Valence states, impurities and electrocrystallization behaviors during molten salt electrorefining for preparation of high-purity titanium powder from sponge titanium

High-purity titanium powder was prepared by molten salt electrorefining from sponge titanium in NaCl-KCl-TiClx salts. The titanium valence, purity and electrocrystallization during electrolysis process were studied. The XPS analysis showed that the titanium valences are mainly ＋4, ＋3 and ＋2 at the earlier, medium and later stages of electrolysis, respectively. During the electrolysis process, the contents of impurities Si, Cr, Mn, Al vary little, and the contents of impurities Fe, Cu, Ni decrease markedly, while the contents of impurities O, N, H increase obviously. The residual impurities are usually distributed in small tunnel of dendritic crystals. Enhancing the electrolysis temperature and prolonging the electrolysis time can increase the titanium particle size. The TEM analysis showed that the electrodeposited titanium is not a single crystal, but contains many nanostructured grains and subgrains, with grain size of 100-500 nm. The electrolysis mechanisms were also discussed.

Minimizing pest aluminum in magnesium for the production of high-purity titanium

It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the aluminum impurities in the titanium sponge are inherited from the magnesium used to reduce titanium tetrachloride. However, it remains elusive for decades why magnesium produced through the silicothermic reduction method contains a high content of aluminum impurities with large fluctuations. By recourse to thermodynamic calculations and comparative experiments, we demonstrate that fluorite, a material used as a catalyst in the silicothermic reduction method to produce magnesium, is the chief culprit for the pest aluminum and propose a mechanism to rationalize the observed phenomena. Our findings indicate that one practical way to produce qualified magnesium for the production of high-purity titanium is to abandon fluorite during the production of magnesium with the silicothermic reduction method.

Equilibrium between titanium ions and high-purity titanium electrorefining in a NaCl-KCl melt

TiClx （x=2.17） was prepared by using titanium sponge to reduce the concentration of TiCl4 in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiClx melt was employed as the electrolyte, and two parallel crude titanium plates and one high-purity titanium plate were used as the anode and cathode, respectively. A series of electrochemical tests were performed to investigate the influence of electrolytic parameters on the current efficiency and quality of cathodic products. The results indicated that the quality of cathodic products was related to the current efficiency, which is significantly dependent on the current density and the initial concentration of titanium ions. The significance of this study is the attainment of high-purity titanium with a low oxygen content of 30× 10^-6.

Multiple factors influencing high-purity indium electrolytic refining

The effects of various contaminants in the electrolytic refinement of indium were investigated using a glow discharge mass spectrometer(GDMS).The effects of several factors such as the indium ion(In3+)concentration,the sodium chloride(NaCl)concentration,the current density,the gelatin concentration,the pH,and the electrode distance,were examined.Significant variations in impurity levels concerning gelatin concentration were observed.Both the gelatin and In3+concentration were moderately positively correlated with the Pb content.The Sb concentration was associated positively with the NaCl concentration,while the Ti concentration had an adverse correlation with the NaCl concentration.The Bi element content was positively linked to the electrode distance.As the current density increased,Cu,Pb,and Bi impurities initially rose and then eventually declined.Notably,a critical current density of 45 A·m^(-2) was identified in this behavior.

Polydopamine-modified metal-organic frameworks nanoparticles enhance the corrosion resistance and bioactivity of polycaprolactone coating on high-purity magnesium

Biodegradable magnesium(Mg)and its alloys exhibit excellent biocompatibility and mechanical compatibility,demonstrating tremendous potential for applications in orthopedics.However,the rapid degradation rate has limited their clinical application.Polycaprolactone(PCL)is commonly employed as a polymer coating to impede the rapid degradation of Mg.Unfortunately,its long-term anti-corrosion capability and bioactivity are inadequate.To address these issues,polydopamine(PDA)-modified zeolitic imidazolate framework-8(PZIF-8)bioactive nanoparticles are fabricated and incorporated into the PCL coating.The PZIF-8 particles,featuring catechol motifs,can enhance the compactness of the PCL coating,reduce its defects,and possess biomineralization ability,thereby effectively improving its anti-corrosive and bioactive properties.Moreover,the active substances released from the degradation of the PZIF-8 particles such as Zn^(2+)and PDA are beneficial for osteogenesis.The corrosion tests indicate that the corrosion current density of PCL-treated sample decreases by more than one order of magnitude and the amount of H_(2)released decreases from 0.23±0.12 to 0.08±0.08 ml cm^(-2)after doping with the PZIF-8.Furthermore,the improved corrosion resistance and released PDA and Zn^(2+)from the coating can promote osteogenic differentiation by up-regulating the expression of alkaline phosphatase activity,related osteogenic genes,and proteins.In addition,in vivo implantation experiments in rabbit femur defects further offer strong evidence that the doping of PZIF-8 nanoparticles accelerates bone reconstruction of the PCL coating.In summary,this work implies a new strategy to fabricate a PCL-based coating on Mg-based implants by introducing the PZIF-8 particles for orthopedic applications.

Enhanced recovery of high-purity Fe powder from iron-rich electrolytic manganese residue by slurry electrolysis

Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.

Artificial neural network-based method for discriminating Compton scattering events in high-purity germaniumγ-ray spectrometer

To detect radioactive substances with low activity levels,an anticoincidence detector and a high-purity germanium(HPGe)detector are typically used simultaneously to suppress Compton scattering background,thereby resulting in an extremely low detection limit and improving the measurement accuracy.However,the complex and expensive hardware required does not facilitate the application or promotion of this method.Thus,a method is proposed in this study to discriminate the digital waveform of pulse signals output using an HPGe detector,whereby Compton scattering background is suppressed and a low minimum detectable activity(MDA)is achieved without using an expensive and complex anticoincidence detector and device.The electric-field-strength and energy-deposition distributions of the detector are simulated to determine the relationship between pulse shape and energy-deposition location,as well as the characteristics of energy-deposition distributions for fulland partial-energy deposition events.This relationship is used to develop a pulse-shape-discrimination algorithm based on an artificial neural network for pulse-feature identification.To accurately determine the relationship between the deposited energy of gamma(γ)rays in the detector and the deposition location,we extract four shape parameters from the pulse signals output by the detector.Machine learning is used to input the four shape parameters into the detector.Subsequently,the pulse signals are identified and classified to discriminate between partial-and full-energy deposition events.Some partial-energy deposition events are removed to suppress Compton scattering.The proposed method effectively decreases the MDA of an HPGeγ-energy dispersive spectrometer.Test results show that the Compton suppression factors for energy spectra obtained from measurements on ^(152)Eu,^(137)Cs,and ^(60)Co radioactive sources are 1.13(344 keV),1.11(662 keV),and 1.08(1332 keV),respectively,and that the corresponding MDAs are 1.4%,5.3%,and 21.6%lower,respectively.

Timing of granite pegmatite-type high-purity quartz deposit in the Eastern Qinling,China:constraints from in-situ LA-ICP-MS trace analyses of quartz and monazite U–Pb dating

Eastern Qinling,China is one of the important rare metal metallogenic provinces with extensively distributed granite pegmatite dikes.The No.5 granite pegmatite intruded into the granitic gneiss of the Qinling Group,and the major minerals are quartz(39.8%),K-feldspar(18.8%),albite(36.3%),muscovite(3.4%),and garnet(1.1%).Monazite U–Pb isotopic dating indicates that the No.5 pegmatite from the Eastern Qinling was emplaced at ca.420.2±2.2 Ma,which confirms that highpurity quartz mineralization probably formed during the Early Devonian.In-situ laser ablation inductively coupled plasma mass spectrometry analysis of quartz show that quartz samples from Eastern Qinling have total trace element concentrations(Al,Ti,Sc,Li,B,Cr,Mn,and Fe)ranging from 23.2 to 52.8 ppm,slightly higher than the quartz(impurity element content from 13.4 to 25.9 ppm)of the Spruce Pine high-purity quartz deposit in western North Carolina.The No.5 pegmatite of Eastern Qinling could be defined as one high-purity quartz deposit of China.

Preparing high-purity iron by direct reduction?smelting separation of ultra-high-grade iron concentrate

A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced time of 5 h,and CaO content of 2.5wt%,a DRI with a metallization rate of 96.5%was obtained through coal-based direct reduction of ultra-high-grade iron concentrate.Then,an HPI with a Fe purity of 99.95%and C,Si,Mn,and P contents as low as 0.0008wt%,0.0006wt%,0.0014wt%,and 0.0015wt%,respectively,was prepared by smelting separation of the DRI using a smelting temperature of 1625°C,smelting time of 45 min,and CaO content of 9.3wt%.The product of the pilot test with a scale of 0.01 Mt/a had a lower impurity content than the Chinese industry standard.An HPI with a Fe purity of 99.98wt%can be produced through the direct reduction?smelting separation of ultra-high-grade iron concentrate at relatively low cost.The proposed process shows a promising prospect for application in the future.

The Status Quo and Development Trend of High-purity Gold Sputtering Targets

This article gives a brief introduction to manufacturers and markets of sputtering targets as well as the manufacturing technology thereof. Then, it analyzes the application of high-purity gold sputtering targets in the fields of integrated circuit, information storage, flat panel display, etc. Based on the above, the article analyzes the processing development trend for the high-purity gold sputtering targets in aspects of ultra-high purity, manufacturing technology, analysis and testing technologies.

Flow stress behavior of high-purity Al-Cu-Mg alloy and microstructure evolution

The flow stress behavior of high-purity Al-Cu-Mg alloy under hot deformation conditions was studied by Gleeble-1500,with the deformation temperature range from 300 to 500 °C and the strain rate range from 0.01 to 10 s-1. From the true stress-true strain curve, the flow stress increases with the increasing of strain and tends to be constant after a peak value, showing dynamic recover, and the peak value of flow stress increases with the decreasing of deformation temperature and the increasing of strain rate.When the strain rate is 10 s-1 and the deformation temperature is higher than 400 °C, the flow stress shows dynamic recrystallization characteristic. TEM micrographs were used to reveal the evolution of microstructures. According to the processing map at true strain of 0.7, the feasible deformation conditions are high strain rate(>0.5 s-1) or 440-500 °C and 0.01-0.02 s-1.

Use of various MgO resources for high-purity Mg metal production through molten salt electrolysis and vacuum distillation

A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.

Atomic Emission Spectrographic Analysis of High-purity Gallium with Prior Partial Dissolution of Matrix

An improved method has been developed for enriching and determining trace In,Pt,Sn,Co,Hg,Pb,Ni, Bi,Pd,Cu and Ag in high-purity gallium.Sample was treated by PDM(partial dissolution of matrix)with HCl(11mol/L)-HNO_3(0.5mol/L)to a small residue of which Ga was then removed by extraction with 1 ml isopropyl ether.The concentrated impurities were determined by AES procedure.The recoveries for the ele- ments at the range of 0.02～0.2 μg are 95～103％;the relative standard deviations for determined impurities overa rangeofn.10^(-7)～n·10^(-8)％ are 4.3～12％;the detection limit of most elements can reach n·10^(-7)～ n·10^(-8)％ level with the exception of Hg and Pt.This method has been successfully used to analyze many sam- ples sent by factories and institutes.

Present Situation and Prospects of High-purity Elements in China

1.IntroductionHigh-purity elements are the basic materials in electronics,communication,aerospace,atomicenergy and semiconductor material industries.Its development is a decisive factor for high-tech in-dustries.The high-purification of non-ferrous metals is of great significance.It conduces to determining

Production of high-purity Mg metal from dolomite through novel molten salt electrolysis and vacuum distillation

In this study,a novel Mg production process for producing high-purity Mg metal from dolomite was developed.When the electrolysis of calcined dolomite was conducted using Cu cathode and C anode in MgF_(2)–LiF molten salt at 1083–1173 K by applying an average current of 1.42–1.46 A for 9.50–21.0 h,the current efficiency of 66.4–88.6%was obtained.The produced Mg alloys consisted of MgCu_(2)and Cu(Mg)or MgCu_(2)and CuMg_(2)phases,depending on the Mg concentration in the Mg alloy.When the electrolysis of calcined dolomite was conducted in MgF_(2)–LiF–CaF_(2)molten salt at 1083 K,the current efficiency was 40.9–71.4%,owing to undesired reactions such as electroreduction of Ca^(2+)or/and CO_(3)^(2−)ions.Meanwhile,the current efficiency increased from 40.9%to 63.2%by utilizing a Pt anode,because the occurrence of CO_(3)^(2−)ions in the molten salt was prevented.After vacuum distillation of the obtained Mg alloys at 1300 K for 10 h,Mg metal with a purity of 99.9996–99.9998%was produced.Therefore,the feasibility of this novel process for the production of high-purity Mg metal from dolomite was demonstrated.

Production of high-purity hydrogen from paper recycling black liquor via sorption enhanced steam reforming

Environmentally friendly and energy saving treatment of black liquor(BL),a massively produced waste in Kraft papermaking process,still remains a big challenge.Here,by adopting a NieCaOeCa_(12)Al_(14)O_(33) bifunctional catalyst derived from hydrotalcite-like materials,we demonstrate the feasibility of producing high-purity H_(2)(~96%)with 0.9 mol H_(2) mol^(-1) C yield via the sorption enhanced steam reforming(SESR)of BL.The SESRBL performance in terms of H_(2) production maintained stable for 5 cycles,but declined from the 6th cycle.XRD,Raman spectroscopy,elemental analysis and energy dispersive techniques were employed to rationalize the deactivation of the catalyst.It was revealed that gradual sintering and agglomeration of Ni and CaO and associated coking played important roles in catalyst deactivation and performance degradation of SESRBL,while deposition of Na and K from the BL might also be responsible for the declined performance.On the other hand,it was demonstrated that the SESRBL process could effectively reduce the emission of sulfur species by storing it as CaSO_(3).Our results highlight a promising alternative for BL treatment and H_(2) production,thereby being beneficial for pollution control and environment governance in the context of mitigation of climate change.

Integrated high-performance and accurate shaping technology of low-cost powder metallurgy titanium alloys: A comprehensive review

The practical engineering applications of powder metallurgy (PM) Ti alloys produced through cold compaction and pressure-less sintering are impeded by poor sintering densification, embrittlement caused by excessive O impurities, and severe sintering deforma-tion resulting from the use of heterogeneous powder mixtures. This review presents a summary of our previous work on addressing the above challenges. Initially, we proposed a novel strategy using reaction-induced liquid phases to enhance sintering densification. Near- complete density (relative density exceeding 99%) was achieved by applying the above strategy and newly developed sintering aids. By focusing on the O-induced embrittlement issue, we determined the onset dissolution temperature of oxide films in the Ti matrix. On the basis of this finding, we established a design criterion for effective O scavengers that require reaction with oxide films before their dissol-ution. Consequently, a ductile PM Ti alloy was successfully obtained by introducing 0.3wt% NdB6 as the O scavenger. Lastly, a powder- coating strategy was adopted to address the sintering deformation issue. The ultrafine size and shell-like distribution characteristics of coating particles ensured rapid dissolution and homogeneity in the Ti matrix, thereby facilitating linear shrinkage during sintering. As a result, geometrically complex Ti alloy parts with high dimensional accuracy were fabricated by using the coated powder. Our fundament-al findings and related technical achievements enabled the development of an integrated production technology for the high-performance and accurate shaping of low-cost PM Ti alloys. Additionally, the primary engineering applications and progress in the industrialization practice of our developed technology are introduced in this review.

Microstructure evolution and strengthening mechanism of high -performance powder metallurgy TA15 titanium alloy by hot rolling

Hot deformation of sintered billets by powder metallurgy(PM)is an effective preparation technique for titanium alloys,which is more significant for high-alloying alloys.In this study,Ti–6.5Al–2Zr–Mo–V(TA15)titanium alloy plates were prepared by cold press-ing sintering combined with high-temperature hot rolling.The microstructure and mechanical properties under different process paramet-ers were investigated.Optical microscope,electron backscatter diffraction,and others were applied to characterize the microstructure evolution and mechanical properties strengthening mechanism.The results showed that the chemical compositions were uniformly dif-fused without segregation during sintering,and the closing of the matrix craters was accelerated by increasing the sintering temperature.The block was hot rolled at 1200℃ with an 80%reduction under only two passes without annealing.The strength and elongation of the plate at 20–25℃ after solution and aging were 1247 MPa and 14.0%,respectively,which were increased by 24.5%and 40.0%,respect-ively,compared with the as-sintered alloy at 1300℃.The microstructure was significantly refined by continuous dynamic recrystalliza-tion,which was completed by the rotation and dislocation absorption of the substructure surrounded by low-angle grain boundaries.After hot rolling combined with heat treatment,the strength and plasticity of PM-TA15 were significantly improved,which resulted from the dense,uniform,and fine recrystallization structure and the synergistic effect of multiple slip systems.

Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Comparison of electrochemical behaviors of Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe and Ti-6Al-4V titanium alloys in NaNO_(3) solution

The Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe(β-CEZ)alloy is considered as a potential structural material in the aviation industry due to its outstanding strength and corrosion resistance.Electrochemical machining(ECM)is an efficient and low-cost technology for manufacturing theβ-CEZ alloy.In ECM,the machining parameter selection and tool design are based on the electrochemical dissolution behavior of the materials.In this study,the electrochemical dissolution behaviors of theβ-CEZ and Ti-6Al-4V(TC4)alloys in NaNO3solution are discussed.The open circuit potential(OCP),Tafel polarization,potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),and current efficiency curves of theβ-CEZ and TC4 alloys are analyzed.The results show that,compared to the TC4 alloy,the passivation film structure is denser and the charge transfer resistance in the dissolution process is greater for theβ-CEZ alloy.Moreover,the dissolved surface morphology of the two titanium-based alloys under different current densities are analyzed.Under low current densities,theβ-CEZ alloy surface comprises dissolution pits and dissolved products,while the TC4 alloy surface comprises a porous honeycomb structure.Under high current densities,the surface waviness of both the alloys improves and the TC4 alloy surface is flatter and smoother than theβ-CEZ alloy surface.Finally,the electrochemical dissolution models ofβ-CEZ and TC4 alloys are proposed.