Fluoride Salts Research Articles

Faster and Safer "In situ" Synthesis of Germanane and Silicane.

Germanane (GeH) and silicane (SiH), members of the Xanes family, have garnered significant attention as 2D materials due to their diverse properties, which hold promise for applications in electronics, optoelectronics, energy storage, and sensing. Typically, highly concentrated hydrochloric acid (HCl) or hydrofluoric acid (HF) is employed in the synthesis of these Xanes, but both routes are problematic due to slow kinetics and safety concerns, respectively. Here for the first time, a faster and safer method is demonstrated for Xanes synthesis that harnesses the generation of HF "in situ" using a solution of HCl and lithium fluoride (LiF) salt, overcoming the key challenges of the conventional methods. A variety of characterization techniques to establish a baseline is utilized for both Xanes and to provide a holistic knowledge regarding this method, the possible consequences of this approach, and the possibility of applying it to other layered Zintl phases. The novel synthesis protocol results in high-quality GeH and SiH with bandgaps (Eg) of 1.75 and 2.47eV respectively, highlighting their potential suitability for integration into semiconductor applications.

Highly enhanced fluoride removal from aqueous systems via solvent extraction utilizing trialkyl phosphine oxide as an efficient extractant

Solvent extraction (SX) has been recognized as an efficient approach for the large-scale removal of impurities, demonstrating considerable potential for fluoride extraction in industrial applications. However, existing fluoride extraction methods typically require the incorporation of additives to form complexes with fluoride for its removal. Due to the excessive additive requirements for efficient fluoride removal, these methods inevitably result in secondary contamination of feed solution, necessitating additional purification efforts to remove them. In this study, four extractants (trioctyl amine, tributyl phosphate, trioctyl phosphate, and trialkyl phosphine oxide (TRPO)) were investigated for fluoride removal via hydrogen bonding with hydrofluoric acid (HF). Various parameters, including the concentrations of extractants and stripping agents, pH values, extraction time, and temperature were initially optimized. It was found that TRPO exhibits the highest extraction efficiency for HF, with a single-stage extraction rate exceeding 70 %. Complete fluoride removal (> 99.9 %) was achieved through a consecutive four-stage extraction process. Further experiments, including maximum loading and slope analysis, combined with FT-IR and 19F NMR characterization, and DFT calculations elucidate the mechanism of the extraction. The transfer of HF into the organic phase is accomplished by the formation of a 1:1 hydrogen-bonded complex with TRPO. The loaded fluoride in the organic phase can be easily stripped by a base to get a fluoride salt. This study paves the way for the construction of novel SX systems to remove fluoride as HF.

A fast and efficient Al-5Ti-1B grain refiner prepared by gas-assisted continuous casting and extrusion process

The feasibility of preparing Al-Ti-B alloy wires based on a novel technology of gas-assisted continuous casting and extrusion (GAC) was investigated. Results show that Al-5Ti-1B alloy wire with fine and uniform distribution of the second phase can be prepared by combining the fluoride salt method and the GAC process. When the wire was added into an industrial pure aluminum at 730 °C with an addition of 0.2 wt%, the pure aluminum grains could be refined into equiaxed crystals with an average size of about 140 μm by contacting time of 60 s, which showed the characteristics of rapidity and high efficiency.

Calcium-driven hydrolysis mechanisms of secondary aluminum dross (SAD) in the hydrometallurgical process to simultaneous denitrification, desalination, and fluoride fixation

Secondary aluminum dross (SAD) contains large amounts of toxic components (AlN, fluoride, and chloride salts), which limits its large-scale utilization. Problems such as high acid or alkali usage and high liquid–solid ratio make it difficult to industrialize the disposal of SAD. In the previous study, authors achieved self-driven hydrolysis of SAD, and the double-edged effects of Na/K aluminosilicates generation on denitrification and desalination during the leaching process of SAD were also revealed. Based on this, a new approach for simultaneous denitrification, desalination, and fluoride fixation of SAD by calcium-driven hydrolysis was proposed in this study. Thermodynamic analysis indicated that calcium aluminosilicates are more easily precipitated than sodium and potassium aluminosilicates in solution. Kinetic analysis showed that the denitrification reaction was controlled by a mixture of chemical reaction and diffusion, the dissolution of Al(OH)3 inclusions to Al(OH)4- was the limiting link. Mechanistic analysis revealed that Ca2+ replaced Na+ and K+ and preferentially reacted with Al(OH)4- and H3SiO4- to form calcium aluminosilicates, which promoted the removal of Na and K. Calcium aluminosilicates exhibited a greater ability to promote the dissolution of Al(OH)4- than sodium and potassium aluminosilicates, which further enhanced denitrification. As a bonus, Ca2+ also realized the fixation of soluble F-. Under the optimal conditions (L/S=1.5, T=80 ℃, t = 300 min, CaCl2(wt.%) = 10%), the denitrification rate was increased to 91.12%, Na and K contents were reduced to 0.24 wt% and 0.14 wt%, respectively, the removal of Cl was 99.30%, and the fixation rate of F was 99.00%.

Formation of YOF on Y2O3 through surface modification with NH4F and its plasma-resistance behavior

Yttrium oxyfluoride (YOF) is known for exhibiting superior plasma-resistance properties compared to Y2O3, particularly in a fluorocarbon plasma environment. The formation of the YOF layer directly on the surface of Y2O3 via surface modification may be considered as a viable and cost-effective method. In this study, we employed ammonium fluoride (NH4F) salt for the surface modification of Y2O3. By using a 40 wt% NH4F aqueous salt solution, the YOF layer with a thickness of about 8.6 μm was efficaciously formed in-situ on the surface of Y2O3 based on the fluorination mechanism. The composition and microstructure of the modified Y2O3 surface was thoroughly characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis revealed the formation of distinct intermediate ammonium yttrium fluoride phases depending upon the heat treatment temperature (150 − 500 °C) through the fluorination of Y2O3 with NH4F. A stable YOF phase was formed ultimately at 300 °C. Plasma etching tests were performed using a mixture of CF4/Ar/O2 gases for 1 h. The microstructures of specimens are observed by SEM before and after plasma treatments. Plasma exposure tests demonstrated that specimens heat-treated at 500 °C for 2 h exhibit excellent plasma-resistance behavior with minimal surface damage, which is attributed to the presence of stable and dense YOF phase.

Exploring the molarity of Lithium Fluoride in minimally intensive layer delamination (MILD) method for efficient room temperature synthesis of high quality Ti3C2Tx free-standing film

In recent years, MXene has become the most demanding material in the 2D family, leading to their increased use in research for a diverse range of applications, such as energy storage, water purification, optoelectronics, electromagnetic interference (EMI) shielding and medicine. However, recent research has made it increasingly important to synthesize high-quality MXene in a safe, reliable, fast, reproducible, and good-yielding single-step method. To achieve high-quality MXene by etching the MAX phase precursors, it is very important to critically optimize synthesis parameters, such as etching method, etchant concentrations, temperature, time, etc. Minimally intensive layer delamination (MILD) method for MXene synthesis using Lithium Fluoride (LiF) salt and hydrochloric (HCl) acid seems to be a better choice in the context of improved performance in different applications as well as its scalability and reproducibility. Here, the molar ratio of HCL/LIF is critical for Aluminium etching at room temperature to produce a high-quality MXene with = O, -OH, -F termination groups in the MILD method. However, in case of MILD method the effect of LiF/HCL concentrations on quality of MXene need to be addressed. In this study, we focus on room temperature etching of Ti3AlC2 using MILD method to synthesize quasi two-dimensional carbide (Ti3C2) MXene. The influence of molarity concentration of etchants (LiF and HCl) on quality of MXene has been thoroughly investigated. Different molar concentrations of Lithium Fluoride (LiF) with fixed HCL concentration were tested at room temperature for 24 h in the etching process. The crystal structure, microstructure and composition of the MXene were characterized using X-ray diffraction, Raman spectroscopy, and electron microscopy. Flexible free-standing MXene film with largest shift in the characteristic (002) peak, indicating large interplanar spacing, has been successfully achieved repeatedly for an optimum molar concentration of etchants at room temperature.

Uncovering accurate values of the polarization resistance in molten fluorides using electrochemical impedance spectroscopy

High-temperature operation and the presence of oxidizing impurities in molten chloride and fluoride salts pose significant corrosion risks to structural alloys in molten salt nuclear reactors. Electrochemical impedance spectroscopy (EIS) offers an operando, real-time method to study the instantaneous corrosion behavior of these materials non-destructively. However, signal noises may originate from sources extraneous to the electrochemical systems that limit the ability to perform quality impedance measurements in low-frequency regime where polarization resistance (Rp) dominates. Using the exposure of pure Cr in molten LiF-NaF-KF containing 1 wt% EuF3 at 600 °C as a model corrosion system, the extent of Non-Uniform Current and Potential (NUCP) distribution during an AC perturbation associate with the disk electrodes is evaluated in terms of two dimensionless correction factors kfRct(=Rct/Reff) and kfCdl(=Cdl/Ceff). Results show that a small area Cr disk electrode increases the transition frequency that marks the dominance of Rp to a conventional terminational frequency above 10−2 Hz, enabling a reliable charge-transfer resistance (Rct) value to be determined via circle fitting of an electrical equivalent circuit model (ECM) model. Experimental results were supported by EIS simulations considering commonly used ECM models that factor in the NUCP effect of disk geometries.

Verification and Demonstration of One-Dimensional Freezing Model in SAM for Salt-Cooled Reactor Analysis Applications

This work presents the development and implementation of the one-dimensional freezing model in system analysis code SAM (System Analysis Module), code verification using analytical solutions, and code demonstration of a postulated overcooling transient for a fluoride salt–cooled high-temperature reactor (FHR) system and safety analysis applications. This paper first summarizes the freezing model, finite element numerical method, and special numerical treatment for handling transitions between single- and two-phase conditions. Analytical solutions are derived for two cases, with and without solid walls, for code verification purposes. As expected, the numerical results predicted by SAM agree very well with the analytical solution. A code demonstration is then performed on a postulated protected overcooling transient event of a generic reference pebble bed FHR design. The code was found to successfully predict salt freezing during such a postulated event. However, due to the lack of salt freezing testing data, code validation is not performed in this work, but will be pursued in future studies when such data become available.

Preparation of polymeric aluminum chloride from secondary aluminum dross and its water purification effect

ABSTRACT Aluminum dross is solid waste generated by the aluminum industry. Currently, a large amount of aluminum dross is produced annually year. Aluminum dross, a hazardous waste, contains harmful substances such as aluminum metal, aluminum nitride, fluoride and chlorine salts, which pose a serious threat to human health and also cause damage to the ecological environment. Thus, it is important to recycle secondary aluminum dross and realise its high-value utilisation. Polymeric aluminum chloride (PAC) is a polymer flocculant, at present, China's annual use of PAC in the field of water treatment is about 5 × 105 t, and with the continuous improvement of water purification requirements, the annual use of PAC increased year by year. Here secondary aluminum dross was used as a raw material to prepare PAC by hydrochloric acid (HCl) leaching, followed by the addition of sodium carbonate. The optimal conditions for the acid leaching of secondary aluminum dross for the preparation of PAC were as follows: HCl concentration, 18%; liquid-to-solid ratio, 4.5:1; stirring rate, 200 r/min; reaction temperature, 90 °C; and 60 min. An aluminum leaching rate of 85.5% was obtained under these conditions. The results showed that the acid leachate after adding sodium carbonate, under the conditions of polymerisation temperature of 70 °C, polymerisation time of 6 h, and polymerisation pH value of 3.0, the PAC prepared had an alumina content of 10.19%, salinity of 32.37%, density of 1.32 g/cm3, 1% aqueous solution pH 4.3. The water purification effect of the prepared PAC surpassed that of the commercially available PAC. The utilisation of secondary aluminum dross can reduce the environmental pollution caused by aluminum slag.

An Electrochemical Phase Field Model Applied to Molten Salt Dealloying Corrosion of Ni-Alloys

Metal alloys in contact with molten salts are known to corrode via a dealloying process, wherein the less-noble alloy elements (e.g. Cr) are selectively oxidized and dissolved, leaving behind a corroded structure that is enriched in the more-noble elements (e.g. Ni). In some cases, this can lead to molten salt infiltration into the alloy through discrete channels along specific microstructural features (e.g. grain boundaries). However, in other cases the dealloying process promotes a more full-scale attack of the alloy, generating a fine-scale ligament structure. This process can severely degrade the alloy’s structural integrity, which limits the practicality of these material systems in otherwise promising applications (e.g. molten salt-cooled power reactors).The thermokinetic conditions for dealloying corrosion depend on the salt chemistry and the metal microstructure, which together inform the reaction process occurring at their interface. The salt chemistry and oxidant content set the electrochemical potential for selective oxidation of the less-noble elements. The associated oxidation rate is expected to depend on the presence of an interfacial structure (e.g. double layer) and also on the transport rates of reactants towards the interface (e.g. species diffusion in the metal and oxidizer transport in the salt) and reaction products away from the interface (cation transport in the salt). The corrosion rate and morphology will also depend strongly on the rate of transport laterally along the metal-salt interface, since the reorganization of the more-noble species (Ni) towards ligament formation facilitates the attack of the alloy by the corrosive agent. It has been hypothesized that molten salts enhance this rate of solute diffusion along the metal interface.In this work, we propose an electrochemical phase field model to predict the microstructural evolution of model Ni-alloys undergoing dealloying corrosion in molten fluoride salts. The model incorporates metal oxidation and dissolution via experimentally determined redox potentials and activity coefficients for metal species in the molten salt. We show that the corrosion rate and development of pores is strongly dependent on solute transport rates within the metal and also along their solid-liquid interface. In particular, we reveal a mechanism in which grain boundaries couple with the solid-liquid corrosion front to promote rapid dealloying and molten salt attack. Oxidant content in the salt and double-layer formation at the interface are discussed for their roles in setting the electrochemical potential and reaction rate at the metal-salt interface. Finally, we discuss how the model leverages insights from atomistic modeling and highlight key knowledge gaps in the mesoscale modeling of electrochemical molten salt corrosion.

Investigation of the Relationship between Molten Fluoride Salt Structure and Fluoroacidity Using Chromium As a Probe Redox Ion

Molten fluoride salts have been studied for decades due to their applications in the production of aluminum as well as in the operation of advanced nuclear reactors. Advanced fission and fusion nuclear reactor designs may include molten fluoride salts as coolants, fuel carriers (fission), or fuel breeding blankets (fusion). Relevant to their nuclear applications are the thermophysical and thermochemical properties of the salt. These include viscosity and thermal conductivity, as well as density, vapor pressure, and heat capacity. Underlying these properties are the interactions of the ions constituting the liquid, characterized by their coordination number, correlation times, and the possible formation of polymeric networks in the melt. The composition and structure of a melt, that is, what ions are present and how they interact, dictates the macroscopic properties relevant to reactor operation. Fluoroacidity, or the activity of dissociated fluoride anions, is one metric that may be used to describe the relationship between salt chemistry and structure. Overall, understanding the relationship between molten fluoride salt chemistry and structure enables deeper understanding and, thus, prediction of property changes that may take place throughout a reactor’s lifetime.In this poster, we present cyclic and square wave voltammetry studies of chromium speciation and diffusivity in various molten fluoride salts, connecting results with current understanding of the structure of the melts. Chromium is a thermodynamically favored corrosion product in molten salt systems, and in this study, it serves as a probe ion in different fluoride melts. Chromium trifluoride is added to various fluoride solvents and the diffusion coefficients of its various oxidation states are calculated and interpreted in light of salt structure. Experimental apparatus design and know-how for high-temperature molten salt electrochemistry are also highlighted.

Molecular dynamics simulation on thermal and transport properties of LiF-KF

Molten fluoride is considered as an attractive heat transfer and storage medium in advanced energy utilization facilities, but it is short of the necessary thermal and transport properties at high temperature. In this paper, the thermal and transport properties of the binary LiF-KF mixtures at 1073–1473 K are obtained by classical molecular dynamics. The deviation of simulated thermal conductivity of binary LiF-KF at 1073 K from experimental value is less than 19 %. Moreover, the deviation of simulated viscosity of pure LiF at different temperatures from experimental value is around 10 %. It is indicated that reverse non-equilibrium molecular dynamics (RNEMD) is acceptable for describing fluoride salts. An exponential correlation is established between molar fraction of LiF and thermal conductivity at different temperatures. Furthermore, the macroscopic thermal and transport properties correlated with local structure are analyzed, especially the dependence of local structure on temperature and composition of LiF is discussed deeply. With temperature increasing, ion clusters are considered to be formed and overall structure become loose, which leads to reductions in density, thermal conductivity and viscosity. An increase in composition of LiF results in higher specific heat capacity, thermal conductivity and viscosity, which is related to the reduction of Li-Li bond length and the enhancement of interactions between F−. The comparison of properties enhancement of different compositions is completed through the analysis of the synergy coefficient of macroscopic properties. This work provides the basic data for the accurate design of high-temperature heat transfer system.

Rapid and ultra-sensitive trace water determination in organic solvents utilizing nitrobenzoxadiazole (NBD)-based fluorescent sensing system

The presence of minute quantities of water in organic solvents can affect the progress of many reactions and cause unnecessary losses and even safety accidents in the chemical industry, especially in the productions process of organic fine chemicals. Therefore, it is necessary to carry out high-performance strategies for trace water detections in commonly used organic solvents. In this work, a fluorescent sensing system based on competitive binding of protons has been developed, demonstrating remarkable responses by UV–vis absorption and fluorescence two-modes toward a trace amount of water in organic solvents including 1,4-dioxane (Diox), tetrahydrofuran (THF), acetonitrile (MeCN), acetone (ACE), dimethylsulfoxide (DMSO) and mixed organic solvents (THF: MeCN=1: 1). The key component of the sensing system is a newly designed fluorophore NBD-PMA, which can be deprotonated to form a dynamic non-luminescent adduct, namely NBD-PMA-F, by an organic fluoride salt tetrabutylammonium fluoride (TBAF). NBD-PMA-F can be reprotonated via using trace water, exhibiting fluorescence turn on of the system. The as-prepared sensing system shows superior sensitivity, low detection limits (v/v, 0.0007 %), quick response speed (≤1.2 s) and good reversibility. Moreover, naked-eye visual rapid detection has also been successfully realized at ambient temperature, which demonstrated their practical applications value for trace water determinations.

Elucidating the role of Cr migration in Ni-Cr exposed to molten FLiNaK via multiscale characterization

Structural materials used in nuclear reactor environments are subjected to coupled extremes such as high temperature, irradiation, and corrosion which act in concert to degrade their functional performance. Connecting alloy microstructure such as grain boundaries, and accumulating point defects with corrosion attack and pore morphology is critical to understanding underlying mechanisms. We uncover the compositional variations and morphology at multiple length scales in corrosion-damaged Ni-Cr alloy after exposure to oxidants in molten fluoride salts. A complex network of dense corrosion pores is detected by surface-level SEM observations. The corrosion pores take on a 1-dimensional morphology and are enriched with Ni and depleted of Cr 1–5 µm from the pore surface. STEM-EDS and 4D-STEM strain maps acquired simultaneously highlight the local variations in composition and structure of a ≤ 200 nm Cr-rich layer identified from a cross-section taken at the bottom of an isolated corrosion pore between the Ni-Cr alloy matrix and the embedded salt. However, the absence of an observed interface between the Ni-Cr alloy matrix and the FCC-structured Cr-rich layer suggests that Cr plating from the salt did not transpire. These findings support a proposed Cr lattice diffusion mechanism rather than Cr-precipitation from the salt to accommodate temperature transient conditions during sample cooling. Through the development of a 1D phase field model, these results are rationalized by formation energies for the Ni- and Cr-oxidation into the molten salt. This study reveals the locally altered microstructure caused by high temperature corrosion in non-steady-state molten salt nuclear reactor environments.

Thermophysical properties of Molten FLiNaK: A moment tensor potential approach

Fluoride salts demonstrate significant potential for applications in next-generation nuclear reactors, necessitating a comprehensive understanding of their thermophysical properties for technological advancements. Experimental measurement of these properties poses challenges, due to factors such as high temperatures, impurity control, and corrosion. Consequently, precise computational modeling methods become essential for predicting the thermophysical properties of molten salts. In this work, we performed molecular dynamics (MD) simulations of several thermophysical properties of the eutectic salt mixture LiF-NaF-KF (FLiNaK) melt, including density, self-diffusion coefficients, viscosity, and thermal conductivity. We demonstrated the successful application of moment tensor potentials (MTP) as an accurate model for interatomic interactions in FLiNaK. Our results on thermophysical properties calculations exhibit strong agreement with experimental data. An important aspect of our methodology is the incorporation of an active learning scheme, which enables the generation of a robust and accurate potential, while maintaining a moderate-sized training dataset.

Measurements of UF4/UF3 ratio for redox potential control in u-bearing fluoride salt

Redox potential control is important in mitigating corrosion in molten salt reactors (MSRs) during operation. This study has developed a methodology for establishing the operational boundaries, both upper and lower, of the ratio of UF4 to UF3 (UF4/UF3) for redox potential control in U-bearing fluoride salts by measuring the equilibrium quotient. The upper limit for UF4/UF3 is determined by the potential for chromium dissolution, while the formation of uranium carbides governs the lower limit. By applying the methodology, the research experimentally determined the UF4/UF3 ratio in NaF-KF-UF4 salt at temperatures ranging from 873 K to 1023 K. To determine a stable operational range, the range of the operation temperature of the MSR must be considered, the stable range of the ratio is depicted as a trapezoid, with the upper and lower limits serving as the bases of the trapezoid.

Stability of a Ni/NiF2 Reference Electrode with a Metallic Membrane for Use in Molten Fluoride Salts

In this study, an experimental high-temperature fluoride salt reference electrode (RE) developed by HiFunda LLC was tested in molten FLiNaK at 550 °C. The high-temperature reference electrode (HTRE), based on the Ni/NiF2 redox couple, was tested over a period of 13 d for short-term stability, long-term stability, and electrochemical analysis capabilities. The HTRE was tested using open circuit potentiometry (OCP), cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The HTRE reference potential was measured against changes in salt composition by increasing FeF2 concentrations in the melt across six additions from 0 to 0.1 mol% FeF2. The long-term stability of the electrode was then tested over ten days at a constant composition of 0.1 mol% FeF2. OCP, SWV, and CV were used to calculate an average potential drift between 7–10 mV per day. Using CV and SWV, the number of electrons transferred for iron reduction and the diffusion coefficient of Fe2+ were measured.

On excess reactivity control of the advanced high temperature reactor (AHTR)

The Advanced High Temperature Reactor (AHTR) is a large Fluoride salt cooled High temperature Reactor (FHR) with a thermal power of 3400 MWt, utilizing hexagonal fuel elements with TRISO fuel spheres embedded in graphite fuel plates. While its cycle length is relatively short (less than one year), its specific power is high, resulting in high cycle burnup and consequently high initial excess reactivity that needs to be controlled. This is achieved by using both Eu2O3 burnable poison spheres and molybdenum-hafnium-carbon control rods. This work details studies developing and implementing these two reactivity control features over representative AHTR fuel cycles. Various Eu2O3 densities are considered to evaluate both the achieved reactivity control and the residual reactivity penalty of burnable poison at end of cycle. Control rod studies are performed to find integral and partial insertion reactivity worth for control rod banks at various radial locations. Axial power impacts are also evaluated. Focus then shifts toward control rod movement strategies. A manually generated insertion scheme leading to a critical configuration is first investigated to serve as a reference point for automated schemes to follow. Next, automated insertion and withdrawal strategies are evaluated based on their radial power peaking performance. Control rod insertions into the core locations with the highest local power are shown to be more stable than control rod withdrawals from core locations with the lowest local power. Finally, a methodology is introduced for finding a critical control rod insertion configuration. The methodology is intended to be used over a depletion sequence where the positions of the control rods are automatically adjusted to maintain criticality over cycle. In summary, this work presents a possible implementation of AHTR reactivity control and introduces automated control rod movement strategies for use in multi-physics depletion analyses.

Development and characterization of plasma electrolytic oxidation containing hydroxyapatite coating on selective laser melted Ti6Al4V porous scaffold

Ti6Al4V porous scaffolds are designed and fabricated to solve the elastic modulus mismatch between bone and an implant. Bioactive coating is applied on the surface of the implant to improve biocompatibility of titanium implants and form chemical bonds with surrounding bone. Therefore, this study aims to develop a bio-functional coating on Selective Laser Melting (SLM) manufactured porous Ti6Al4V scaffold produced using plasma electrolytic oxidation technique (PEO). Hydroxyapatite (HAp) and fluorapatite (FAp) were formed on the scaffold surface and field emission scanning electron microscopy (FESEM) was used to study the surface morphology and thickness of the coating. The chemical composition of the coatings was investigated by using an energy dispersive spectroscopy (EDS), X-ray diffractometer (XRD), and X-ray photoelectron spectroscopy (XPS). The coating formation was non-homogeneous with Ca/P ratio range of 1.24 to 1.41, approaching ratio of tricalcium phosphate compound. In vitro bioactivity test using a simulated body fluid (SBF) was conducted and the apatite formation on the coating was analyzed. PEO coatings on Ti6Al4V SLM-manufactured porous scaffolds containing fluoride and calcium salt have shown good bioactivity with the apatite formation that can be observed on all coated scaffolds. It was concluded that the combination of bio-functional coating on the surface of the SLM-manufactured porous scaffold provides synergistic effects, which was beneficial in improving the biocompatibility of orthopedic porous metallic implants. Hence, SLM-PEO approach potentially can be adapted to develop a bioactive titanium implant with tunable mechanical properties for orthopedic applications.

Controlling lithium cobalt oxide phase transition using molten fluoride salt for improved lithium-ion batteries

LiCoO2 is a historic lithium-ion battery cathode that continues to be used today because of its high energy density. However, the practical capacity of LiCoO2 is limited owing to the harmful phase transition at high voltages, which prevents the realization of its theoretical capacity. Here, we treat LiCoO2 particles with a molten salt of MgF2–LiF as a reaction accelerator to facilitate the diffusion and doping of magnesium into bulk LiCoO2 and to form a stable coating layer on the particle surface. Ex situ X-ray diffraction analysis confirms the inhibition of the harmful phase transition and the emergence of a different phase as the modified LiCoO2 was charged up to 4.7 V. The modified LiCoO2 shows high electrochemical performance during high-voltage operation. This technology provides a guideline for the suppressing fundamental degradation associated with phase transition and achieving ultra-high energy density LiCoO2 cathodes.