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Li metal batteries (LMBs) are among the most promising options for next-generation secondary batteries under the rapidly growing demand for high-energy-density electrochemical energy storage. However, the implementation of LMBs are hindered by major obstacles such as dentritic Li deposition and low cycling Coulombic efficiency. A practical functional separator is developed in this study, which consists of a Lewis acidic mixed oxide of ZrO 2 -SiO 2 -Al 2 O 3 as a functional coating with anion anchoring ability to modulate ion transport in the vicinity of the Li metal anode, delivering a high Li + transference number of 0.88 in carbonate electrolytes that suppresses dendrite formation. The strong Lewis acid sites in ZrO 2 -SiO 2 -Al 2 O 3 originate from coordinatively unsaturated Zr 4+ ions, which immobilize anions and reduce their decomposition rate. This significantly improves the chemical stability of the electrolyte and induces a more stable solid electrolyte interphase layer. The modified separator enables an anode-free cell containing a high-loading LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode to present stable charge and discharge cycling for 150 cycles at 0.5C. By effectively suppressing Li dendrite growth and supporting the long-term operation of anode-free LMBs, this study offers a novel approach to rationally design mixed oxides with high Lewis acidity for functional separators., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Titanium and its alloys are widely used in high-end manufacturing fields. However, their low high-temperature oxidation resistance has limited their further application. Recently, laser alloying processing has attracted researchers to improve the surface properties of Ti, for which Ni coated graphite system is an excellent prospect due to its outstanding properties and metallurgical bonding between coating and substrate. In this paper, nanoscaled rare earth oxide Nd 2 O 3 addition was added to Ni coated graphite laser alloying materials to research its influence on the microstructure and high-temperature oxidation resistance of the coating. The results proved that nano-Nd 2 O 3 has an outstanding effect on refining coating microstructures, thus the high-temperature oxidation resistance was improved. Furthermore, with the addition of 1. 5 wt.% nano-Nd 2 O 3 , more NiO formed in the oxide film, which effectively strengthened the protective effect of the film. After 100 h of 800 °C oxidation, the oxidation weight gain per unit area of the normal coating was 14.571 mg/cm 2 , while that of the coating with nano-Nd 2 O 3 addition was 6.244 mg/cm 2 , further proving that the addition of nano-Nd 2 O 3 substantially improved the high-temperature oxidation properties of the coating., Competing Interests: The authors declare no conflict of interest.

Ni35 coatings were fabricated on 45 steel using a CO 2 laser at various parameters. A relatively large spot (10 mm diameter) was adopted, which was beneficial to the coating quality and the cladding efficiency. The cross-sectional geometry, phase constituent, and microstructure of the coatings were investigated. With a lower specific energy, coating height increased, while coating width, melted depth, dilution rate, width to height ratio and contact angle decreased. Ni35 coating primarily consisted of γ-Ni, FeNi 3 , Ni 3 B, Cr 23 C 6 , and Cr 5 B 3 . Dendrites with flower-like, fishbone-like, pearl-like, and column-like morphologies were observed. The fraction of flower-like dendrites increased gradually with the decrease in scanning velocity due to the dendrite growth direction evolution. With the decrease in scanning velocity, the microstructure of the heat-affected zone transformed from martensite to martensite + sorbite and finally sorbite. The maximum microhardness of the Ni35 coating reached 451.8 HV 0.2 , which was about double that of the substrate (220 HV 0.2 ).

Laser alloying has attracted significant attentions due to the advantages of high processing precision, good controllability and low heat effects on the substrate. However, the complexity of laser alloying requires further attentions on its processing parameters. This study aims at improving the wear resistance of the Ti-6Al-4V substrate by means of laser surface alloying with Ni-coated graphite (G@Ni). The effect of laser scanning speed is explored. The result suggests that the coating has a high surface quality and excellent metallurgical bonding with the substrate. NiTi and NiTi 2 have a eutectic microstructure as well as in the TiC ceramic-reinforced phase as dendrites distribute in the γ-Ni matrix of the coatings. At higher scanning speeds, the lower energy density and shorter existence time of the molten pool refines the microstructure of the coating, improving its microhardness. At the scanning speed of 15 mm/s, the coating has the lowest wear weight loss due to its high microhardness and dense structure. This paper explores the influence of scanning speed on the microstructure and properties of the coatings, expanding the application of laser alloying on the surface modification of Ti-6Al-4V alloys.

Titanium alloys are widely used in high-tech fields, while its disadvantages such as low hardness, high coefficient of friction and poor wear resistance have restricted its applications. This study focuses on improving the friction and wear resistance of Ti-6Al-4V titanium alloys by means of laser surface alloying with Ni-coated graphite (G@Ni). The results suggest that Ni acts as a protective layer to hinder the direct contact and reaction of C and Ti in the molten pool. A part of graphite is unmelted and finally remains to form a self-lubricating wear-resistant composite coating with a compact structure. The average hardness of the coating is approximately four times that of the substrate owing to the TiC hard phase and compact microstructures as the reinforcing phase. The residual graphite in the coating plays a friction-reduction role during the wear test. The wear resistance is increased to 8.53 times that of the substrate according to wear mass loss. This study can effectively enhance the performance and expand the application of the titanium alloys by improving the wear resistance and reducing the friction.

The application of Li metal anodes is currently hindered by the uncontrolled growth of Li dendrites. Herein, the effects of a modified separator with a high Li + transference number (t + ) on the structure and electrochemical performance of Li metal anodes are reported. Stable and dendrite-free plating/stripping cycles are achieved under current densities up to 5 mA cm -2 and areal capacities up to 20 mAh cm -2 . The uniformly grown Li grains under the high t + environment also exhibit well-defined textures (preferred orientations). At a low plating capacity, epitaxial growth takes place on the {100} textures already existing in the rolled Li foils and the uniform Li + flux strengthens this preferred orientation. Increasing the plating capacity to 20 mAh cm -2 , the later-grown textures change to {110} due to the reduced space charges and alleviated transport limits of Li + under the high t + environment, which favor the exposure of the close-packed {110} planes. Compression-induced <111> fiber textures are also resolved and the content increases with the plating capacity. Identification of the textures is meaningful for the exploration of advanced epitaxial substrates beyond Cu foils for high-energy-density Li metal batteries. LiS pouch cells are finally evaluated for the potential application of the modified separator., (© 2021 Wiley-VCH GmbH.)

Laser cladding coatings with excellent wear resistance behaviors are prepared on a titanium alloy substrate with a new precursor material system comprising nanoscale B 4 C and Ni60A self-fluxing alloy powder. Structural analysis reveals the existence of micron-size spherical or nearly spherical graphitic phases in the prepared coatings, which are composed of graphene-like microstructures closely associated with other reinforcement phases of high hardness such as TiC and CrB. The formation mechanism of these graphitic phases involves in situ superassembly of uncombined C atoms via repeated growth and reorientation of the graphene-like microstructures and is closely related to the laser processing parameters as well as the precursor compositions. The coexistence of these heterogeneous phases enable the obtained coatings with high wear resistance and low friction coefficient. It was found that the wear resistance of the coating has a remarkable 43.67 times enhancement than that of the titanium alloy while simultaneously showing a low friction coefficient (∼0.35). The understanding of the formation mechanism on the graphene-related novel microstructures with significantly improved mechanical properties is expected to lay the foundation for future developments and applications of graphene and its related carbon materials, such as large-scale production and further incorporation into composite materials with desired local structures., Competing Interests: The authors declare no competing financial interest., (© 2020 The Authors. Published by American Chemical Society.)

Four additives (Na 2 WO 4 , nano-hydroxyapatite, K 2 TiF 6 and NaF) were added into the Na 5 P 3 O 10 + NaOH + C 3 H 8 O 3 base electrolyte according to the orthogonal design of four factors three levels (L 9 (3 4 )). Nine different micro-arc oxidation (MAO) coatings were fabricated on Mg-2Zn-0.5Ca alloys through orthogonal experiments. The effects of four additives on the microstructure, mechanical properties, corrosion resistance and biocompatibility of MAO coatings were investigated through X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), electrochemical corrosion test and in vitro degradation test. The addition of nano-hydroxyapatite and K 2 TiF 6 showed self-sealing effects and contributed to the corrosion resistance of the samples significantly. The addition of 0.5 g L -1 Na 2 WO 4 markedly elevated the bonding strength of the coatings with the substrate. The optimal combination of factors and levels considering both mechanical properties and corrosion resistance was: 0.5 g L -1 Na 2 WO 4 , 0 g L -1 NaF, 5 g L -1 n-HAp, 5 g L -1 K 2 TiF 6 . The growth mechanism of MAO coatings combining with the visual phenomenon was discussed as well., Competing Interests: The authors declare that they have no competing interests., (This journal is © The Royal Society of Chemistry.)

In this work, carbon-coated manganese silicate (MnSiO 3 /C) nanocomposite with excellent cycling stability was fabricated via a cost-effective process. The carbon coating followed with a CO 2 heat treatment process on the manganese silicate results in mixed-valent hierarchically-porous nanoparticles, which tightly connects with an ultrathin (∼1.5 nm) and ordered carbon coating layer. This composite features rectangular-like cyclic voltammetry curve with two couples of redox peaks, suppressing the irreversible reactions and thus providing a broad and stable working voltage. By fitting the CV curves, the MnSiO 3 /C demonstrates a capacitive energy-storage behavior. The as-assembled activated carbon//MnSiO 3 /C asymmetric supercapacitor in 1 M Na 2 SO 4 aqueous electrolyte is found to have excellent cycling stability, with 95.5% retention of initial after 10,000 cycles. This device could deliver 25.8 W h kg -1 energy density at the power density of 1 kW kg -1 with ∼10 mg cm -2 high mass loading, suggesting a bright prospect in practical application., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Magnesium-based alloys exhibit biodegradable, biocompatible and excellent mechanical properties which enable them to serve as ideal candidate biomedical materials. In particular, their biodegradable ability helps patients to avoid a second surgery. The corrosion rate, however, is too rapid to sustain the healing process. Alloying is an effective method to slow down the corrosion rate. However, currently magnesium alloys used as biomaterials are mostly commercial alloys without considering cytotoxicity from the perspective of biosafety. This article comprehensively reviews the status of various existing and newly developed degradable magnesium-based alloys specially designed for biomedical application. The effects of critical alloying elements, compositions, heat treatment and processing technology on the microstructure, mechanical properties and corrosion resistance of magnesium alloys are discussed in detail. This article covers Mg-Ca based, Mg-Zn based, Mg-Sr based, Mg-RE based and Mg-Cu-based alloy systems. The novel methods of fabricating Mg-based biomaterials and surface treatment on Mg based alloys for potential biomedical applications are summarized.

The applications of magnesium (Mg) alloys as biodegradable orthopedic implants are mainly restricted due to their rapid degradation rate in the physiological environment. In this study, Si-CaP micro-arc oxidation (MAO) coatings were prepared on a Mg-Zn-Ca alloy by a second-step MAO process at different voltages in order to decrease the degradation rate and increase the bioactivity of the alloy. The microstructure and morphology of the samples were characterized using XRD, FT-IR SEM and EDS. The degradation behaviours of samples were evaluated using electrochemical techniques, and immersion tests in simulated body fluid (SBF). The results indicate that the morphology of the Si-CaP coatings changed significantly with the increase in Ca/P ratio as the second-step voltage increased. The Si-CaP containing coating produced at 450 V could significantly decrease the degradation rate of Mg and caused a slow increase in pH of the SBF solution. The haemolysis test concluded that the coating C3 did not cause a haemolytic reaction. The corrosion resistance of Mg alloy was greatly improved with the Si-CaP coatings, and the Mg alloy with Si-CaP coating prepared at 450 V had the best corrosion resistance, which indicates that the Si-CaP coatings are promising for improving the biodegradation properties of Mg-based orthopedic implants. Haemolysis tests indicated that the Si-CaP coating prepared at 450 V conforms to the given standard (YY/T0127.1-93)., Competing Interests: We declare we have no competing interests.

Micro-arc oxidation (MAO) is a plasma-assisted electrochemistry method to prepare protective ceramic coatings on aluminium alloys. Alloy elements of the Al-alloy substrate, such as Si, Cu, Mg and Li, have effects on the microstructure and composition of the MAO coatings. Usually, silicon distributes in the cast Al-Si alloy substrate as small laths and they cover approximately 10% of the substrate surface. Therefore, their effects on the growth process and microstructure of the MAO coatings are worthy of notice. In the present study, oxide coatings with a thickness of 15-18 µm were prepared on the ZL109 Al-Si alloy by MAO. The phase content, surface morphology and element distribution of the coatings were investigated by X-ray diffraction, grazing incidence X-ray diffraction, scanning electron microscope, and electron probe micro-analysis respectively. The average hardness of the coatings was 622.3 ± 10.2 HV 0.05 . The adhesive strength of the coatings is 40.55 ± 2.55 N, and the adhesion of the coatings could be rated as 5B by tape test according to ASTM D3359-17 standard test methods, which indicated a high adhesive strength between the MAO coating and substrate. The effects of silicon laths on surface morphology and composition of the coatings were discussed, and a model was put forward to describe the growth process of the MAO coatings on cast Al-Si alloys. The authors believe that the high silicon content of the substrate has no adverse influence on the structure and properties of the MAO coating on the ZL109 alloy., Competing Interests: The authors declare that they have no competing interests.

Microarc oxidized calcium phosphate (CaP) ceramic coatings were fabricated on Mg-2Sr alloy from silicate electrolytes with different concentration gradient poly(ethylene glycol) (PEG 1000 ). The microstructure, phase and degradability of the ceramic coatings were evaluated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and simulation body fluid (SBF) immersion tests respectively. An electrochemical workstation was used to investigate the electrochemical corrosion properties of the coatings. It is found that microstructure, thickness, adhesive strength and degradation rate are influenced by PEG 1000 incorporation through adjusting the electrolyte activity and then altering the coating growth mechanism. Similar thicknesses (39.0-42.2 μm) are observed in PEG 1000 -containing coatings while their PEG 1000 -free counterparts possess the maximum value (51.5 μm). The weight gain in the first two days of SBF immersion suggests that a new layer containing CaP apatites is generated. Results show that ceramic coatings prepared in the electrolyte containing 8 g L -1 PEG 1000 exhibits the highest corrosion resistance and lowest degradation rate., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Articular cartilage (AC) defects lack the ability to self-repair due to their avascular nature and the declined mitotic ability of mature chondrocytes. To date, cartilage tissue engineering using implanted scaffolds containing cells or growth factors is the most promising defect repair method. Scaffolds for cartilage tissue engineering have been comprehensively researched. As a promising scaffold biomaterial for AC defect repair, the properties of chitosan are summarized in this review. Strategies to composite chitosan with other materials, such as polymers (including collagen, gelatin, alginate, silk fibroin, poly-caprolactone, and poly-lactic acid) and bioceramics (including calcium phosphate, calcium polyphosphate, and hydroxyapatite) are presented. Methods to manufacture three-dimensional porous structures to support cell attachment and nutriment exchange have also been included., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Magnesium alloys are potential biodegradable implants for biomedical applications, and calcium (Ca) is one kind of ideal element being examined for magnesium alloys and biodegradable ceramic coatings owing to its biocompatibility and mechanical suitability. In this study, microarc oxidation (MAO) coatings were prepared on Mg-xCa alloys to study the effect of Ca on the microstructure and corrosion resistance of Mg-xCa alloys and their surface MAO coatings. The electrochemical corrosion behavior was investigated using an electrochemical workstation, and the degradability and bioactivity were evaluated by soaking tests in simulated body fluid (SBF) solutions. The corrosion products were characterized by scanning electron microscopy, x-ray diffractometry, and Fourier transform infrared spectrometry. The effects of Ca on the alloy phase composition, microstructure, MAO coating formation mechanism, and corrosion behavior were investigated. Results showed that the Mg-0.82Ca alloy and MAO-coated Mg-0.82Ca exhibited the highest corrosion resistance. The number and distribution of Mg 2 Ca phases can be controlled by adjusting the Ca content in the Mg-xCa alloys. The proper amount of Ca in magnesium alloy was about 0.5-0.8 wt. %. The pore size, surface roughness, and corrosion behavior of microarc oxidized Mg-xCa samples can be controlled by the number and distribution of the Mg 2 Ca phase. The corrosion behaviors of microarc oxidized Mg-Ca in SBF solutions were discussed.

Bone defects are a common disease threatening the health of many people. Calcium phosphate (CaP) is an ideal bone substitutive material that is widely used for bone repair due to its excellent biological properties including osteoinductivity, osteoconductivity and biodegradability. For this reason, investigation of these properties and the effects of various influencing factors is vital for modulating calcium phosphate during the design process to maximally satisfy clinical requirements. In this study, the latest studies on the biological properties of CaP biomaterials, including hydroxyapatite (HA), tricalcium phosphate (TCP), and biphasic calcium phosphate (BCP), have been summarized. Moreover, recent advances on how these properties are altered by different factors are reviewed. Considering the limited mechanical strength of CaP materials, this study also reviews CaP composites with different materials as improvement measures. Finally, perspectives regarding future developments of CaP materials are also provided., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Magnesium alloys are the most promising implant materials due to their excellent biodegradability. However, their high degradation rate limits their practical application. In this study, we produced a calcium-phosphate (Ca-P) coating and a calcium-phosphate-silicon (Ca-P-Si) coating via one-step and two-step micro-arc oxidation processes, respectively. The microstructure and chemical composition of the MAO coatings were characterized using SEM, XRD and EDS. The degradation behaviors of the MAO coatings and the substrate were investigated using electrochemical techniques and immersion tests in simulated body fluid (SBF). The results show that the silicate was successfully incorporated into the Ca-P coating in the second MAO step, and this also increased the thickness of the coating. The Ca-P-Si coatings remarkably reduced the corrosion rate of the Mg alloy and Ca-P coating during 18 days of immersion in SBF. In addition, the bone-like apatite layer on the sample surface demonstrated the good biomineralization ability of the Ca-P-Si coating. Potentiodynamic polarization results showed that the MAO coating could clearly enhance the corrosion resistance of the Mg alloy. Moreover, we propose the growth mechanism of the MAO coating in the second step.

Calcium phosphate coatings were prepared on the surface of self-designed Mg-Zn-Ca-Mn alloy using microarc oxidization technology. To characterize the microstructures, cross-section morphologies, and compositions of the coatings, the authors used scanning electron microscopy equipped with an energy-disperse spectrometer, x-ray diffraction, and Fourier transform infrared spectroscopy. Potentiodynamic polarization in the simulated body fluid (SBF) was used to evaluate the corrosion behaviors of the samples. An SBF immersion test was used to evaluate the coating bioactivity and degradability. After the immersion tests, some bonelike apatite formed on the coating surfaces indicate that bioactivity of the coatings is excellent. The coating prepared in electrolyte containing (NaPO3)6 had slower degradation rate after immersion test for 21 days.

Calcium phosphate (CaP) ceramic coatings were fabricated on pure magnesium (Mg) and self-designed Mg-0.6Ca, Mg-0.55Ca-1.74Zn alloys by microarc oxidation (MAO). The coating formation, growth and biomineralization mechanisms were discussed. The coating degradability and bioactivity were evaluated by immersion tests in trishydroxymethyl-aminomethane hydrochloric acid (Tris-HCl) buffer and simulated body fluid (SBF) solutions, respectively. The coatings and corrosion products were characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS) and fourier transform infrared spectrometer (FT-IR). The electrochemical workstation was used to investigate the electrochemical corrosion behaviors of substrates and coatings. Results showed that Mg-0.55Ca-1.74Zn alloy exhibits the highest mechanical strength and electrochemical corrosion resistance among the three alloys. The MAO-coated Mg-0.55Ca-1.74Zn alloy has the potential to be served as a biodegradable implant., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We prepared Si-containing and Si-free coatings on Mg-1.74Zn-0.55Ca alloy by micro-arc oxidation. The dissolution and precipitation behaviors of Si-containing coating in simulated body fluid (SBF) were discussed. Corrosion products were characterized by scanning electron microscope (SEM), X-ray diffractometer (XRD), fourier transform infrared spectrometer (FT-IR) and X-ray photoelectron spectrometer (XPS). Electrochemical workstation, inductively coupled plasma atomic emission spectrometer (ICP-AES), flame atomic absorption spectrophotometer (AAS) and pH meter were employed to detect variations of electrochemical parameter and ions concentration respectively. Results indicate that the fast formation of calcium phosphates is closely related to the SiOx(n-) groups, which induce the heterogeneous nucleation of amorphous hydroxyapatite (HA) by sorption of calcium and phosphate ions., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The application of magnesium alloys as biomaterials is limited by their poor corrosion behavior. Microarc oxidation (MAO) treatment was used to prepare ceramic coatings on ZK60 magnesium alloys in order to overcome the poor corrosion resistance. The process was conducted at different current densities (3.5 and 9.0 A/dm(2)), and the effect of current density on the process was studied. The microstructure, elemental distribution, and phase composition of the MAO coatings were characterized by scanning electron microscopy, energy-dispersive x-ray spectrometry, and x-ray diffraction, respectively. The increment of current density contributes to the increase of thickness. A new phase Mg2SiO4 was detected as the current density increased to 9.0 A/dm(2). A homogeneous distribution of micropores could be observed in the coating produced at 3.5 A/dm(2), while the surface morphology of the coating formed at 9.0 A/dm(2) was more rough and apparent microcracks could be observed. The coating obtained at 3.5 A/dm(2) possessed a better anticorrosion behavior.

Using trimethyl phosphate and calcium nitrate tetrahydrate as the calcium and phosphorus precursors, respectively, HA films were prepared layer by layer by a sol-gel method. The phase constitution, microstructure and calcium/phosphorus (Ca/P) molar ratio of the sol-gel films were studied by X-ray diffraction (XRD) and electronic probe microanalysis (EPMA). The results show that the sol-gel films have high crystallinity and are composed of HA and CaO phases, and the Ca/P ratio is slightly higher than the theoretical value in HA because of the loss of phosphorous element. Two typical cauliflower-like and lamellar structures were observed in the films. Cauliflower-like structure, which increases the biological reactivity of the implant surface towards natural bone, formed mainly at low drying temperature and high calcining temperature, while the lamellar structure formed when the drying temperature is high (500 degrees C or above).

Bioactive hydroxyapatite (HA) films were fabricated by a sol-gel method and triethylphosphate and calcium nitrate were used as the phosphorus and calcium precursors, respectively. The effects of the heat treatment temperature, pH level and substrate materials on the phases and microstructures of HA films were studied by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and electronic probe microanalysis (EPMA) and so on. The results show that all the sol-gel films are composed of the phases of HA, CaO, TiO(2) and CaTiO(3). With increasing the calcining temperature, the crystallinity of the films increases, the structure becomes more compact and changes from granular and lamellar to cellular structure, and the Ca/P ratio increases slightly because of the loss of P in the films. The addition of ammonia (adjusting the pH level to be about 7.5) can increase the HA content in the films, and the difference of substrate materials only has a little influence on the microstructure of the sol-gel films.