2021 Vol. 28, No. 2

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Invited Review
Reduction, reuse and recycle of spent Li-ion batteries for automobiles: A review
Toyohisa Fujita, Hao Chen, Kai-tuo Wang, Chun-lin He, You-bin Wang, Gjergj Dodbiba, and  Yue-zhou Wei
2021, vol. 28, no. 2, pp. 179-192. https://doi.org/10.1007/s12613-020-2127-8
Abstract:

The demand for Li-ion batteries (LIBs) for vehicles is increasing. However, LIBs use valuable rare metals, such as Co and Li, as well as environmentally toxic reagents. LIBs are also necessary to utilize for a long period and to recycle useful materials. The reduction, reuse, and recycle (3R) of spent LIBs is an important consideration in constructing a circular economy. In this paper, a flowsheet of the 3R of LIBs is proposed and methods to reduce the utilization of valuable rare metals and the amount of spent LIBs by remanufacturing used parts and designing new batteries considering the concept of 3R are described. Next, several technological processes for the reuse and recycling of LIBs are introduced. These technologies include discharge, sorting, crushing, binder removal, physical separation, and pyrometallurgical and hydrometallurgical processing. Each process, as well as the related physical, chemical, and biological treatments, are discussed. Finally, the problem of developed technologies and future subjects for 3R of LIBs are described.

Research Article
Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid
Sajjad Ali, Yaseen Iqbal, Inamullah Khan, Ansar Ullah, Muhammad Sadiq, Muhammad Fahad, and  Khizar Hussain Shah
2021, vol. 28, no. 2, pp. 193-200. https://doi.org/10.1007/s12613-020-2069-1
Abstract:

Manganese was leached from a low-grade manganese ore (LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H2SO4 concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ~98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C, manganese ore amount of 5 g, and sulfuric acid concentration of 15vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction (1 − (1 − x)1/3 = kt) mechanism with an apparent activation energy of 40.19 kJ·mol−1.

Research Article
Extraction and kinetic analysis of Pb and Sr from the leaching residue of zinc oxide ore
Xiao-yi Shen, Yuan-yong Liang, Hong-mei Shao, Yi Sun, Yan Liu, and  Yu-chun Zhai
2021, vol. 28, no. 2, pp. 201-209. https://doi.org/10.1007/s12613-020-1972-9
Abstract:

NH4HCO3 conversion followed by HCl leaching was performed and proven to be effective in extracting Pb and Sr from zinc extracted residual. The mechanism and operating conditions of NH4HCO3 conversion, including molar ratio of NH4HCO3 to zinc extracted residual, NH4HCO3 concentration, conversion temperature, conversion time, and stirring velocity, were discussed, and operating conditions were optimized by the orthogonal test. Experimental results indicate that NH4HCO3 conversion at temperatures ranging from 25 to 85°C follows the shrinking unreacted core model and is controlled by inner diffusion through the product layer. The extraction ratios of Pb and Sr under optimized conditions reached 85.15% and 87.08%, respectively. Moreover, the apparent activation energies of Pb and Sr were 13.85 and 13.67 kJ·mol−1, respectively.

Research Article
Tin recovery from a low-grade tin middling with high Si content and low Fe content by reduction–sulfurization roasting with anthracite coal
Jing-cheng Wang, Lei Li, and  Yong Yu
2021, vol. 28, no. 2, pp. 210-220. https://doi.org/10.1007/s12613-020-2038-8
Abstract:

A new method for separating and recovering tin from a low-grade tin middling with high Si content and low Fe content by roasting with anthracite coal was researched by studying the reaction mechanism and performing an industrial test, in which the Sn was sulfurized into SnS(g) and then collected using a dust collector. The Fe–Sn alloy may be formed at roasting temperatures above 950°C, and like the roasting temperature increases, the Sn content and Sn activity in this Fe–Sn alloy decrease. Also, more FeS can be formed at higher temperatures and then the formation of FeO–FeS with a low melting point is promoted, which results in more serious sintering of this low-grade tin middling. And from the thermodynamics and kinetics points of view, the volatilization of the Sn decreases at extremely high roasting temperatures. The results of the industrial test carried out in a coal-fired rotary kiln show that the Sn volatilization rate reaches 89.7% and the Sn is concentrated in the collected dust at a high level, indicating that the Sn can be effectively extracted and recovered from the low-grade tin middling with a high Si content and low Fe content through a reduction–sulfurization roasting process.

Research Article
Carbothermal reduction characteristics of oxidized Mn ore through conventional heating and microwave heating
Yang He, Jian Liu, Jian-hua Liu, Chun-lin Chen, and  Chang-lin Zhuang
2021, vol. 28, no. 2, pp. 221-230. https://doi.org/10.1007/s12613-020-2037-9
Abstract:

For the purpose of exploring a potential process to produce FeMn, the effects of microwave heating on the carbothermal reduction characteristics of oxidized Mn ore was investigated. The microwave heating curve of the mixture of oxidized Mn ore and coke was analyzed in association with the characterization of dielectric properties. The comparative experiments were conducted on the carbothermal reductions through conventional and microwave heatings at temperatures ranging from 973 to 1373 K. The thermogravimetric analysis showed that carbothermal reactions under microwave heating proceeded to a greater extent and at a faster pace compared with those under conventional heating. The metal phases were observed in the microstructures only under microwave heating. The carbothermal reduction process under microwave heating was discussed. The electric and magnetic susceptibility differences were introduced into the thermodynamics analysis for the formation of metal Mn. The developed thermodynamics considered that microwave heating could make the reduction of MnO to Mn more accessible and increase the reduction extent.

Research Article
Selective reduction of carbon dioxide into amorphous carbon over activated natural magnetite
Zhong-qing Liu, Jian Zheng, Yi Wang, and  Xu Liu
2021, vol. 28, no. 2, pp. 231-237. https://doi.org/10.1007/s12613-020-2034-z
Abstract:

Natural magnetite formed by the isomorphism substitutions of transition metals, including Fe, Ti, Co, etc., was activated by mechanical grinding followed by H2 reduction. The temperature-programmed reduction of hydrogen (H2-TPR) and temperature-programmed surface reaction of carbon dioxide (CO2-TPSR) were carried out to investigate the processes of oxygen loss and CO2 reduction. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and energy-dispersive X-ray spectroscopy (EDS). The results showed that the stability of spinel phases and oxygen-deficient degree significantly increased after natural magnetite was mechanically milled and reduced in H2 atmosphere. Meanwhile, the activity and selectivity of CO2 reduction into carbon were enhanced. The deposited carbon on the activated natural magnetite was confirmed as amorphous. The amount of carbon after CO2 reduction at 300°C for 90 min over the activated natural magnetite was 2.87wt% higher than that over the natural magnetite.

Research Article
Effects of operating parameters on the flow field in slab continuous casting molds with narrow widths
Tao Zhang, Jian Yang, Gang-jun Xu, Hong-jun Liu, Jun-jun Zhou, and  Wei Qin
2021, vol. 28, no. 2, pp. 238-248. https://doi.org/10.1007/s12613-020-1988-1
Abstract:

Computational simulations and high-temperature measurements of velocities near the surface of a mold were carried out by using the rod deflection method to study the effects of various operating parameters on the flow field in slab continuous casting (CC) molds with narrow widths for the production of automobile exposed panels. Reasonable agreement between the calculated results and measured subsurface velocities of liquid steel was obtained under different operating parameters of the CC process. The simulation results reveal that the flow field in the horizontal plane located 50 mm from the meniscus can be used as the characteristic flow field to optimize the flow field of molten steel in the mold. Increases in casting speed can increase the subsurface velocity of molten steel and shift the position of the vortex core downward in the downward circulation zone. The flow field of liquid steel in a 1040 mm-wide slab CC mold can be improved by an Ar gas flow rate of 7 L·min−1 and casting speed of 1.7 m·min−1. Under the present experimental conditions, the double-roll flow pattern is generally stable at a submerged entry nozzle immersion depth of 170 mm.

Research Article
Effect of nanosized NbC precipitates on hydrogen-induced cracking of high-strength low-alloy steel
En-dian Fan, Shi-qi Zhang, Dong-han Xie, Qi-yue Zhao, Xiao-gang Li, and  Yun-hua Huang
2021, vol. 28, no. 2, pp. 249-256. https://doi.org/10.1007/s12613-020-2167-0
Abstract:

We investigated the effect of nanosized NbC precipitates on hydrogen-induced cracking (HIC) of high-strength low-alloy steel by conducting slow-strain-rate tensile tests (SSRT) and performing continuous hydrogen charging and fracture analysis. The results reveal that the HIC resistance of Nb-bearing steel is obviously superior to that of Nb-free steel, with the fractured Nb-bearing steel in the SSRT exhibiting a smaller ratio of elongation reduction (Iδ). However, as the hydrogen traps induced by NbC precipitates approach hydrogen saturation, the effect of the precipitates on the HIC resistance attenuate. We speculate that the highly dispersed nanosized NbC precipitates act as irreversible hydrogen traps that hinder the accumulation of hydrogen at potential crack nucleation sites. In addition, much like Nb-free steel, the Nb-bearing steel exhibits both H-solution strengthening and the resistance to HIC.

Research Article
Cell morphology, porosity, microstructure and mechanical properties of porous FeCP alloys
Hamid Sazegaran and  Seyyed Mohsen Moosavi Nezhad
2021, vol. 28, no. 2, pp. 257-265. https://doi.org/10.1007/s12613-020-1995-2
Abstract:

Open cell steel foams were successfully fabricated through the powder metallurgy route using urea granules as the water leachable space holder in the present study. The influence of different amounts of phosphorus (0, 0.5wt%, 1wt%, 2wt%, and 4wt%) was investigated on the cell morphology, porosity, microstructure of cell walls, and mechanical properties of steel foams. The cell morphology and microstructure of the cell walls were evaluated using an optical microscope equipped with image processing software and a scanning electron microscope equipped with an energy dispersive X-ray spectrometer. In addition, the compression tests were conducted on the steel foams using a universal testing machine. Based on microscopic images, the porous structure consists of spherical cells and irregularly shaped pores that are distributed in the cell walls. The results indicated that by increasing the phosphorus content, the porosity increases from 71.9% to 83.2%. The partially distributed ferrite and fine pearlite was observed in the microstructure of the cell walls, and α-Fe and Fe3P eutectic extended between the boundaries of agglomerated iron particles. Furthermore, elastic and long saw-toothed plateau regions were observed before fracture in the compressional stress–strain curves. According to the results, by increasing the phosphorus content from 0 to 4wt%, the plateau region of the stress–strain curves shifts to the right and upward. Therefore, increasing phosphorus content causes improvement in the mechanical properties of steel foams.

Research Article
Microstructure and mechanical properties of nickel-based superalloy fabricated by laser powder-bed fusion using recycled powders
De-cheng Kong, Chao-fang Dong, Xiao-qing Ni, Liang Zhang, Rui-xue Li, Xing He, Cheng Man, and  Xiao-gang Li
2021, vol. 28, no. 2, pp. 266-278. https://doi.org/10.1007/s12613-020-2147-4
Abstract:

Evaluating the recyclability of powders in additive manufacturing has been a long-term challenge. In this study, the microstructure and mechanical properties of a nickel-based superalloy fabricated by laser powder-bed fusion (LPBF) using recycled powders were investigated. Re-melted powder surfaces, satellite particles, and deformed powders were found in the recycled powders, combined with a high-oxygen-content surface layer. The increasing oxygen content led to the formation of high-density oxide inclusions; moreover, printing-induced cracks widely occurred and mainly formed along the grain boundaries in the as-built LPBF nickel-based superalloys fabricated using recycled powders. A little change in the Si or Mn content did not increase the hot cracking susceptibility (HCS) of the printed parts. The changing aspect ratio and the surface damage of the recycled powders might contribute to increasing the crack density. Moreover, the configuration of cracks in the as-built parts led to anisotropic mechanical properties, mainly resulting in extremely low ductility vertical to the building direction, and the cracks mainly propagated along the cellular boundary owing to the existence of a brittle precipitation phase.

Research Article
Effect of groove rolling on the microstructure and properties of Cu–Nb microcomposite wires
Peng-fei Wang, Ming Liang, Xiao-yan Xu, Jian-qing Feng, Cheng-shan Li, Ping-xiang Zhang, and  Jin-shan Li
2021, vol. 28, no. 2, pp. 279-284. https://doi.org/10.1007/s12613-020-2073-5
Abstract:

Cu–Nb microcomposite wire was successfully prepared by a groove rolling process. The effects of groove rolling on the diffraction peaks, microstructure, and properties of the Cu–Nb microcomposite were investigated and the microstructure evolutions and strengthening mechanism were discussed. The tensile strength of the Cu–Nb microcomposite wire with a diameter of 2.02 mm was greater than 1 GPa, and its conductivity reached 68% of the International Annealed Copper Standard, demonstrating the Cu–Nb microcomposite wire with high tensile strength and high conductivity after groove rolling. The results show that an appropriate groove rolling method can improve the performance of the Cu–Nb microcomposite wire.

Research Article
Surface modifications of biometallic commercially pure Ti and Ti–13Nb–13Zr alloy by picosecond Nd:YAG laser
Slađana Laketić, Marko Rakin, Miloš Momčilović, Jovan Ciganović, Đorđe Veljović, and  Ivana Cvijović-Alagić
2021, vol. 28, no. 2, pp. 285-295. https://doi.org/10.1007/s12613-020-2061-9
Abstract:

The effects of picosecond Nd:YAG laser irradiation on chemical and morphological surface characteristics of the commercially pure titanium and Ti–13Nb–13Zr alloy in air and argon atmospheres were studied under different laser output energy values. During the interaction of laser irradiation with the investigated materials, a part of the energy was absorbed on the target surface, influencing surface modifications. Laser beam interaction with the target surface resulted in various morphological alterations, resulting in crater formation and the presence of microcracks and hydrodynamic structures. Moreover, different chemical changes were induced on the target materials’ surfaces, resulting in the titanium oxide formation in the irradiation-affected area and consequently increasing the irradiation energy absorption. Given the high energy absorption at the site of interaction, the dimensions of the surface damaged area increased. Consequently, surface roughness increased. The appearance of surface oxides also led to the increased material hardness in the surface-modified area. Observed chemical and morphological changes were pronounced after laser irradiation of the Ti–13Nb–13Zr alloy surface.

Research Article
Influence of multi-stage heat treatment on the microstructure and mechanical properties of TC21 titanium alloy
Wei Long, Song Zhang, Yi-long Liang, and  Mei-gui Ou
2021, vol. 28, no. 2, pp. 296-304. https://doi.org/10.1007/s12613-020-1996-1
Abstract:

Duplex-structured TC21 alloy samples were first solution-treated at a higher temperature in the α + β region (940°C) with furnace cooling (FC), air cooling (AC), and water cooling (WC), followed by a second-stage solution treatment at a lower temperature in the α + β region (900°C), and then finally aged at 590°C. The effects of the morphology and quantity of α phases on the structure and properties of the TC21 alloy after the different heat treatments were analyzed. The in-situ tensile deformation process and crack propagation behavior were observed using scanning electron microscopy (SEM). The quantity of equiaxed α phases as well as the thickness of lamellar α phases reduced, the tensile strength increased firstly and then decreased, the elongation decreased with the increasing cooling rate after the first-stage solution treatment. The amount and size of lamellar α phases increased after the second-stage solution treatment because of sufficient diffusion of the alloying elements, thereby leading to increased tensile strength. The amount of dispersed α phases increased after the third-stage aging treatment owing to the increase in the nucleation rate, resulting in a noteworthy strengthening effect. After the third-stage aging treatment, the first-stage FC sample exhibited better mechanical properties because it contained more equiaxed α and βtrans phases than the first-stage AC and WC samples.

Research Article
Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi0.8Co0.15Al0.05O2 cathode
Hao-yang Wang, Xue Cheng, Xiao-feng Li, Ji-min Pan, and  Jun-hua Hu
2021, vol. 28, no. 2, pp. 305-316. https://doi.org/10.1007/s12613-020-2145-6
Abstract:

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials (LiNi0.8Co0.15Al0.05O2, NCA), lithium lanthanum titanate (LLTO) nanofiber and carbon-coated LLTO fiber (LLTO@C) materials were introduced to polyvinylidene difluoride in a cathode. The enhancement of the conductivity was indicated by the suppressed impedance and polarization. At 1 and 5 C, the cathodes with coupling conductive paths had a more stable cycling performance. The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C. In the pristine cathode, the propagation of lattice damaged regions, which consist of high-density edge-dislocation walls, destroyed the bulk integrity of NCA. In addition, the formation of a rock-salt phase on the surface of NCA caused a capacity loss. In contrast, in the LLTO@C modified cathode, although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred, they were limited to a scale of several atoms, which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention. Only NiO phase “pitting” occurred. A mechanism based on the synergistic transport of Li ions and electrons was proposed.

Research Article
Preparation of Al2O3–SiO2 composite aerogels and their Cu2+ absorption properties
Xiao-guang Liu, Qiu-shuo Mao, Yue Jiang, Yan Li, Jia-lin Sun, and  Fei-xue Huang
2021, vol. 28, no. 2, pp. 317-324. https://doi.org/10.1007/s12613-020-2111-3
Abstract:

In order to remediate heavy metal ions from waste water, Al2O3–SiO2 composite aerogels are prepared via a sol–gel and an organic solvent sublimation drying method. Various characterisation techniques have been employed including X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), scanning electron microscope (SEM), Energy-dispersion X-ray spectroscopy (EDX), Brunauer–Emmett–Teller (BET) N2 adsoprtion isotherm, and atomic absorption spectrometer (AAS). XRD and FTIR suggest that the aerogels are composed of mainly Al2O3 and minor SiO2. They have a high specific surface area (827.544 m2/g) and high porosity (86.0%) with a pore diameter of ~20 nm. Their microstructures show that the distribution of Al, Si, and O is homogeneous. The aerogels can remove ~99% Cu2+ within ~40 min and then reach the equilibrium uptake (~69 mg/g). Preliminary calculations show that the Cu2+ uptake by the aerogels follows pseudo second-order kinetics where chemical sorption may take effect owing largely to the high surface area, high porosity, and abundant functional groups, such as Al–OH and Si–OH, in the aerogel network. The prepared aerogels may serve as efficient absorbents for Cu2+ removal.

Research Article
Effect of pH on the photocatalytic removal of silver ions by β-MnO2 particles
Sin-Ling Chiam, Anh Thi Le, Swee-Yong Pung, and  Fei-Yee Yeoh
2021, vol. 28, no. 2, pp. 325-334. https://doi.org/10.1007/s12613-020-2062-8
Abstract:

The presence of silver ions (Ag(I)) in wastewater has a detrimental effect on living organisms. Removal of soluble silver, especially at low concentrations, is challenging. This paper presents the use of β-MnO2 particles as a photocatalyst to remove Ag(I) ions selectively from aqueous solution at various pH levels. Inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), field emission electron microscope (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron microscopy (XPS) were employed to determine the removal efficiency and to characterize the deposition of silver onto the surface of β-MnO2 particles. The optimum pH for the removal of Ag(I) ions was at pH 4 with 99% removal efficiency under 1 h of visible light irradiation. This phenomenon can be attributed to the electrostatic attraction between β-MnO2 particles and Ag(I) ions as well as the suppression of electron–hole recombination in the presence of H+ ions.