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Research Progress on Lightning Strike Protection Materials for Aircraft

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1605-1619
Currently,composite materials,such as carbon fiber materials,have become key materials in the aviation field due to their low density,high specific strength,high specific modulus,and excellent structural design flexibility. Compared with metallic materials,while meeting aircraft structural design requirements,carbon fiber composites offer distinct advantages in weight reduction,significantly improving the economic efficiency of aircraft. However,the electrical conductivity of these composite materials is markedly inferior to that of metals,preventing them from rapidly dissipating current like metallic materials when struck by lightning. This results in damage to carbon fiber composites,affecting aircraft flight safety. Therefore,to ensure flight safety,carbon fiber composites must undergo treatment to enhance their lightning protection capabilities. To enhance the lightning strike protection (LSP)capability of carbon fiber composites,the most mature solution involves metallic protective layers. These products utilize metals such as copper or aluminum to create either embedded conductive meshes or surface-coated conductive layers on the composite substrate. This approach improves the composite material's conductivity,mitigates localized thermal ablation caused by heat accumulation,and reduces lightning-induced damage. However,metallic protective materials present drawbacks,including excessive weight and poor interfacial bonding with carbon fiber composites,necessitating the development of alternative solutions. In comparison to metallic LSP materials,non-metallic alternatives like graphene and carbon nanotube-based protective layers offer significantly lower density and superior weight reduction advantages. While these materials demonstrate excellent theoretical performance at the nanoscale,their macroscopic assemblies often exhibit substantially compromised properties,with conductivity remaining orders of magnitude below that of metals. Their lightning protection effectiveness still lags considerably behind commercial copper mesh solutions. To address these limitations,numerous researchers are conducting modification treatments to enhance these non-metallic materials,aiming to meet the dual requirements of high conductivity and current-carrying capacity for protective layers. Importantly,beyond material modification,the manufacturing processes significantly influence the final product's performance. Therefore,the synergistic integration of material innovation and process optimization serves as both a pathway for performance enhancement and an effective strategy for promoting industrial applications. With continuous technological advancements and the implementation of more engineering solutions,carbon-based composites are demonstrating strong potential to become the next-generation LSP materials. Their superior performance characteristics,excellent modifiability,outstanding weight reduction effects,and considerable development potential suggest promising application prospects in this field. The future development of aircraft LSP materials will be characterized by distinct interdisciplinary integration and deep technological convergence. The development of multifunctional carbon fiber composites will expand material performance across multiple dimensions and create cross-domain application value,overcoming the traditional trade-offs between added weight and compromised strength for functional requirements. This systemic innovation will achieve the coexistence of lightweight and high-strength properties,synergistic functional optimization,and manufacturing process revolution in composite materials,providing novel solutions for overall aircraft performance enhancement. Artificial intelligence-powered lightning simulation technology is driving revolutionary changes in aircraft LSP design,enabling optimal protection performance. We firmly believe that aircraft LSP materials will embrace even broader development prospects,providing robust support for the safety,efficiency,and sustainable development of the aviation industry.
DOI: 10.13373/j.cnki.cjrm.XY25050006 Cited: 0 Download: 0

Research Progress and Application Prospects in Production,Purification and Detection Technologies of Rubidium and Cesium Metals

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1620-1634
Rubidium and cesium resources in China were abundant,but they were difficult to utilize due to cost issues. Rubidium and cesium metals exhibited excellent physicochemical properties such as high chemical reactivity,low melting points,easy ionization,and excellent photoelectric effects. They had great potential for applications in energy,quantum,detection,etc. To enhance the utilization of rubidium and cesium resources,developing high-value-added rubidium and cesium metal products was one of the key approaches. The primary methods for producing rubidium and cesium metals included electrolysis,thermal decomposition,and thermal reduction. Initially,rubidium and cesium metals were prepared by electrolyzing molten rubidium chloride and cesium cyanide-barium cyanide melt,respectively.However,the electrolysis methodremained in laboratory settings due to its high operating temperatures,low efficiency,and chlorine pollution issues. The thermal decomposition method could produce high-purity metals with a purity of 99.998%,but its inefficiency and difficulty in collection made it unsuitable for industrial-scale production.Thermal reduction,with its simple process,showed the greatest potential for industrialization. Cesium salts,rubidium salts,and pollucite could be reduced to produce rubidium and cesium metals by metal reductants (such as lithium,sodium,magnesium,calcium,zirconium,and yttrium),achieving yields of 90% and purity of 99.98%. However,yield and purity were significantly influenced by raw materials,process conditions,and equipment performance.The purification methods primarily included distillation and segregation. Distillation could achieve 4N~5N (99.99%~99.999%) high-purity metals through multiple distillations,with high efficiency and low metal loss,but high operational temperatures and rigorous equipment requirements. Segregation could achieve 6N~9N (99.9999%~99.9999999%) high-purity metals with low temperature and simple operation,but high metal loss. For the production of high-purity metals,the synergistic application of thermal reduction and purification processes was typically required.Analytical techniques were facing challenges of high cost,operational complexity,and low efficiency,failing to meet high-purity metal testing requirements. It was urgent to develop rapid and precise simultaneous multi-impurity detection methods and establish corresponding standardized analytical protocols.Although most applied research was at the laboratory stage,the demand for rubidium and cesium metal continued to grow. In controlled nuclear fusion,the injection speed of cesium metal was 50 mg‧h−1 by cesium oven. In electric propulsion,a thruster assembly could carry 175 g of 6N cesium metal. In thermoelectric conversion,the mass flow rate of metallic cesium typically ranged from 0.2~0.5 g‧s−1. Additionally,to generate ion clouds,4 kg of cesium metal was consumed for a single test. In the quantum field,rubidium and cesium metals vapor cells wereindispensable in lasers and quantum precision measurement. In the detection field,rubidium and cesium metals were used in sputtering ion sources and hollow cathode lamps for atomic absorption spectroscopy. The prohibitive costs of rubidium and cesium metals hindered the industrial-scale adoption of applied research. Therefore,future technological development should concentrate on establishing standardized quality control systems and developing scaled-up thermal reduction-purification production technology.
DOI: 10.13373/j.cnki.cjrm.XY25020012 Cited: 0 Download: 0

Temperature Dependence of Electromagnetic and Microwave Absorption Characteristics of Co2Si Alloy Powder

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1503-1515
Electromagnetic waves play a vital role in human production and life. However,the increasing popularity and wide application of wireless communication systems and high-power motors have caused serious electromagnetic pollution,which poses a threat to human health and information security. Therefore,solving the problem of electromagnetic waves is one of the hot topics in scientific research. Absorbing material is a kind of functional material with special electromagnetic properties. Its core function is to absorb and transform the incident electromagnetic wave energy efficiently. It has important application value in high-tech fields such as electromagnetic protection,radar stealth and military camouflage. Studies have shown that cobalt materials not only have excellent dielectric loss characteristics,but also exhibit adjustable permeability characteristics in the GHz frequency band. These characteristics make it show great application potential in the field of electromagnetic wave absorption. In recent years,many researchers have carried out in-depth exploration on cobalt-based absorbing materials. By adjusting the microstructure of the materials and optimizing the preparation process,the electromagnetic wave absorption performance has been continuously improved,which provides an important idea for the development of a new generation of high-performance absorbing materials. In this paper,cobalt powder and silicon powder with high purity of 99.999 % were used as raw materials,and the ratio was based on the molar ratio of 2∶1 (Co2Si). The powder was ball milled by OECO-PBM-AD-6L all-round ball mill produced by Hunan Deke. In order to prevent the contact oxidation between the powder and the air in the ball mill during the grinding process,the air in the ball mill was first extracted by vacuum pump,and then the protective gas nitrogen (N2)was filled into the ball mill. The prepared Co2Si alloy powder was placed in a graphite oil tank and annealed in a vacuum tube furnace (GSL-1500X)at a heating rate of 5 ℃·min−1. In order to prevent the oxidation of Co2Si alloy powder during annealing,the air in the corundum tube was extracted by a vacuum pump and filled with argon (Ar),which was repeated 5~6 times. The annealing time was 2 h,and the annealing temperature was 500~900 ℃. The phase structure,microstructure,size,electromagnetic parameters and microwave absorbing properties of Co2Si alloy powder samples were analyzed by characterization equipment and test equipment. The effect of annealing temperature on the electrical properties of Co2Si alloy powder was studied. The results of X-ray diffraction (XRD)showed that Co2Si alloy powder was successfully synthesized,and its crystal structure belongs to orthorhombic system. It could be observed that there are obvious diffraction peaks near the diffraction angles of about 44.10°,44.76°,45.34° and 53.68°,which correspond to the (210),(202),(013)and (203)crystal plane. The results showed that the synthesized material was Co2Si alloy without Co and Si. Vibrating sample magnetometer (VSM)study showed that the saturation magnetization did not show a certain change rule. When the saturation magnetization increased from 500 to 700 ℃,the value decreased slowly,and the minimum value was 18.56 emu·g−1 at 700 ℃. The maximum saturation magnetization was 36.14 emu·g−1 when the temperature was increased to 800 ℃,and the saturation magnetization decreased again when the temperature was increased to 900 ℃. When the annealing temperature increases from 500 to 600 ℃,the coercivity gradually increased. However,in the range of 600~900 ℃,the coercivity gradually decreased with the increase of temperature. At 600 ℃,the maximum value was 380.25 Oe. The minimum value was 310.53 Oe at 900 ℃. The results of Vector Network Analyzer (VNA)study showed that when the annealing time was 2 h and the annealing temperature was 500~900 ℃,the prepared Co2Si alloy powders all exhibited excellent microwave absorption properties. The minimum reflection loss values were below –10 dB,and the absorption efficiency of electromagnetic waves could be as high as 90%. When the annealing temperature was 600 ℃,the comprehensive absorbing performance of Co2Si sample was the best. The minimum reflection was –32.22 dB,and the absorption efficiency of electromagnetic wave could be as high as 99.9%. In the frequency range of 2~18 GHz,the attenuation coefficient obtained by annealing at different temperatures increased with the increase of frequency. At 2~14 GHz,the attenuation coefficient of the annealing temperature of 600 ℃ was higher than that of other annealing temperatures. Therefore,when the annealing temperature was 600 ℃,its comprehensive absorbing ability was higher than that of other Co2Si alloy powder samples.
DOI: 10.13373/j.cnki.cjrm.XY25020008 Cited: 0 Download: 0

Progress on Organic Liquid Electrolytes for Rechargeable Magnesium Batteries

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1562-1574
With the rapid advancement of portable electronic devices,electric vehicles,smart grids,and other technologies,there is a pressing need to develop high-performance,cost-effective,and environmentally friendly electrochemical energy storage systems. Currently,the principal electrochemical energy storage systems in use include lead-acid batteries,lithium-ion batteries (LIBs),and flow batteries. In comparison to lead-acid batteries which are characterized by low energy density and significant environmental concerns,and flow batteries which exhibit low specific energy,LIBs have gained widespread adoption across various applications. This preference is attributed to their outstanding advantages,including high energy density,extended cycle life,and rapid charge and discharge capabilities. However,the limited availability of mineable lithium resources has led to a continuous increase in the cost of LIBs,necessitating the urgent exploration of alternative,low-cost energy storage technologies. Rechargeable magnesium batteries (RMBs) have emerged as a promising candidate for large-scale energy storage applications. Their potential is bolstered by the abundant reserves of magnesium,which contribute to lowering overall costs. Additionally,RMBs possess a high theoretical volumetric capacity of 3833 mAh·cm−3 and demonstrate a reduced propensity for dendrite formation during the deposition and dissolution processes. These factors have attracted significant interest from researchers in recent years,positioning RMBs as a viable alternative to traditional battery technologies. In the research and development of RMBs,the choice of magnesium-based electrolyte,as the medium for charge transfer,plays a vital role in the overall electrochemical characteristics of the battery. It not only dominates the solvation structure of magnesium ions but also deeply participates in the micro-electrochemical reactions at the electrolyte-electrode interface,directly determining key performance parameters such as the voltage window and battery reaction kinetics. Therefore,optimizing the electrolyte is one of the key challenges in the development of RMBs. An ideal magnesium-based electrolyte should possess the following core characteristics:first,it should enable reversible deposition/dissolution of the magnesium anode. Second,high ionic conductivity coupled with a wide voltage window ensures efficient battery operation and stability. Furthermore,good compatibility with cathode materials is indispensable. Last but not least,high safety is a basic requirement that magnesium-based electrolytes must meet in practical applications. In comparison to solid-state electrolytes,organic liquid electrolytes remain the mainstream choice for magnesium battery electrolyte research. This preference is due to their favorable properties,including high ionic conductivity,significant ionic transference numbers,excellent reversibility,prolonged cycling performance,ease of handling,as well as low viscosity. Historically,as early as 2000,Aurbach and his team successfully assembled the first prototype of an RMB based on Grignard reagent-based electrolyte (DCC,notably known as the first-generation magnesium-based electrolyte). However,Grignard reagent-based electrolytes were hampered by several drawbacks,including high nucleophilicity,inadequate oxidation stability,poor compatibility with cathode materials,low conductivity,and high cost,posing challenges for large-scale commercial application. Subsequently,a series of novel magnesium-based organic liquid electrolyte systems have emerged,showcasing diverse characteristics. For instance,hexamethyldisilazide (HMDS)-based electrolytes were developed as non-nucleophilic electrolytes and demonstrated application in high-capacity magnesium-sulfur batteries. Inorganic salt-based electrolytes,represented by magnesium aluminum chloride complex (MACC),exhibited significant advantages in safety,ease of preparation,and economic feasibility. Non-chloride simple magnesium salts,exemplified by magnesium bis(trifluoromethanesulfonimide)(Mg(TFSI)2)and magnesium trifluoromethanesulfonate (Mg(OTf)2),are noteworthy for their high oxidation stability and non-corrosive properties. Organic boron-based electrolytes,characterized by large anions,showed excellent voltage windows and compatibility with both anode and cathode materials. Despite the significant progress made by the aforementioned novel organic liquid electrolyte systems in the research and development of RMBs,they still have many shortcomings. The high cost and complex synthesis process of HMDS-based electrolytes limit their widespread application. Chloride-containing inorganic salt-based electrolytes suffer from severe corrosion phenomena. Additionally,TFSI-based electrolytes exhibit severe passivation of the magnesium anode,leading to excessively high deposition/dissolution overpotentials,while OTf-based electrolytes demonstrate poor solubility in ether solvents. The preparation of organic boron-based electrolytes is often complicated and costly,with unresolved issues regarding ion transport at the interface and decomposition behaviors. Based on a systematic summary of the research status,the organic liquid electrolyte systems that are expected to achieve breakthroughs in the future are mainly concentrated in the chloride-free simple magnesium salts electrolytes and organic boron-based systems. Regarding chloride-free simple magnesium salt systems,strategies such as solvent regulation engineering,the introduction of salt additives for modification,and design regulation of the solid-electrolyte interphase (SEI) films can be employed to inhibit anode passivation and enhance magnesium salt solubility. For organic boron-based electrolytes,there is a dual need to develop new weakly coordinating boron-centered anionic electrolytes to further improve performance,as well as to explore entirely new preparation processes to reduce costs and enhance efficacy. This review highlighted the research progress of various organic liquid electrolytes for RMBs,introducing the structures,compositions,modification strategies,and associated electrochemical properties of different types of electrolytes. Furthermore,it provided insights into future research directions for organic liquid electrolytes in RMBs.
DOI: 10.13373/j.cnki.cjrm.XY25020006 Cited: 0 Download: 0

Microstructure and Tribological Behavior of WC-Ni45 Composite Coatings by High-Speed Laser Cladding

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1527-1540
High-speed laser cladding (HSLA)is an advanced surface engineering technology capable of fabricating wear-resistant and corrosion-resistant coatings with high bonding strength. 316L stainless steel has been widely utilized in the nuclear field to manufacture high-temperature and corrosion-resistant components due to its outstanding corrosion resistance,good welding performance,and excellent oxidation resistance. Aiming at the issues of surface strengthening and improvement of wear resistance of 316L stainless steel,this paper employed HSLA technology to prepare a defect-free metal/ceramic composite coating with a high ceramic phase content of 55%WC-Ni45 on the surface of 316L stainless steel sheets. Among them,Ni45 self-fluxing alloy powder had a favorable combination of strength and toughness,and WC ceramic particles possessed extremely high hardness and a relatively low thermal expansion coefficient,with good wettability between the two. Under the process conditions of a laser power of 1.2 kW,a scanning speed of 3000 mm·min−1,and a lap rate of 60%,the composite coating was successfully prepared by using the ultra-high-speed laser cladding technology. Subsequently,X-ray diffraction (XRD),scanning electron microscopy (SEM),Vickers hardness tester,and universal mechanical testing machine were utilized to analyze the microstructure and mechanical properties of the cladding coating. Moreover,a wear testing machine was adopted to conduct wear resistance tests on 316L substrate and 55%WC-Ni45 composite coating. The results showed that 55%WC-Ni45 composite coating was mainly composed of Ni-based solid solution,WC,W2C and M23C6 carbides. Compared with XRD diffraction peaks of the mixed powder,the peak position of Ni-based solid solution shifts to the left,indicating that W with a larger atomic size might be dissolved in it. The dissolution of W atoms could play a strengthening role,thereby enhancing the hardness and wear resistance of Ni45 metal phase. During the solidification process of the coating,the differences in temperature gradient and solidification rate at different positions led to the growth law of Ni45 microstructure changing from cellular crystals,columnar crystals to dendrites and equiaxed crystals from the bottom to the top. WC particles in the coating were uniformly distributed,and different degrees of dissolution-diffusion and precipitation occurred around them,and bright white structures were formed near WC particles. From the bottom to the top of 55%WC-Ni45 composite coating,the area of the bright white structures near WC particles gradually decreased,indicating that the degree of dissolution-diffusion of WC gradually decreased. This was mainly due to the gradual increase in the cooling rate (R) from the bottom to the top of 55%WC-Ni45 composite coating. The results of energy dispersive spectroscopy (EDS)characterization showed that W element was mainly distributed inside the unmelted WC particles,partly diffused into the white blocky and lamellar structures around WC particles,and a small amount of W element was also diffused into Ni45 dendritic structures far away from WC particles. Fe,Cr and Ni elements were mainly distributed in the dendritic structures,with a small amount diffused into the interior of WC particles. The element diffusion phenomenon between WC and Ni45 microstructure was obvious,and good metallurgical bonding was achieved. The average hardness of WC ceramic phase in the composite coating was HV0.2 2634.46,and that of Ni45 metal phase was HV0.2 758.67. The average hardness of 55%WC-Ni45 composite coatingwasHV10 1151.10,which was approximately five times that of the substrate. 55%WC-Ni45 composite coating formed good metallurgical bonding with the substrate,with a shear strength of 252.19 MPa. The main fracture mode of 55%WC-Ni45 composite coating was brittle fracture. The average friction coefficient of 55%WC-Ni45 composite coating was approximately 0.61,which was lower than that of 316L stainless steel (0.76),and the volume wear rate was 2.14×10−8 mm3·N−1·m−1,which as reduced by approximately 89.7% compared with 316L substrate. After the friction and wear test,the surface of 316L substrate formed typical "V"-shaped wear marks,with a large number of ploughing grooves and micro-cutting marks inside the wear marks,and the deepest part of the wear marks reached more than 30 μm. However,after the friction and wear test of 55%WC/Ni45 composite coating,only Ni45 metal phase within the wear mark range was removed by grinding,WC hard phase particles were hardly worn and obviously protrude from the surface,and the maximum depth of the wear mark was only about 10 μm. The main wear mechanism of 55%WC/Ni45 composite coating was abrasive wear. The multiple strengthening mechanisms of the metal/ceramic composite coating,such as solid solution strengthening,dispersion strengthening,and fine grain strengthening,jointly improved the overall hardness of the coating,which was the main reason for the improvement of the coating's wear resistance. WC particles were uniformly distributed in the coating,playing a role in supporting the coating structure and resisting wear.
DOI: 10.13373/j.cnki.cjrm.XY24110034 Cited: 0 Download: 0

Investigation of Magnetic Properties and Coercivity Mechanisms in PrCo5/Nd2Fe14B Nanocrystalline Magnets

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1635-1643
RE-Fe-B based magnets exhibit excellent magnetic properties (high magnetization and coercivity) at room temperature but poor magnetic properties at high temperatures;whereas RE-Co based magnets present high thermal stability but their magnetization and energy product values are low compared with RE-Fe-B based magnets. If RE-Co based magnets with higher temperature stabilities are mixed with RE-Fe-B magnets with excellent magnetic properties,a hybrid magnet with outstanding magnetic properties,high temperature stability could be obtained. Thus,the respective disadvantages of the two magnets would be improved. The hybrid magnets consisting of RE-Fe-B and RE-Co are desirable from a magnetic perspective. In this work we presented recent studies of nanoscale hybrid magnets containing PrCo5 and Nd2Fe14B hard magnetic phases produced via hot-pressed and hot-deformed method using spark plasma sintering (SPS) technology,from mixtures of ball-milled powders obtained from nanocrystalline melt-spun ribbons. The effects of height reduction on anisotropy,magnetic interactions,coercivity mechanisms,and microstructure of the magnets were investigated. XRD patterns indicated that the dominant phases in the hot-pressed magnets were PrCo5,Nd2Fe14B and α-Fe. The height reduction played a key role in inducing the crystallographic alignment in the magnets. For the hot deformed magnets,the intensity of the diffraction peaks (006) and (105)representing the c-axis texture of Nd2Fe14B phase were enhanced compared to the hot pressed magnet,but they were still not the strongest peaks;meanwhile the (002) diffraction peak representing PrCo5 phase had a lower intensity than the hot pressed magnet,indicating that the deformation of Nd2Fe14B and PrCo5 was not synchronized during the deformation process,which might affect the anisotropy of the magnet. In order to characterize the crystallographic alignment quantitatively,the remanence ratio between the easy and hard axis were calculated. By the height reduction of 70%,80% and 90%,the remanence ratios were 0.51,0.53 and 0.49,respectively,suggesting that the crystallographic alignment was already developed to some extent in the hot deformed magnets. The magnetic properties tested show that the remanence of the hot-deformed magnet increased first and then decreases with the increase height reduction,while the coercivity decreased with the increase height reduction. The openness of the recoil loops in hot-pressed and hot-deformed magnets was observed and it increased with the increase of height reduction. Quantitative characterization of the recoil loops indicated that the incomplete exchange coupling in the hot-deformed magnets became more evident with increasing height reduction,which led to the decline of intergranular exchange coupling. To investigate the exchange coupling between the grains,Henkel plot was measured for the hot-pressed and hot-deformed magnets. The Henkel plot of hot-pressed magnet showed a positive value and a larger negative value;differently the hot-deformed magnets only had negative values without positive part,the negative parts showed that there were dipolar interactions between PrCo5 and Nd2Fe14B and the interactions also increased with the increase of height reduction. Minor hysteresis loops were used to investigate the coercivity mechanism. The coercivity mechanisms of hot-pressed and hot-deformed magnets were pinning mechanism,the pinning effect gradually weakened with increasing height reduction. A region of elemental transition was observed in the hot-pressed magnet.
DOI: 10.13373/j.cnki.cjrm.XY24080011 Cited: 0 Download: 0

Electrochemical Properties of Pb-Lignin Composite Anodes for Zinc Electrowinning

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1541-1553
Zinc metal has an active chemistry and is widely used in industries such as galvanised protective film and battery manufacturing. Eighty-five percent of zinc metal is produced by hydrometallurgy. Zinc electrowinning,as a vital part of hydrometallurgy,accounts for 80% of the total energy consumption of the hydrometallurgical process. During the electrowinning of zinc,the anodic oxygen evolution reaction has a high charge transfer energy barrier,which results in the anode generating a large overpotential of oxygen evolution potential. This leads to an increase in tank voltage and energy consumption. Concurrently,the anode material must be used in an environment with high acidity,high oxidation,high current density,and the co-existence of halogen ions. This results in corrosion of the anodes,which consequently reduces their service life. The anode sludge also has an impact on the quality of the zinc cathode. Currently,lead-based anodes are predominant in the wet zinc refining industry. However,lead-based anodes still have problems with high oxygen evolution potential and poor corrosion resistance. Lead-based anodes can be modified by doping functional metal elements. For instance,the incorporation of silver,a noble metal with electrocatalytic properties,can diminish the oxygen evolution potential of lead-based anodes. Nevertheless,silver is unable to enhance the mechanical strength of lead-based anodes,and the introduction of the precious metal silver will also considerably elevate the production cost of the anodes. It is therefore of great significance to identify a renewable and low-cost reinforcing phase that can be used as an effective substitute for silver in order to enhance the oxygen precipitation catalytic activity and corrosion resistance of conventional lead-based anodes. In this study,the sodium lignosulfonate,a byproduct of the paper industry,was employed as the primary raw material. The purified lignin was obtained following desulfurisation and purification. Pb-Lignin composite anodes were prepared by incorporating lignin into Pb-based anodes through the use of powder metallurgy technology. The impact of lignin on the electrochemical performance and corrosion resistance of Pb-xLignin composite anodes (x=0,0.2,0.4,0.6,0.8,1.0,%,mass fraction) was investigated. The prepared lignin was micron-sized spherical,with the benzene ring structure preserved intact. Lignin is rich in oxygen-containing active functional groups and is an excellent electrode active material with high electrochemical reactivity and stability. The doped lignin exhibited a varying degree of modification effect on the lead-based anode. The enhancement of the electrochemical performance and corrosion resistance of the lead-based composite anode by lignin exhibited an initial increase and subsequent decrease with increasing lignin doping under simulated zinc electrowinning conditions. This phenomenon could be attributed to the structural composition of the prepared lignin,which comprised lilac-based and p-hydroxyphenyl structural units,rendering it more prone to accelerate the oxygen precipitation electrocatalytic reaction on the anode surface. When the doping amount exceeded 0.8%,π-π interactions and hydrogen bonding between lignin molecules led to severe agglomeration,resulting in an uneven distribution of lignin on the surface of the lead anode and a weakening of the enhancement effect on the lead-based anode. The optimal modification of the lead-based composite anode was achieved when the doping amount of lignin was 0.8%. At this juncture,the Pb-0.8%Lignin composite anode exhibited a 1.25 and 1.23-fold increase in voltammetric charge,a 1.94 and 1.50-fold enhancement in bilayer capacitance (Cdl),and a higher apparent exchange current density than the pure Pb and Pb-Ag-Ca composite anodes. The oxygen evolution potential steady-state potential was 1.528 V at a current density of 500 A·m−2,which was 125 mV lower than that of the pure Pb electrode. Furthermore,the corrosion rate was reduced by 31.6%,which provided excellent oxygen evolution catalytic activity and corrosion resistance.
DOI: 10.13373/j.cnki.cjrm.XY24060025 Cited: 0 Download: 0

Microstructure and Mechanical Properties of High Strength Container Steel with Cu, Ni, Al, and RE

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1516-1526
With the large-scale development of pressure vessel structures and the gradual improvement of pressure capacity requirements,higher requirements are put forward for the comprehensive mechanical properties of raw materials,so it is necessary to develop new pressure vessel steel with higher strength. How to break the refutation that strong plasticity cannot be balanced,and how to improve the strength of steel materials without significantly reducing plasticity,has been a research hotspot for material scholars for a long time. It was found that by adding different alloying elements to the iron-based alloy and precipitating nano-scale precipitates in the iron-based alloy after solid solution-aging heat treatment,the strength of the iron-based alloy can be significantly improved,while maintaining good plasticity,which brings new inspiration to the material field. In order to study how to improve the strength level of the high-strength container steel without significantly reducing its plasticity,Cu,Ni,Al and rare earth elements (RE)were added to the high-strength container steel individually or in combination,held at 900 ℃ for 30 min,water quenched to room temperature,and then held at 550 ℃ for different times,air cooled to room temperature,isothermal aging heat treatment was carried out namely. Optical microscopy (OM)and field emission scanning electron microscopy (SEM)were used to characterize the microstructure of the test steel after quenching and aging. The evolution of the microstructure during isothermal aging at 550 ℃ was studied. The fine structure and precipitated phase morphology of the test steel after aging were characterized by transmission electron microscopy (TEM). The evolution of mechanical properties of the test steel during isothermal aging at 550 ℃ was analyzed by Vickers hardness test and tensile test,and the macromorphology and micromorphology of tensile fracture were characterized by SEM. OM and SEM results show that the microstructures of the test steel were lath martensite after quenching,and the microstructures of the test steel were sautensite after aging heat treatment. Compared with base steel,the microstructure of the test steel with different alloying elements had different degrees of refinement,the microstructures of Cu steel and NiAl steel were obviously refined,and the microstructure of NiAl steel was more significant,because Cu and Ni had the effect of refining grains,The microstructure size of Cu-NiAl steel with Cu,Ni and Al was between that of Cu steel and NiAl steel,and the microstructure of Cu-NiAl-RE steel was further refined after RE was added,indicating that RE played a role in refining grain. TEM results of the test steel showed that there were a large number of dislocations entangled on the test steel lath,nano-scale rich Cu phase and NiAl phase precipitated on the matrix,RE reduced the width of the lath,but the type of precipitated phase was not changed. The test steel Vickers hardness results showed that during the isothermal aging process of 550 ℃,the hardness of the base steel showed a decreasing trend with the extension of the aging time,which was because the microstructure recovery occurred during the aging process,and the hardness of Cu steel showed an evolution law of first decreasing,then increasing and then decreasing. The hardness of NiAl steel,Cu-NiAl steel and Cu-NiAl-RE steel increased first and then decreased,which indicated that NiAl steel,Cu-NiAl steel and Cu-NiAl-RE steel were precipitation hardening during the isothermal aging process at 550 ℃. The tensile test results of the test steel showed that the strength at the aging peak of the test steel was increased to different degrees,and the yield strength and tensile strength of Cu steel were increased by 136.0 MPa and 113.2 MPa,respectively,which was caused by the precipitation of nano-Cu-rich phase on the matrix. The strength of NiAl steel changed weakly,which was related to the quantity density and size of NiAl phase precipitated in the matrix. The strength of Cu-NiAl steel increased significantly,the yield strength and tensile strength increased to 1271.0 MPa and 1322.0 MPa,respectively,and the elongation and section shrinkage decreased slightly to 18.2% and 58.3%,respectively. The strong plastic matching was good,which was caused by the precipitation of nano-Cu-NiAl co-precipitated phase in the matrix. The strength of Cu-NiAl-RE steel changed little after RE was added further. Plastic deformation is produced in the test steel during the tensile test. The macro fracture of the test steel was cup-cone with certain necking,and the shear lip was obvious in base steel and NiAl steel. No shear lip was observed in Cu steel,Cu-NiAl steel and Cu-NiAl-RE steel with higher strength. The tensile fracture microstructure showed both large and small dimples,which belonged to the typical ductile fracture mode of microporous aggregation. The effects of Cu,Ni,Al,and RE on the distribution,size and quantity density of nanoprecipitated phases were characterized and analyzed by three-dimensional atomic probe technology (APT). The work was in progress,and the research results would be discussed in subsequent reports.
DOI: 10.13373/j.cnki.cjrm.XY24060013 Cited: 0 Download: 0

Research Progress on Advanced Atomic Layer Etching Materials and Key Processes

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1575-1594
For a long time,the semiconductor industry has followed Moore's Law,with transistor sizes constantly shrinking and process nodes constantly advancing. Etching technology,as an important means of pattern transfer in integrated circuit (IC) manufacturing,has long been of great concern to the industry. Currently,advanced processes in the IC industry have entered the nanoscale process node,which requires the etching process to have extremely high precision and selectivity as well as good pattern definition ability. Conventional reactive ion etching,in which reactions occur continuously and simultaneously during the etching process,can be represented by A+B. Where A represents a neutral reaction and B represents the sputtering of energetic ions above the etching threshold. Reactive ion etching is difficult to meet the high pattern fidelity requirements of certain structures (e.g.,high aspect ratio structures,three-dimensional stacked structures) due to the transport-limiting phenomenon of continuous etching,coupling of different fluxes,and so on. However,the emerging atomic layer etching technique,where the reactions during the etching process occur separately and independently,can be represented by A to B. Where A represents the modification step and B represents the removal step of the modified layer. Due to the self-limiting characteristic of the reaction process,it provides a viable solution to realize the device fabrication process with nanoscale size and precision. This article is a review article on atomic layer etching,which begins with a history of the development of etching technology and the origin of reactive ion etching. The current bottlenecks in reactive ion etching were explained,and the optimization and improvement of the process was becoming increasingly difficult and expensive. This led to the need for a revolutionary etching method other than continuous synchronization,i.e.,atomic layer etching,an advanced etching technology. The origin,concept and characteristics of atomic layer etching (ALE) were then described. In this part,the correlation between atomic layer etching and atomic layer deposition in the development of ALE technology,the understanding of the term "atomic layer" in ALE,as well as the three important test methods to characterize the excellence of the ALE process could be seen. Next,the realization of two types of atomic layer etching,namely thermal atomic layer etching and plasma atomic layer etching,was introduced. According to the different modification methods,plasma ALE could be subdivided into four types:"chemical adsorption","deposition","transformation",and "extraction",while thermal ALE had three etching strategies:"fluoride-ligand exchange","transformation-etching",and "oxidation-fluoride-etching". After that,the materials that could be processed by atomic layer etching were summarized and elaborated in detail,mainly including semiconductor materials,dielectric materials,and metal materials used in IC manufacturing. Among them,semiconductor materials included first-generation semiconductor materials (Si,SiGe),second-generation semiconductors (GaAs,InP),and third-generation semiconductors (GaN,etc.);dielectric materials included conventional dielectric materials (SiN,SiO2)and high-K materials (HfO2 and other metal oxides);metal materials introduced interconnect materials (Cu,W),gate metal materials (TiN),and materials for reducing contact resistance (Co,Ni,etc.). Finally,a summary of the whole article was made,analyzing and discussing the opportunities and challenges of ALE. It was believed that through the unremitting efforts of academia and industry,the emerging atomic layer etching technology would be as promising and broad in the future as atomic layer deposition.
DOI: 10.13373/j.cnki.cjrm.XY24060012 Cited: 0 Download: 0

Measuring Sensible Specific Heat Capacity of In718plus Alloy by DSC

Chinese Journal of Rare Metals | Vol.49, Issue 10, 2025 | pp. 1644-1650
Specific heat capacity is a basic thermal physical parameter in the process of material temperature rise,and it is also a key physical quantity in material design and application. At present,the specific heat capacity of materials is tested mostly by the foreign standard ASTM E1269 "Standard test method for Measuring specific heat capacity by differential scanning calorimetry". The measured specific heat capacity is also called sensible specific heat capacity because the material only changes in temperature without phase transformation during the heating process. However,many metal materials are usually composed of a variety of phases at room temperature due to design and use requirements,and phase transformation will inevitably occur during the heating process,accompanied by obvious thermal response and directly reflected in the specific heat capacity curve. This part of the heat absorption or heat release due to phase transformation is called latent heat,and the specific heat capacity obtained by calculation is the specific heat capacity of latent heat. When the specific heat capacity of an unknown material is tested according to the standard test method,the actual specific heat capacity measured should be called the apparent specific heat capacity. That is because it contains both sensible heat capacity and latent heat capacity,and the current test standard does not mention how to distinguish between the two. When the material has no thermal effect,the apparent specific heat capacity measured is the sensible specific heat capacity. When the material includes thermal effect,the apparent specific heat capacity is greater than the sensible specific heat capacity. In many test cases,the apparent specific heat capacity was mistakenly considered as the sensible specific heat capacity of the material,which made the specific heat capacity data value too large,affecting the thermal conductivity characterization of the material. In this paper,the specific heat capacity of In718plus was tested,and the phase transformation in its curve was subjected to thermal insulation water quenching treatment and microstructure analysis,the specific reasons were identified and the data processing method for obtaining the sensible specific heat capacity was proposed. The specific heat capacity of In718plus superalloy was measured by differential scanning calorimetry (DSC). An obvious heat absorption peak appeared during the heating process,resulting in an abnormal increase in the specific heat capacity. After the original microstructure was heated at 700 ℃ in Muffle furnace for 20 min,the η phase and the γ' phase in the grain boundary did not change much. After the original structure was kept at 900 ℃ in Muffle furnace for 20 min and water quenching,η phase on the grain boundary showed a tendency to grow,and the number of γ' phase decreased significantly. Therefore,it could be concluded that the main phase change occurring at the second peak on the DSC thermal analysis curve was the enhanced phase γ' dissolution reaction,which belonged to the first-order phase transition with latent heat. As reported in the literature,In718plus alloy was developed on the basis of In718 alloy by adjusting the chemical composition,and the strengthening phase was more stable γ' -Ni3(Ti,Al,Nb),which increased its service temperature from 649 to 700 ℃. On the DSC curve,the phase transition peak started at 700 ℃ and ended at 900 ℃,which corresponded to the dissolution range of γ' phase. When the sensible specific heat capacity of In718plus itself was measured by DSC,the latent heat of γ' phase dissolution during the heating process had nothing to do with the sensible heat of In718plus itself,and should be distinguished in the test results. It was mentioned in literature that there was a functional relationship between the specific heat capacity and temperature of metal materials in a single-phase structure. Assuming that the material did not undergo phase transition,the specific heat capacity and temperature should meet the formula in the whole temperature range. The temperature points of In718plus alloy without phase transformation were 100,200,300,400,500 and 1000 ℃,and the corresponding specific heat capacity and temperature should meet the above functional relationship. In the case of first-order polynomial fitting,all the other points except the data points at 300 ℃ were distributed on both sides of the line,and the correlation coefficient R2 at this time was 97.5%,with average effect. When quadratic polynomial fitting was used,all the data points were closer to the fitting curve,the fitting effect was better,and the correlation coefficient reached 99.7%. When the third and fourth order polynomials were used,the centers of all data points fell on the fitting curve,and the correlation coefficient was 100%,so the fitting effect was the best. It could be seen that the specific heat capacity of In718plus met the third-order polynomial relationship with temperature. The sensible specific heat capacity of the material was obtained by fitting the data of the temperature range of the phase transition with polynomial fitting. By comparing the correlation coefficient R2,it was found that the R2 reached 100% when the fitting reached the cubic polynomial.
DOI: 10.13373/j.cnki.cjrm.XY24030027 Cited: 0 Download: 1

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