Trend and Development of Semi-Solid Metal Processing

This paper reviewed the trend and development of semi-solid metal technique. The processes and mechanisms for producing slurry of SSM and its industrial applications have been summarized and discussed. Discussions on the basic rheological theory are presented for more applications. Further consideration of the development and application of SSM technique is also proposed.

Energy Dissipation and Apparent Viscosity of Semi-solid Metal during Rheological Processes PartⅡ:Apparent Viscosity

This study investigated the rheological properties of semi-solid metal. An analytical model of apparent viscosity was built up based on analysis of energy dissipation during rheological processes such as slurry preparing, delivering and model filling. The rheological properties of SSM （semi-solid metal） slurry was described by an analytical model in terms of microstructural parameters, which consist of effective solid fraction, particle size and shape, and flow parameters such as mean velocity, fluctuant velocity and relative velocity between liquid and solid phase. The model was verified in the experiment of A356 alloys with a coaxial double-bucket rheometer. And the maximum relative error between the theoretical value and measured one is less than 20%. The results of experiment and theoretical calculation also indicate that the microstructural parameters and flow parameters are two major factors that affect the apparent viscosity of semi-solid alloys, and fluctuant velocity and relative velocity between liquid and solid phase are the key factors to distinguish between steady and transient rheological properties.

Energy Dissipation and Apparent Viscosity of Semi-solid Metal during Rheological Processes PartⅠ: Energy Dissipation

The energy dissipation caused by the viscous force has great effects on the flow property of semi-solid metal during rheological processes such as slurry preparing, delivering and cavity filling. Experimental results in this paper indicate that the viscous friction between semi-solid metal and pipe wall, the collisions among the solid particles, and the liquid flow around particles are the three main types of energy dissipation. On the basis of the hydromechanics, the energy dissipation calculation model is built. It is demonstrated that the micro-structural parameters such as effective solid fraction, particle size and shape, and flow parameters such as the mean velocity, the fluctuant velocity of particles and the relative velocity between the fluid and solid phase, affect the energy dissipation of semi-solid metal.

Numerical simulation of the preparation of semi-solid metal slurry with damper cooling tube method

In semi-solid forming process, preparing the slurry with rosette or globular microstructure is very important. A new approach named the damper cooling tube method （DCT）, to produce the semi-solid metal slurry, has been introduced. To optimize the technical parameters in designing the apparatus, the finite volume method was adopted to simulate the flow process. The temperature effects on the rheological properties of the slurries were also considered. The effects of the technical parameters on the slurry properties were studied in detail.

Influence of surface liquid segregation on corrosion behavior of semi-solid metal high pressure die cast aluminium alloys

The corrosion behavior(in chloride medium) of the surface layer of SSM-HPDC plates of alloys 7075-T6 and 2024-T6 was compared with that of the wrought alloys 7075-T6 and 2024-T6.Potentiodynamic testing was performed in deaerated 3.5%NaCl solution.In separate tests,the open-circuit potential was monitored in aerated 3.5% NaCl for 30 min after immersion.The electrochemical tests show that there is no significant difference in the pitting potential of the wrought alloys and that of the Cu-enriched surfaces of the SSM-HPDC alloys.

Phase-field Simulation of Microstructural Evolution during Preparation of Semi-solid Metal by Electromagnetic Stirring Method

In the process of preparation of semi-solid metal materials, a variety of factors would influence the preparing time and the morphology of non-dendritic microstructure. The aim of this work is using phase-field method to simulate non-dendritic growth during preparation of AI-4Cu-Mg semi-solid alloy by electromagnetic stirring method （EMS method）. Several factors such as the disturbance intensity, anisotropy, the thickness of the interface and the ratio of diffusivity in solid and liquid were considered. It is shown that decreasing the thickness of the interface results in more circular outline of particles, and increasing the diffusivity in solid can reduce degree of microsegregation. The disturbance intensity in the model can be connected with current intensity of stator or magnetic induction density impressed. Simulation results show that the larger the disturbance intensity or magnetic induction density, the more globular morphology the original phase in the matrix.

Designing Conformal Electrode-electrolyte Interface by Semi-solid NaK Anode for Sodium Metal Batteries

Solid-state Na metal batteries(SSNBs),known for its low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of NaK alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the intimate contact of electrode-electrolyte interface.Additionally,the filling of SiO_(2)nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 h.The full cell coupled with Na_(3)V_(3)(PO_(4))_(2)cathodes had an initial discharge capacity of 106.8 mAh·g^(-1)with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1)even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.

Research status and prospects of the fractal analysis of metal material surfaces and interfaces

As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.

Deep eutectic solvents for separation and purification applications in critical metal metallurgy:Recent advances and perspectives

Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Insights into the rheological modeling of semi-solid metals:Theoretical and simulation study

The power law model is the most widely used model for the rheological behavior of semi-solid metals(SSMs)in the numerical simulation of semi-solid processing.However,it is still not known why the anomalous negative flow exponent exists in the power law model for SSMs and its influence on the simulation.In this research,the rheological behavior of semi-solid Al-7Si-0.3Mg aluminum alloy is experimentally studied followed by modeling.The power law model fitting results show flow curves deviate from the experimental data and negative flow exponents,which are physically nonsensical and inapplicable to the simulation of SSMs flow proved by hydrodynamic analysis.This drawback of the power law model stems from neglecting the yield stress of SSMs.By contrast,the model referring Herschel-Bulkley(HB)theory which takes yield stress into consideration has reasonable flow exponent and yields good agreement between the fitting and experimental results.Furthermore,the simulation of die filling process is conducted,suggesting that the power law model over-optimistically predicts the tendency of blistering and misrun defects at low temperature and high filling velocity during semi-solid processing.

A Novel Process in Semi-Solid Metal Casting

In this research a new process for semi-solid casting of ductile iron based on the high nucleation rate combined with locally mechanical stirring is presented. In this process at first fully liquid ductile iron was poured on the peripheral surface of a wheel rotating against pouring direction. At this stage, the solid crystals nucleated at the chilling surface were pushed to the melt by a heat resistance steel cutter and finally the semi-solid slurry was generated. Reheating treatment was done on the samples to achieve more efficiency of semi-solid casting process. The effects of the travelling distance of solid particles during casting, the reheating time and temperature were examined. The results showed that the process effectively changes the dendrite structure to globular one.

Shear bands of as-cast and semi-solid Ti_(48)Zr_(27)Cu_(6)Nb_(5)Be_(14)bulk metallic glass matrix composites

The as-cast Ti_(48)Zr_(27)Cu_(6)Nb_(5)Be_(14)bulk metallic glass matrix composites(BMGMCs)were fabricated using a copper mold suction casting method.Then,the semi-solid BMGMC samples were obtained following an isothermal treatment(heating at 900°C for 10 min,then cooling with water).The microstructure and compression property were investigated by scanning electronic microscopy(SEM)and universal mechanical tester.As a result of the isothermal treatment,the crystal shapes change from fine,granular,and dendritic to spherical or vermicular,and the average crystal size of the as-cast and semi-solid samples is 2.2μm and 18.1μm,respectively.The plasticity increases from 5.31%in the as-cast to 10.23%in the semi-solid samples,with an increase of 92.66%.The shear bands from different areas of the side surfaces of as-cast and semisolid compression fracture samples were observed.The characteristic changes of multiplicity,bend,branch and intersection of shear bands in different areas indicate that the deformation of as-cast and semi-solid samples is non-uniform during compression.It is found that poor plasticity of the as-cast samples or good plasticity of the semi-solid samples are reflected by characteristics of the shear bands.The semi-solid isothermal treatment improves the plasticity by forming large crystals which can block the expansion of shear bands and promote the multiplicity of shear bands.

Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

From Liquid to Solid‑State Lithium Metal Batteries:Fundamental Issues and Recent Developments

The widespread adoption of lithium-ion batteries has been driven by the proliferation of portable electronic devices and electric vehicles,which have increasingly stringent energy density requirements.Lithium metal batteries(LMBs),with their ultralow reduction potential and high theoretical capacity,are widely regarded as the most promising technical pathway for achieving high energy density batteries.In this review,we provide a comprehensive overview of fundamental issues related to high reactivity and migrated interfaces in LMBs.Furthermore,we propose improved strategies involving interface engineering,3D current collector design,electrolyte optimization,separator modification,application of alloyed anodes,and external field regulation to address these challenges.The utilization of solid-state electrolytes can significantly enhance the safety of LMBs and represents the only viable approach for advancing them.This review also encompasses the variation in fundamental issues and design strategies for the transition from liquid to solid electrolytes.Particularly noteworthy is that the introduction of SSEs will exacerbate differences in electrochemical and mechanical properties at the interface,leading to increased interface inhomogeneity—a critical factor contributing to failure in all-solidstate lithium metal batteries.Based on recent research works,this perspective highlights the current status of research on developing high-performance LMBs.

Laser‑Induced and MOF‑Derived Metal Oxide/Carbon Composite for Synergistically Improved Ethanol Sensing at Room temperature

Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.

Towards advanced zinc anodes by interfacial modification strategies for efficient aqueous zinc metal batteries

Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.

On the thermodynamics of plasticity during quasi-isentropic compression of metallic glass

Entropy production in quasi-isentropic compression (QIC) is critically important for understanding the properties of materials under extremeconditions. However, the origin and accurate quantification of entropy in this situation remain long-standing challenges. In this work, a framework is established for the quantification of entropy production and partition, and their relation to microstructural change in QIC. Cu50Zr50is taken as a model material, and its compression is simulated by molecular dynamics. On the basis of atomistic simulation-informed physicalproperties and free energy, the thermodynamic path is recovered, and the entropy production and its relation to microstructural change aresuccessfully quantified by the proposed framework. Contrary to intuition, entropy production during QIC of metallic glasses is relativelyinsensitive to the strain rate ˙γ when ˙γ ranges from 7.5 × 10^(8) to 2 × 10^(9)/s, which are values reachable in QIC experiments, with a magnitudeof the order of 10^(−2)kB/atom per GPa. However, when ˙γ is extremely high (>2 × 10^(9)/s), a notable increase in entropy production rate with˙γ is observed. The Taylor–Quinney factor is found to vary with strain but not with strain rate in the simulated regime. It is demonstrated thatentropy production is dominated by the configurational part, compared with the vibrational part. In the rate-insensitive regime, the increase inconfigurational entropy exhibits a linear relation to the Shannon-entropic quantification of microstructural change, and a stretched exponential relation to the Taylor–Quinney factor. The quantification of entropy is expected to provide thermodynamic insights into the fundamentalrelation between microstructure evolution and plastic dissipation.

Effect of Interface Form on Creep Failure and Life of Dissimilar Metal Welds Involving Nickel-Based Weld Metal and Ferritic Base Metal

For dissimilar metal welds(DMWs)involving nickel-based weld metal(WM)and ferritic heat resistant steel base metal(BM)in power plants,there must be an interface between WM and BM,and this interface suffers mechanical and microstructure mismatches and is often the rupture location of premature failure.In this study,a new form of WM/BM interface form,namely double Y-type interface was designed for the DMWs.Creep behaviors and life of DMWs containing double Y-type interface and conventional I-type interface were compared by finite element analysis and creep tests,and creep failure mechanisms were investigated by stress-strain analysis and microstructure characterization.By applying double Y-type interface instead of conventional I-type interface,failure location of DMW could be shifted from the WM/ferritic heat-affected zone(HAZ)interface into the ferritic HAZ or even the ferritic BM,and the failure mode change improved the creep life of DMW.The interface premature failure of I-type interface DMW was related to the coupling effect of microstructure degradation,stress and strain concentrations,and oxide notch on the WM/HAZ interface.The creep failure of double Y-type interface DMW was the result of Type IV fracture due to the creep voids and micro-cracks on fine-grain boundaries in HAZ,which was a result of the matrix softening of HAZ and lack of precipitate pinning at fine-grain boundaries.The double Y-type interface form separated the stress and strain concentrations in DMW from the WM/HAZ interface,preventing the trigger effect of oxide notch on interface failure and inhibiting the interfacial microstructure cracking.It is a novel scheme to prolong creep life and enhance reliability of DMW,by means of optimizing the interface form,decoupling the damage factors from WM/HAZ interface,and then changing the failure mechanism and shifting the failure location.