(75WC_(C)-15(W+C)_(UF))-10Co,which could be ascribed to the enhanced densification and unblemished grains.However,the fracture toughness of the(75WC_(C)-15(W+C)_(UF))-10Co is 23.5 MPa·m^(1/2),higher than that of the(75WC_(C)-15WC_(UF))-10Co due to the uniform WC-Co structure and flexible binder phase.

Pulsed laser interference patterning of transition-metal carbides for stable alkaline water electrolysis kinetics

We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.

Influence of Carbon Content on Element Diffusion in Silicon Carbide-Based TRISO Composite Fuel

The coating layers of Tri-structural Isotropic Particles(TRISO)serve to protect the kernel and act as barriers to fission products.Sintering aids in the silicon carbide matrix variably react with TRISO coating layers,leading to the destruction of the coating layers.Investigating how carbon content affects element diffusion in silicon carbide-based TRISO composite fuel is of great significance for predicting reactor safety.In this study,silicon carbide-based TRISO composite fuels with different carbon contents were prepared by adding varying amounts of phenolic resin to the silicon carbide matrix.X-ray Diffraction(XRD)and Scanning Electron Microscopy(SEM)were employed to characterize the phase composition,morphology,and microstructure of the composite fuels.The elemental content in each coating layer of TRISO was quantified using Energy-Dispersive X-ray Spectroscopy(EDS).The results demonstrated that the addition of phenolic resin promoted the uniform distribution of sintering aids in the silicon carbide matrix.The atomic percentage(at.%)of aluminum(Al)in the pyrolytic carbon layer of the TRISO particles reached its lowest value of 0.55%when the phenolic resin addition was 1%.This is because the addition of phenolic resin caused the Al and silicon(Si)in the matrix to preferentially react with the carbon in the phenolic resin to form a metastable liquid phase,rather than preferentially consuming the pyrolytic carbon in the outer coating layer of the TRISO particles.The findings suggest that carbon addition through phenolic resin incorporation can effectively mitigate the deleterious reactions between the TRISO coating layers and sintering aids,thereby enhancing the durability and safety of silicon carbide-based TRISO composite fuels.

Research on Silicon Carbide Dispersion-Reinforced Hypereutectic Aluminum-Silicon Electronic Packaging Materials

The objective of this study is to improve the mechanical properties and machining performance of high thermal conductivity and low expansion silicon carbide dispersion-strengthened hypereutectic aluminum-silicon electronic packaging materials to meet the needs of aviation,aerospace,and electronic packaging fields.We used the powder metallurgy method and high-temperature hot pressing technology to prepare SiC/Al-Si composite materials with different SiC contents(5vol%,10vol%,15vol%,and 20vol%).The results showed that as the SiC content increased,the tensile strength of the composite material first increased and then decreased.The tensile strength was the highest when the SiC content was 15%;the sintering temperature significantly affected the composite material’s structural density and mechanical properties.Findings indicated 700℃was the optimal sintering and the optimal SiC content of SiC/Al-Si composite materials was between 10%and 15%.Besides,the sintering temperature should be strictly controlled to improve the material’s structural density and mechanical properties.

Influence of band microstructure on carbide precipitation behavior and toughness of 1 GPa-grade ultra-heavy gauge low-alloy steel

This study investigated the influence of band microstructure induced by centerline segregation on carbide precipitation behavior and toughness in an 80 mm-thick 1 GPa low-carbon low-alloy steel plate.The quarter-thickness(1/4t)and half-thickness(1/2t)regions of the plate exhibited similar ductility and toughness after quenching.After tempering,the 1/4t region exhibited~50%and~25%enhancements in both the total elongation and low-temperature toughness at-40°C,respectively,without a decrease in yield strength,whereas the toughness of the 1/2t region decreased by~46%.After quenching,both the 1/4t and 1/2t regions exhibited lower bainite and lath martensite concentrations,but only the 1/2t region exhibited microstructure bands.Moreover,the tempered 1/4t region featured uniformly dispersed short rod-like M_(23)C_(6)carbides,and spherical MC precipitates with diameters of~20–100 nm and<20 nm,respectively.The uniformly dispersed nanosized M_(23)C_(6)carbides and MC precipitates contributed to the balance of high strength and high toughness.The band microstructure of the tempered 1/2t region featured a high density of large needle-like M3C carbides.The length and width of the large M3C carbides were~200–500 nm and~20–50 nm,respectively.Fractography analysis revealed that the high density of large carbides led to delamination cleavage fracture,which significantly deteriorated toughness.

Application of silicon carbide temperature monitors in 49-2 swimming-pool test reactor

High purity SiC crystal was used as a passive monitor to measure neutron irradiation temperature in the 49-2 research reactor.The SiC monitors were irradiated with fast neutrons at elevated temperatures to 3.2×10^(20)n/cm^(2).The isochronal and isothermal annealing behaviors of the irradiated SiC were investigated by x-ray diffraction and four-point probe techniques.Invisible point defects and defect clusters are found to be the dominating defect types in the neutron-irradiated SiC.The amount of defect recovery in SiC reaches a maximum value after isothermal annealing for 30 min.Based on the annealing temperature dependences of both lattice swelling and material resistivity,the irradiation temperature of the SiC monitors is determined to be~410℃,which is much higher than the thermocouple temperature of 275℃ recorded during neutron irradiation.The possible reasons for the difference are carefully discussed.

Mesoporous molybdenum carbide for greatly enhanced hydrogen evolution at high current density and its mechanism studies

Currently the catalysis of hydrogen evolution reaction(HER)is mainly focused on the inherent electrocatalytic activity at relatively lower current densities while scarce at high current densities.Nevertheless,the latter is highly demanding in efficient mass-production of hydrogen.A SiO_(2) nanospheres template-synthesis is used to prepare mesoporous molybdenum carbide nanocrystals-embedded nitrogen-doped carbon foams(mp-Mo_(2)C/NC).The material shows much more excellent catalytic activity than the non-etched Mo_(2)C/NC toward hydrogen evolution reaction(HER)in acidic medium.More interestingly mp-Mo_(2)C/NC still has larger overpotential than Pt/C at lower current densities,but possess remarkably smaller overpotential than the latter at higher current densities for much better electrocatalytic performance.An approach is developed to investigate the electrode kinetics by Tafel plots,especially with eliminating the diffusion effect,indicating that Pt/C and mp-Mo_(2)C/NC display different reaction mechanisms.At low current densities the former presents reversible reaction,while the latter shows mixed electrochemical polarization/reversible electrode process.In the region of higher current densities,the former becomes totally gas-diffusion controlled with large overpotential,while the latter can still retain an electrode polarization process for much lower overpotential at the same current density.Result endorses that the meso-porously structured mp-Mo_(2)C/NC plays a critical role in avoiding gas diffusion control-resulting large overpotential at high current densities.This work holds great potential for an inexpensive catalyst better than Pt/C in practical applications of mass-production hydrogen at high current densities,while clearly shedding fundamental lights on designs of rational HER catalysts for the uses at high current densities.

Carbides Formation in MarM247 Directional Solidified during Stress-Rupture Test at High Temperature

In our study, stress-rupture tests were conducted at elevated temperatures to examine the impact of high temperature on MarM247 LC (low carbon). Our main objective was to investigate the alterations in the microstructure, particularly the carbon precipitation, during long-term stress-rupture tests. It was observed that cracks developed near the sample neck, following the path of the carbides and the gamma matrix, rather than occurring in the gamma-gamma prime eutectic. This occurred despite the formation of carbides because of prolonged exposure to high temperature and load, and the crack propagation did not follow that path. Based on these findings, we suggest that a reduction in the carbon content of Mar-M247 LC can enhance the sample's lifespan when subjected to temperatures below 760˚C and a stress of 690 MPa.

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.