Alloy Surface Research Articles

Investigating the Roles of Protein on the Cobalt Alloy Surface Degradation for Biomedical Implant Through Tribocorrosion Mechanisms

Previous investigation has established the formation of tribofilm is influenced by tribochemical reactions between the electrolyte and the articulating surface of cobalt alloy through sliding tests in various simulated fluids. Although it has successfully characterized the film composition via spectroscopy analysis and indicated to have impact on material loss, a comprehensive understanding of the material degradation mechanism in tribocorrosion condition was still lacking. Therefore, this study aims to investigate the role of protein in the tribocorrosive degradation of cobalt-chromium-molybdenum (CoCrMo) alloy in different simulated physiological electrolytes. Using a similar testing protocol, tribocorrosion tests were conducted with reciprocating ceramic ball against CoCrMo samples immersed in saline and culture medium, compared to both electrolytes diluted with 25% fetal bovine serum (FBS). Synergistic and mechanistic approaches were employed to model the tribocorrosive degradation. Results reveal that protein plays a beneficial role in reducing corrosive (electrochemical) surface degradation under tribocorrosion condition, whilst increasing mechanical wear degradation in the process. Despite studies have shown that tribocorrosion behavior in metal alloys is highly influenced by the presence of organic matter, this study provides a more clarity of the roles played by protein in tribocorrosive degradation on CoCrMo surface as its novel finding.

Characterization of Physical and Mechanical Properties of Tungsten Alloy Surfaces for Electroplasticity-Assisted Dry Cutting Machining

Characterization of Physical and Mechanical Properties of Tungsten Alloy Surfaces for Electroplasticity-Assisted Dry Cutting Machining

Nickel nitride-mediated nitric oxide generation for combating implant-associated infections

NiTi alloys are widely used in the fabrication of biomedical implants, and it is essential to endow them with selective antibacterial properties to avoid implant-associated infection. In this study, nickel nitride (Ni3N), as a promising new inorganic nitric oxide (NO) donor, was in situ constructed on the surface of NiTi alloys through a straightforward two-step plasma immersion ion implantation (PIII) strategy. Nickel sites were first exposed by physical bombardment with argon or metal plasma, followed by reaction with nitrogen plasma to form Ni3N. Ni3N can disrupt the transmembrane proton electrochemical gradient by capturing protons to produce ammonia species (NHx), resulting in the accumulation of reactive oxygen species (ROS) as a result of bacterial metabolic disruption. On the other hand, the generated NHx can further react with ROS to produce NO and reactive nitrogen species (RNS). As a result, the Ni3N films exhibited more than 99 % antibacterial efficiency against both gram-negative and gram-positive bacteria. They also demonstrated effective antibacterial properties in a rat subcutaneous implant model. In addition, the modified NiTi alloys exhibit good corrosion resistance and cytocompatibility. This study provides a green, safe, and inexpensive method for constructing metal nitride films on implant surfaces and offers new ideas for the clinical design and fabrication of novel antibacterial implants.

Surface characteristics of additively manufactured γ-TiAl intermetallic alloys post-processed by electrochemical machining

Electron beam melting (EBM) process is the most preferable powder bed fusion process for high melting point alloys. γ-TiAl alloys are intermetallic chemical compounds, which are lightweight and resistant to oxidation and heat, and have low ductility as well. EBM is the best manufacturing process for such alloys to produce aerospace parts, but poor surface quality is the main drawback of this process. Thus, surface post-processing is needed after the EBM process. This study presents the surface characteristics of EBM γ-TiAl alloy surfaces post-processed by electrochemical machining (ECM). The surfaces were ECM and the surface roughness values (Sa, Sq and Sz) have been reduced significantly. The mean reduction values of the experiments are 98.6 %, 98.5 % and 95.3 % for Sa, Sq and Sz, respectively. Additionally, it is observed that the surface roughness is inversely proportional to the electrolyte conductivity up to a limit value (115 mS/cm), and after that the roughness increases via the stray current transition. Sq values decrease with the increased feed rate via the increased current density. However, an increase in feed rate negatively affects the Sku values, which statistically describe the sharpness or spread of surface roughness. Also, XRD results showed that Ti2AlN layer is formed on the surface via the HIP operation. This layer inhibits the electrochemical dissolution of γ-TiAl alloy and caused surface defects.

In-Depth Insight into Corrosion Inhibition Performance of Sweet Potato Leaf Extract as a Green and Efficient Inhibitor for 6N01 Al Alloy in the Seawater: Experimental and Theoretical Perspectives.

Corrosion protection of metal has become an important and urgent topic, which requires the development of an inexpensive, environmentally friendly, and highly efficient corrosion inhibitor. Herein, a sweet potato leaf extract (SPL) was obtained by a simple water-based extraction method and then as a green corrosion inhibitor for 6N01 Al alloy in the seawater was well investigated by the weight loss method and various electrochemical tests. Fourier transform infrared (FT-IR) and ultraviolet-visible (UV-vis) spectroscopies were carried out to investigate the compositions of SPL. The findings from the potentiodynamic polarization (PDP) curves suggest that SPL functions as a typical mixed-type corrosion inhibitor. Notably, the maximum corrosion inhibition efficiency reaches 94.6% following a 36 h immersion period at 25 °C. The adsorption behavior of SPL on the Al alloy surface belongs to the Langmuir adsorption isotherm. The Gibbs free energy value illustrates that the adsorption of SPL contains both physisorption and chemisorption. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) indicate that SPL is firmly attached to the Al alloy surface by making a protective layer, which can effectively inhibit the corrosion of the Al alloy in the seawater. Furthermore, quantum chemical calculations were applied to validate the chemical adsorption and elucidate the relationship between the electronic structure of the active components in SPL and their effectiveness in corrosion inhibition.

Primary dendrite growth within binary Fe71Ge29 eutectic alloy under duplex levitation states

The primary β-Fe3Ge2 dendrite growth kinetics within liquid Fe71Ge29 eutectic alloy was studied by both acoustic levitation and electrostatic levitation techniques, with maximum experimental undercoolings of 130 and 143 K, respectively. At small undercoolings, (α1 + β-Fe3Ge2) eutectic growth proceeded and then transformed to lamellar (ε-Fe3Ge + β-Fe3Ge2) microstructure by peritectoid reaction. Once liquid undercooling reached 56 K, β primary phase started to nucleate preferentially and its maximum growth velocity attained 13.5 mm/s at 143 K undercooling. By acoustic levitation processing, β dendrites were distributed inside the alloy droplet. Under electrostatic levitation state, β dendrites were distributed both at the periphery and within the interior of alloy droplet, and their volume fraction was significantly higher than that under acoustic levitation. Numerical simulation results indicated that a duplex flow was induced by alloy droplet shape oscillation and acoustic streaming. The flow exhibited maximum intensity near the alloy surface, which inhibited the achievement of larger undercoolings during acoustic levitation.

Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First‐principle Screening with Consideration of H‐coverage

The highly selective hydrogenation to remove olefins is a significant refining approach for the reformate. Herein, a library of transition metal for reformate hydrogenation is tested experimentally to validate the predictive level of catalytic activity from our theoretical framework, which combines ab initio calculations and microkinetic modeling, with consideration of surface H‐coverage effect on hydrogenation kinetics. The favorable H coverage of specific alloy surface under relevant hydrogenation condition, is found to be determined by its corresponding alloy composition. Besides, olefin hydrogenation rate is determined as a function of two descriptors, i.e. H coverage and binding energies of atomic hydrogen, paving the way to computationally screen on metal component in the periodic table. Evaluation of 172 bimetallic alloys based on the activity volcano map, as well as benzene hydrogenation rate, identifies prospective superior candidates and experimentally confirms that Zn3Ir1 outperforms pure Pd catalysts for the selective hydrogenation refining of reformate. The insights into H‐coverage‐related microkinetic modelling have enabled us to both theoretically understand experimental findings and identify novel catalysts, thus, bridging the gap between first‐principle simulations and industrial applications. This work provides useful guidance for experimental catalyst design, which can be easily extended to other hydrogenation reaction.

Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First-principle Screening with Consideration of H-coverage.

The highly selective hydrogenation to remove olefins is a significant refining approach for the reformate. Herein, a library of transition metal for reformate hydrogenation is tested experimentally to validate the predictive level of catalytic activity from our theoretical framework, which combines ab initio calculations and microkinetic modeling, with consideration of surface H-coverage effect on hydrogenation kinetics. The favorable H coverage of specific alloy surface under relevant hydrogenation condition, is found to be determined by its corresponding alloy composition. Besides, olefin hydrogenation rate is determined as a function of two descriptors, i.e. H coverage and binding energies of atomic hydrogen, paving the way to computationally screen on metal component in the periodic table. Evaluation of 172 bimetallic alloys based on the activity volcano map, as well as benzene hydrogenation rate, identifies prospective superior candidates and experimentally confirms that Zn3Ir1 outperforms pure Pd catalysts for the selective hydrogenation refining of reformate. The insights into H-coverage-related microkinetic modelling have enabled us to both theoretically understand experimental findings and identify novel catalysts, thus, bridging the gap between first-principle simulations and industrial applications. This work provides useful guidance for experimental catalyst design, which can be easily extended to other hydrogenation reaction.

High-efficiency and low-damage modification of engineering metal materials by oxygen-mixing atmospheric pressure cold plasma jets

Engineering metal materials have been widely developed and applied in aviation, aerospace and biomedicine fields. Wettability improvement of these materials can alleviate problems caused by low adhesion and poor bioactivity, thereby facilitating their practical applications. Compared with other methods, atmospheric pressure cold plasma treatment has better versatility and can efficiently improve wettability without causing serious damages, and has therefore been widely used in polymer hydrophilization. However, when treating metal materials, the cold plasma may induce surface breakdown or have low efficiency. In this paper, we developed a new cold plasma jet by mixing oxygen into working gas to achieve high-efficiency and low-damage modification. When oxygen mixing ratio was 0.4 %, the cold plasma jet could modify TC4 titanium alloy surface to be superhydrophilic within 20 s, which was much more efficient than traditional plasma jet (120 s). We then further investigated the mechanism contributing to higher efficiency, and found that the oxygen-mixing plasma jet did not cause serious damages, while generating more polar groups by higher-concentration active particles, as confirmed by surface energy calculation and optical emission spectra. Besides titanium alloy, the oxygen-mixing plasma jet could also achieve rapid hydrophilization of various engineering metal materials, showing promising application prospects.

Selective Cleavage of α-Olefins to Produce Acetylene and Hydrogen.

Acetylene production from mixed α-olefins emerges as a potentially green and energy-efficient approach with significant scientific value in the selective cleavage of C-C bonds. On the Pd(100) surface, it is experimentally revealed that C2 to C4 α-olefins undergo selective thermal cleavage to form surface acetylene and hydrogen. The high selectivity toward acetylene is attributed to the 4-fold hollow sites which are adept at severing the terminal double bonds in α-olefins to produce acetylene. A challenge arises, however, because acetylene tends to stay at the Pd(100) surface. By using the surface alloying methodology with alien Au, the surface Pd d-band center has been successfully shifted away from the Fermi level to release surface-generated acetylene from α-olefins as a gaseous product. Our study actually provides a technological strategy to economically produce acetylene and hydrogen from α-olefins.

The microstructure and electrochemical performance of the Al-10Si-3.5Fe-xZn-yGa alloys for hot-dip galvanizing in low-chloride environments

The microstructure and electrochemical performance of Al-10Si-3.5Fe-xZn-yGa alloys in low-chlorine environments were studied by SEM observation and electrochemical analysis. The microstructure of Al-10Si-3.5Fe-xZn-yGa alloys consisted of Si phase, τ6, and α-Al matrix. The addition of Zn or Ga did not affect the morphology and phase of the microstructure. Pitting corrosion, galvanic corrosion of α-Al matrix with Si phase and τ6, and anisotropic corrosion of τ6 occur in the low-chloride environments for the alloys. The addition of Zn not only promoted the development of pitting pits on the α-Al matrix but also reduced the electrode potential of the α-Al matrix, increased the galvanic corrosion potential difference, and accelerated the corrosion rate of the α-Al matrix. The addition of Ga could induce pitting corrosion on the surface of intact τ6 and α-Al matrix synchronously, reducing both electrode potential and accelerating the alloy's corrosion rate. The synergistic action of Zn and Ga could promote the alloy's sustained activation. Corroded τ6 developed cracks and fragmentation, with the resulting cracks serving as pathways for the ingress and egress of Cl− and other particles, leading to internal corrosion of the alloy. The stress generated during the fragmentation process of τ6 promoted extensive delamination of the alloy surface, preventing corrosion products from covering the alloy's surface.

Sub-5 nm ultrathin IGO film transistor printed by micro-doped InGa liquid alloy

In this study, we introduce a novel perspective that the formation of the atomically ultrathin oxide layer on the surface of liquid alloys is primarily governed by thermodynamic laws and is additionally influenced by the surface tension of the liquid alloys. In this case, we control the competition of Gibbs free energy and surface tension to effectively address the severe segregation problem of Ga2O3 and realize the precise doping of Ga2O3 in the preparation process of two dimensional IGO film through the liquid InGa alloy printing approach. Importantly, the Ga2O3 content in the IGO films can be tailored in the full range and a sub-5 nm ultrathin IGO film transistor is innovatively fabricated. The oxidation law, band gap, Fermi level, field-effect mobility, subthreshold swing, and other properties of IGO films in sub-5 nm scale are systemically investigated in detail. It has been demonstrated that the incorporation of Ga2O3 in the doping process dramatically reduced the device's turn-off current and enhanced its ability to resist ultraviolet interference. This novel doping process opens up a significant opportunity for future developments of atomically ultrathin transparent conducting film.

Research Progress in the Failure Behavior on the Interface of Thermal Barrier Coatings

This paper mainly introduces the research progress on interface failure behavior in hightemperature alloy surface thermal barrier coating systems. The degradation failure and structural evolution behavior during high-temperature service were analyzed for the matrix/bonding layer interface, bonding layer/TGO interface, and TGO/ceramic layer interface in thermal barrier coatings. The research focus and direction that affect the interface performance of thermal barrier coatings were proposed.

In-situ construction of bioactive nanostructures on Ti alloy surfaces through ultra-low concentration alkali treatment and low-temperature annealing

Osseointegration is crucial for the long-term stability of orthopedic implants. Nanosurfacing can impart osteoinductivity to the implant. However, the application potential of most available nanotechnologies in surface modification of implants is limited, and there is an urgent need to develop new effective nanosurfacing techniques with greater practicality. In this study, we for the first time, utilized an ultra-low concentration NaOH solution (0.55 mM) combined with low-temperature annealing to achieve solid-state dewetting (SSD) on Ti alloy surfaces, resulting in well-defined TiO2 nanoisland-like crystals. In vitro cell experiments demonstrated that the constructed nanostructures significantly affected the adhesion, proliferation, and osteogenic differentiation capability of MC3T3-E1 cells. The nanostructures formed at 550 °C exhibited the most pronounced enhancement of cell osteogenic differentiation capability. This method is simple, easy to operate, and scalable, holding significant application potential in the surface modification of Ti alloys.

The electrochemical corrosion behavior of Ti-5Al-5Mo-5V-1Cr-1Fe titanium alloy with different initial microstructures

The corrosion behavior of Ti-5Al-5Mo-5V-1Cr-1Fe titanium alloy with different initial microstructures was investigated by conducting a series of electrochemical tests. Based on the experimental data, the effects of NaCl solution concentration and corrosion time on the electrochemical polarization curves, corrosion rates, electrochemical impedance spectroscopy (EIS), and impedance of the alloy with two initial microstructures were analyzed. The assessment of the corrosion current density (Icorr) and corrosion rate (CR) for the alloy under different corrosion conditions reveals a general pattern of initial decrease followed by increase in their values with extended corrosion time and elevated solution concentration, whereas the capacitive reactance arc exhibits an opposite trend. For alloys with initial equiaxed microstructures, the Icorr value is 0.1892 μA/cm2, and the CR value is 0.000413 mm/year; these values are lower than those of 1.298 μA/cm2 and 0.002842 mm/year for alloys with initial lamellar microstructures. Whereas the capacitive reactance arc and the impedance value are greater for the titanium alloy with initial equiaxed microstructure. Based on the adsorption kinetics principles, the effects of temperature on corrosion rate of alloys with different initial microstructures at a consistent concentration were analyzed. Compared to the alloy with initial lamellar microstructure of 3054 kJ/mol, the alloy with initial equiaxed microstructure had an activation energy of 4155 kJ/mol. As the temperature rises, the rate of corrosion tends to increase. The results suggested that the alloy with initial equiaxed microstructure presented the superior corrosion resistance than the alloy with the initial lamellar microstructure. Additionally, the corrosion morphologies after polarization of the alloy were characterized. And the results show that the surfaces of titanium alloys with initial lamellar microstructure display a comparatively greater incidence of pitting corrosion upon assessment of the corrosion morphology.

Adhesive strength of ice on solid surfaces under dynamic heating condition

A clear and comprehensive understanding of the dynamic changes in ice adhesion during the operation of thermal de-icing systems on an airplane can help in realizing safer operation of these systems. In this study, we aim to elucidate the ice adhesion decay pattern on different materials under thermal de-icing conditions. Molds are used to form ice on the surfaces of aluminum alloy, stainless steel, titanium alloy, and polytetrafluoroethylene (PTFE), and then their initial and dynamic ice adhesive strengths are measured. The effects of surface roughness and heating rate are also explored. The results show that the residual adhesive strength is almost linearly proportional to the instant temperature before it rises to −0.5 °C for the three types of metallic surfaces. However, for PTFE surfaces, instead of a reduction in the adhesive strength caused by heat, adhesive failure occurs due to the high stress induced by thermal deformation of the substrate. Under dynamic heating conditions, the impact of substrate’s roughness on the adhesive strength is significantly weakened, and the heating rate has a minor effect on the relationship between adhesive strength and instant temperature.

Optimization of Mg-Al Layered Double Hydroxide Film Preparation and Corrosion Resistance Study on AZ91D Mg Alloy by Multivariate Polynomial Regression Fitting.

Layered double hydroxide (LDH) films have received extensive attention for their unique physical barrier function and ion exchange properties, which make them promising candidates for corrosion protection of magnesium alloys. In this paper, we used the multiple polynomial regression fitting method to establish a regression equation for the electrochemical corrosion resistance with the reaction temperature (T), pH, and reaction time (t) of the Mg-Al LDH film on the AZ91D magnesium alloy. The goodness of fit, confidence, and residual analyses confirmed the high accuracy of the model equation. According to the calculation using the fmincon function, the best corrosion resistance of the prepared samples could be achieved when the parameters are T = 135 °C, pH = 12.0, and t = 15 h. Then, the experimental results showed that the corrosion current density (Icorr) of the obtained LDH film under the above conditions could be 1.07 × 10-7 A/cm2, approximately 3 orders of magnitude lower than the magnesium alloy substrate, after immersion in a 3.5 wt % NaCl solution for 180 h, the surface structure of the LDH film did not change significantly, and the Icorr was still 2 orders of magnitude higher than that of the magnesium alloy substrate. Hence, a synergistic effect equation for the reaction temperature, pH, and reaction time on the corrosion resistance of the LDH film on a magnesium alloy surface prepared by the hydrothermal method was obtained. Moreover, using this equation, we obtained an LDH film with good corrosion resistance and durability, providing theoretical guidance for optimizing the process of preparing the LDH film by the hydrothermal method in practical applications.

Shot peening of AZ31 magnesium alloy: role of surface microstructure and iron diffusion on corrosion behaviour

ABSTRACT In the present work, surface grain refined AZ31 magnesium (Mg) alloy was produced by shot peening (SP). X-ray diffraction analysis demonstrated iron diffusion into the surface of AZ31 Mg alloy during SP. Higher hardness, increased surface energy and decreased corrosion resistance were observed for the shot-peened surface due to nanostructured grains resulted from SP. From the immersion studies in a simulated physiological solution carried out for 3 days, higher level of biomineralization was observed for the shot peened AZ31 compared with the base alloy that dominated the adverse effect of iron diffusion in resisting the biocorrosion. The results suggest that the nano-structuring of AZ31 Mg alloy surface helps to enhance the biomineralization to control the degradation. However, the selection of processing medium is crucial to eliminate the effect of chemical composition change during the process in tailoring the corrosion behaviour of AZ31 Mg alloy for biomedical implant applications.

Quality control of NiCr-Cr3C2-hBN@Ni coating on thin-walled GH4169 alloy surface prepared by plasma spraying

As equipment lightweight trends progress, thin-walled structures have seen extensive application in critical aerospace components. Nevertheless, the aero-engine tail nozzle flaps are exposed to the harsh operating conditions of high-temperature friction, so there is an urgent requirement to prepare wear-resistant, self-lubricating coatings with a wide range of temperatures for their protection. Due to the poor rigidity and weak strength of thin-walled workpieces and complex forms of structural stresses, the processing is extremely difficult. In order to solve the thermal deformation problem of coating workpieces prepared by spraying on the surface of thin-walled workpieces, the effects of spraying path, cooling airflow, and spraying interval on the thermal force field of thin-walled workpieces to prepare NiCr-Cr3C2-hBN@Ni coating are investigated in this study using finite element simulation. As a result, the deformation and stress of thin-walled workpieces can be minimized by adding back-side cooling air during the spraying process and moving the cooling air with the gun in a set interval, with the maximum warpage and maximum stress being less than 2.366 mm and 0.177 GPa, respectively. During the spraying process by simulating the optimum spraying process, no significant warpage of the substrate occurred and the coating was sprayed with uniform thickness. Typically, the thickness error rate is 16.7 %, and the coating hardness reaches 15–20 GPa, with excellent tribological properties in a wear rate of 10−5 mm3·N−1·m−1 and 10−6 mm3·N−1·m−1, which protects the workpiece effectively.

Comprehensive Unveiling of the Oxidation Resistance and Corrosion Protection of an Oxide Layer Formed on the Gd-Alloyed AZ80 Alloy Surface

Comprehensive Unveiling of the Oxidation Resistance and Corrosion Protection of an Oxide Layer Formed on the Gd-Alloyed AZ80 Alloy Surface