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.

Effect of Al addition on corrosion behavior of high-purity Mg in terms of processing history

In this study,the effects of Al addition on the corrosion behavior of pure Mg with controlled impurity contents were systematically analyzed according to the processing history.The results revealed that the corrosion behavior of high-purity Mg-Al alloys is strongly related to changes in the microstructure,including theβphase and Al-Mn or Al-Fe phases,and the protectiveness of the surface film according to the Al content and processing history.In the as-cast alloys,the corrosion rate increased due to the increase ofβphase as the Al content increased,but in the as-extruded alloys,the corrosion rate,which was high due to intermetallic compounds caused by impurities in the low Al alloy,decreased as the Al content increased,and then increased again.This is due to the combined effect of the increase of theβphase and decrease of the impurity effect,and the increase of the dissolved Al content.The results suggest that it is necessary to analyze the effect of alloying elements on the corrosion behavior of pure Mg with information concerning the impurity content and processing history.

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.

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.

High-purity Mg and Mg-1Ca alloys:Comparative assessment of the merits regarding degradation,osteogenesis,and biosafety for orthopedic applications

High-purity magnesium(HP Mg)and Mg-1Ca,as representations of Mg-matrix implants produced by purifying and alloying,are employed in biomedical applications primarily because of their bioactivity and degradability.The superiority of both degradation properties,the match between degradation and osteo-genesis in vivo,and biosafety are critical problems that will decide future purifying or alloying to construct Mg-based implants and promote clinical translation.The present study investigated the benefits and limitations of degradation behavior and biosafety of HP Mg and Mg-1Ca according to the electro-chemical experiment,hydrogen evolution test,immersion test,and in vivo bone implantation assay.The results indicated that due to its Mg 2 Ca phase,Mg-1Ca exhibited a considerably higher corrosion current density and hydrogen production than HP Mg in vitro.Furthermore,HP Mg and Mg-1Ca display a favorable match between their degradation and the surrounding osteogenesis,resulting in no significant variation in degradation in vivo during 26 weeks.Additionally,the implantation and degradation of HP Mg and Mg-1Ca do not result in major organ dysfunction or pathological abnormalities.This work is expected to lay the foundation for future clinical translation of Mg and Mg alloy orthopedic implants.

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.

不同预时效挤压态Mg−Gd−Y−Zn−Zr合金的再结晶行为和强化机制

通过控制预时效时间制备3种不同状态的试样,研究不同预时效状态对挤压态Mg−9.5Gd−4Y−2.2Zn−0.5Zr(质量分数,%)合金的动态再结晶行为(DRX)和性能的影响。结果表明,欠时效挤压(UAE)样品的细晶体积分数为17.4%,而峰时效挤压(PAE)和过时效挤压(OAE)样品的细晶体积分数分别达到89.7%和50.4%。在晶粒内部和晶界处分布的致密、细小的β颗粒相通过粒子激发形核机制显著提高了形核位点和位错密度。然而,致密针状γ'相抑制位错滑移,延迟DRX形核。PEA和OAE样品中细小晶粒的差异归因于原始颗粒相的数量和尺寸的不同,而其拉伸性能的差异归因于不同的显微组织。由于晶界强化和析出强化机制的贡献更大,PAE样品具有更优异的拉伸性能。

铸造增压压力对汽车用AlSi9Mg铝合金组织和力学性能的影响

通过改变低压铸造过程中不同增压压力来研究其对AlSi9Mg合金显微组织与力学性能的影响。结果表明,在高增压压力制备的AlSi9Mg合金样品具有更加致密的显微组织及更接近球形的共晶Si颗粒。同时,由于具有更好的填充能力,高增压压力下合金的气孔缺陷大大减少,合金具有更优异的力学性能。在90、150、210 kPa3种不同级别的增压压力下,晶粒尺寸呈逐渐减小的趋势,对应的合金晶粒尺寸和二次枝晶臂间距分别为246、197、149μm,44.9、37.3、31.1μm;3种增压压力对应的密度和孔隙率分别为2.656、2.659、2.674 g/cm^(3),0.96%、0.79%、0.38%;AlSi9Mg合金的抗拉强度、屈服强度和伸长率分别为238.76、174.68 MPa和3.14%;252.43、177.47 MPa和4.61%;256.10、178.81 MPa和6.85%,分别提高了7.26%、2.36%、118.15%。

MXene材料Nb_(2)CCl_(x)与Ti_(2)CCl_(x)对Mg储氢性能的改性研究

镁是众多固态储氢材料中一类深受关注的材料,具有很高的储氢容量(7.6%(质量分数))和可逆吸放氢等优点。但是Mg吸放氢所需温度高,放氢动力学缓慢等影响了其实用性。采用熔盐刻蚀法以n(Mg)∶n(MXene)=10∶1的比例制备了两种不同类型的MXene(Nb_(2)CCl_(x)和Ti_(2)CCl_(x)),并研究不同种类MXene的添加对金属Mg的微观结构和吸放氢性能的影响。结果表明,材料的相组成未发生改变,但球磨后材料的颗粒尺寸进一步减小,增大了其比表面积。Nb_(2)CCl_(x)和Ti_(2)CCl_(x)的引入则使Mg的性能得到明显提升,可以有效提高材料的吸放氢速率,Mg@Nb_(2)CCl_(x)在200 s内就可以放出5.0%(质量分数)的氢气,Mg@Ti_(2)CCl_(x)在250 s内也可以放出5.3%(质量分数)的氢气。同时也可以降低材料的初始吸放氢温度,10%(质量分数)Nb_(2)CCl_(x)使纯Mg的初始吸氢和放氢温度分别降低了125℃和175℃,10%(质量分数)Ti_(2)CCl_(x)则使纯Mg的初始吸氢和放氢温度分别降低了100和125℃。根据Chou模型进行吸放氢动力学拟合的结果表明,MXene的加入使Mg的控速步骤由表面渗透控制向扩散控制转变,从而提高了Mg的吸放氢动力学性能。

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.

血清MG7-Ag水平检测与新型胃癌评分系统在胃癌高危人群风险评估中的价值

目的:研究血清MG7-Ag与新型胃癌评分系统在胃癌高危人群风险评估中的临床价值。方法:纳入2021年1月至2022年12月在本院接受胃镜检查及活检的163例胃癌癌前病变患者和42例胃癌患者作为研究对象。收集一般资料,包括年龄、性别、血清幽门螺杆菌抗体(呼气试验C13/C14)、胃蛋白酶原I/胃蛋白酶原II比值(PGR)、胃泌素17(G17)、内镜检查及病理诊断结果:根据新型胃癌筛查评分系统将入组患者分为低危组、中危组、高危组,采用酶联免疫吸附法进行MG7-Ag检测,分析影响胃癌诊断的影响因素,评价MG7-Ag和新型胃癌评分系统在胃癌高危人群风险评估中的价值。结果:胃癌癌前病变和胃癌组患者一般资料差异无统计学意义,具有可比性。所有205例患者中,新型胃癌评分系统分为高危34例、中危63例和低危108例,其中胃癌检出率分别为24(73.53%)例、13(20.63%)例、5(4.63%)例。以MG7-Ag表达的中位数分为高表达组和低表达组,其中高表达组41例、低表达组164例,其中胃癌检出率分别为33(80.49%)例、9(5.49%)例。单因素和多因素分析显示,新型胃癌评分系统和MG7-Ag检测均为影响胃癌诊断的影响因素之一。通过ROC曲线分析新型胃癌评分系统和MG7-Ag检测在癌前病变和胃癌中的诊断价值,结果显示,新型胃癌评分系统的曲线下面积(AUC)为0.71(95%CI:0.65~0.74),MG7-Ag检测的AUC为0.78(95%CI:0.75~0.80),两者联合诊断的AUC为0.86(95%CI:0.81~0.90),两者联合诊断的价值明显优于单独诊断。结论:血清MG7-Ag与新型胃癌评分系统联合诊断在筛选胃癌高危人群中的价值明显优于单独检测,对未来胃癌癌前病变和胃癌的诊断具有很高的临床指导价值。

Mg-8Gd-(0,3)Sm-0.5Zr合金的动态再结晶生长动力学

利用铸造法制备了Mg-8Gd-(0,3)Sm-0.5Zr合金,并进行了525℃均匀化处理8 h,随后在温度为350~500℃及应变速率为0.002~1 s^(-1)的条件下进行热压缩试验,绘制并分析合金热压缩后的真应力-真应变曲线,构建其动态再结晶生长动力学双参数模型,并分析了合金生长动力学曲线特点及显微组织特征。结果表明:两种合金在热压缩时均发生了动态再结晶,通过双参数模型绘制动态再结晶动力学曲线,发现在高温低应变速率热压缩时,在真应变约0.2时,合金的动态再结晶的体积分数迅速增加至90%以上。对比分析Sm元素添加后的动态再结晶动力学曲线,发现Sm元素促进动态再结晶的进行,尤其在高温低应变速率热压缩时,在变形初期Sm的促进作用更明显。

Al-Mg系合金中合金化元素作用及其对力学性能的影响

铝镁合金是轻量化材料应用领域中一种重要的金属材料,属于中高强度铝合金,具有较高的塑性、良好的耐蚀性以及优良的焊接性等优势,目前在航空航天、交通运输和军工制造等领域具有广阔的应用前景。笔者综述了铝镁合金力学性能特点以及用途,介绍了Al-Mg系合金中的强化机制,重点阐述了Al-Mg系合金中主合金化元素Mg及其含量对合金微观组织和力学性能的影响规律及机理,详细论述了Mn、Zr、Ti、Sc、Er、Y等微合金化元素的作用以及对Al-Mg系合金微观组织和力学性能的影响规律。最后,结合Al-Mg系合金当前研究现状,提出了今后值得研究的方向。

Cu含量以及Cu/Mg比对Al-Si-Cu-Mg合金组织和力学性能的影响

研究了Cu含量和Cu/Mg比对Al-Si-Cu-Mg合金组织和力学性能的影响。结果表明Al-Si-Cu-Mg合金凝固组织是否形成Mg_(2)Si、Q-Al_(5)Cu_(2)Mg_(8)Si_(6)以及θ-Al_(2)Cu取决于Cu含量以及Cu/Mg比。当Cu/Mg比相对低时形成Mg_(2)Si中间相,而Cu/Mg比高时则倾向于生成Q-Al_(5)Cu_(2)Mg_(8)Si_(6)和θ-Al_(2)Cu相。当Cu/Mg比相同时,高Cu含量和高Mg含量都会促进Q相θ相的形成。通过观察T6热处理后的组织发现Cu含量以及Cu/Mg比控制了初生相的溶解以及析出相的形成,从而影响合金的强度与韧性。通过控制Cu含量及Cu/Mg比使Al-9Si-2Cu-0.5Mg合金中析出较少数量的初生相,再通过热处理析出大量的Q′强化相,使合金具有较高的强度和相对适中的伸长率。

不同矿浆温度下Ca^(2+)、Mg^(2+)对黄铁矿可浮性的影响

这是一篇矿物加工工程领域的论文。通过单矿物浮选实验、浮选溶液化学、Zeta电位、XPS,研究了不同矿浆温度下Ca^(2+)、Mg^(2+)对黄铁矿浮选效果的影响机理,结果表明:低温能够明显抑制黄铁矿的浮选,且温度降低能够明显弱化Ca^(2+)、Mg^(2+)对黄铁矿浮选的抑制作用。当矿浆温度从20℃降至5℃时,矿浆中带电粒子运动速度减慢,Zeta电位增大,生成氢氧化钙镁沉淀的临界pH值增大,纯水矿浆中黄铁矿表面的FeO/OH的比例减小,Ca^(2+)、Mg^(2+)矿浆中黄铁矿表面FeO/OH含量的降低幅度减小,减少了黄铁矿表面的氧化程度和活性吸附位点,减少了Ca^(2+)、Ca(OH)+,Mg^(2+)和Mg(OH)+等离子在黄铁矿表面的吸附;但低温并不改变Ca^(2+)、Mg^(2+)在黄铁矿表面的存在形式和吸附状态,pH值为9时,钙镁均以Ca^(2+)、Ca(OH)+、Mg^(2+)、Mg(OH)+的形式存在并吸附在黄铁矿表面。

热处理对激光粉末床熔融AlSi10Mg合金热物理性能的影响

采用激光粉末床熔融(laser powder bed fusion,LPBF)法成功制备AlSi10Mg合金样品,研究130℃/4 h时效处理、236℃/10 h退火处理和540℃/1 h固溶处理三种热处理工艺对AlSi10Mg合金样品的微观组织的影响,以及热处理后AlSi10Mg合金在室温~400℃的温度范围内热膨胀系数和热导率演变规律。结果表明:时效处理后铝基体中析出球状的Si颗粒,仍然保留完整的网状共晶硅组织;退火后,网状共晶硅完全消失,球化Si颗粒均匀分布在基体中;固溶处理后出现大的块状Si颗粒,尺寸在1~3μm;经过热处理之后AlSi10Mg合金的热物理性能均优于打印态。退火处理后的合金样品在室温到400℃的热膨胀系数为1.64×10^(−5)~2.1×10^(−5)℃^(−1),平均热导率为179.6 W·m^(−1)·K^(−1),性能优于时效处理和固溶处理。

一种双靶磁控溅射制备的Mg掺杂的NiO薄膜

采用磁控溅射“共溅射”方法,将Ar气作为溅射气体,高纯NiO和MgO双陶瓷靶作为溅射靶材。当控制NiO和MgO靶的溅射功率分别为190 W和580 W,溅射真空度为2 Pa,衬底温度为300℃时,得到了Mg掺杂的NiO(Ni_(0.61)Mg_(0.39)O)薄膜。该薄膜是一种具有(200)择优取向的晶态薄膜。薄膜表面比较平整,晶粒分布致密,晶粒尺寸约46.9 nm。(200)衍射峰位置相对未掺杂的NiO薄膜向小角度偏移约0.2°。合金薄膜在可见光波段具有较大的透过率,而在300 nm附近透过率陡然下降,其光学带隙向高能方向移动到了3.95 eV。该研究为采用磁控溅射制备高质量的Mg掺杂的NiO薄膜提供了技术支撑。