Metal Surface Research Articles

Alkaloid extract of seed Citrullus colocynthis as novel green inhibitor for mild steel corrosion in one molar HCl acid solution: DFT and MC/MD approaches

The study was designed to explore the corrosion prevention capabilities of Citrullus colocynthis seeds alkaloid-rich extract (CSEA) on MS in a 1 M HCl environment by use of electrochemical and theoretical methods. Notably, Electrochemical Impedance Spectroscopy (EIS) and potentiodynamic polarization were used to probe the impact of immersion time and temperature. Energy-dispersive X-ray spectroscopy (EDX) and spanning electron microscopy (SEM) were used to confirm the presence of a protective layer on the substrate surface. Density functional theory (DFT) method was used to optimize the investigated species by use of B3LYP/6–31 + G(d, p) level of theory. The global and local quantum chemical reactivity descriptors were calculated to explore the inhibition corrosion efficiency and to identify the most favorable sites for electrophilic and nucleophilic attacks. Monte Carlo (MC) and molecular dynamics simulation (MDS) methods were used to study the interactions between corrosion inhibitor and metal surface. Noteworthy, results showed that CSEA exhibited an impressive inhibition efficiency, which reached 94.3% with a concentration of 2 g/L at 298 K. Potentiodynamic polarization revealed that the extract acted as a mixed-type inhibitor. Nyquist graphs showed that charge-transfer resistance and dæouble-layer capacitance both rised with increasing CSEA concentration, suggesting better inhibition efficiency. Notably, the Langmuir adsorption isotherm is well-aligned with the adsorption of inhibitor compounds. Importantly, all aforementioned theoretical methods were in agreement with the experimental findings. The outcome of the present work supported using Citrullus colocynthis seeds alkaloid-rich extract as ecofriendly agents to prevent corrosion.

Thermally stable high-loading single Cu sites on ZSM-5 for selective catalytic oxidation of NH3

Rigorous comparisons between single site- and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst.

Electroless Copper Plating on a Cotton Surface: Effect of Metal Ion Ligand Stability Constant on Reduction Deposition.

Electroless plating facilitates the metallization of nonconductive substrate surfaces, and of note, the precise control of the bath stability constant influences the deposition process of metal particles. In this paper, trisodium citrate, potassium sodium tartrate, nitrogen triacetic acid, thiourea, and ethylenediamine tetraacetic acid disodium were selected as coordination agents, and the effect of the metal ion ligand stability constant on the reduction deposition was studied. Coordination bonds can be established between the Cu2+ and O/N/S particles in the ligand because paired electrons in O/N/S hybrid orbitals tend to occupy empty Cu2+ hybrid orbitals and establish coordination bonds. More importantly, the copper-potassium sodium tartrate ligand exhibits the lowest stability constant and lowest reduction barrier. As an exception, a consecutive Cu-plated coating with an excellent crystallinity property was deposited on the cotton surface when potassium sodium tartrate was used as the coordination agent in the plating solution. The deposition amounts are 55.2% and 74.1% after 1 and 4 h of electroless copper plating, respectively. The surface resistivity of Cu-plated cotton is 0.38 Ω/cm2, and additionally, the surface resistivity ratio before and after 1000 cycles fluctuated between 0.9 and 1.1, indicating that the Cu-plated cotton exhibits outstanding flexibility. In this paper, the deposition rate can be optimized by adjusting the copper particle ligand stability constant in the plating solution, aiming to achieve optimal results.

Growth Mediated Disassembly of Cucurbit[8]uril Cross‐linked Static Cubic Self‐assembly of Silver Nanoparticles

Static self‐assembly resides in thermodynamically stable global minima of the energy landscape, whereas dynamic self‐assembly occupies local minima of the energy profile and remain in the ordered state for a limited time via dissipation of energy to surroundings. This makes the spatiotemporal control over assembly and disassembly mechanism easily controllable in case of dynamic self‐assembly. But due to higher thermal stability of static self‐assembly, it is very challenging to perform reverse engineering upon these types of systems. Herein we report growth reaction based reversal of static silver cubes obtained via cucurbit[8]uril (CB[8]) crosslinked self‐assembly of silver nanoparticles (AgNP). The AgNP building units with variable CB[8] surface coverage have been used as seed onto which deposition of gold via growth reaction has been performed. The disassembly of supracube structure has been controlled by the formation of [AuCl4]¯‒CB[8] complex and successive reduction of [AuCl4]¯ to Au0 on the surface of seed. The resulting monodispersed isotropic nanoparticles, formed from the CB[8] based cubic self‐assembly after growth, exhibit Au‐Ag bimetallic nature. Quenching of the fluorogenic response from the hydrophobic dye coumarin‐7, added after growth, suggests direct interaction with the metallic nanoparticle surface after disassembly and thereby confirms successful growth reaction mediated reversal of self‐assembly.

Analysis of Opaque, Peel-Off and Flex Rejects in the Electro Plating Process Using the Six Sigma Dmaic Method

The modern manufacturing industry is faced with increasing pressure to achieve high levels of quality while remaining efficient in its production processes. One of the challenges faced by PT. Plating services in electroplating production have a high reject rate, which can cause increased costs and have a negative impact on the company's reputation. PT. Jasa Plating in the production process still has a high number of rejects, the rejects are dominated by opaque, peel-off and spots. PT. Plating services for each production contribute a high average of 2% defects per day, DPMO 20,000 and Sigma value 3.55. Quite a few rejections resulted in a decrease in turnover and increased production costs. The costs incurred due to these rejects are an average of Rp. 1,268,593 per day and an average of Rp. 35,698,907 per month as a result of data collection from January – September 2023. In this business process, this is very detrimental for the company. The aim of this research is to suppress blurry rejects, peel-offs and spots in the electro plating process at PT. Plating Services. The steps taken in conducting research include: identification stage, data collection and processing, analysis and recommendations for improvement, and conclusions. The method used in this research is the Six Sigma DMAIC (Define, Measure, Analysis, Improvement, Control) method. Through analysis, you can find several factors that cause high reject rates, including operational errors, discrepancies in the production process, or raw material quality problems. After implementing the improvement plan, then evaluate the results. This can include re- measuring the DPMO, analysis of the resulting products to see a decrease in reject rates, and comparisons between before and after implementing improvements. From the comparison results after the repairs were carried out, the data before the repairs were carried out, the NG amount was 1.99%, the DPMO was 6,646 and the Sigma value was 3.98. After improvements to NG 0.84%, DPMO 2,791 sigma value 4.28. Factors causing high levels of blurring, peel-off and spots, namely insufficient or excessive cleaning of the metal surface before the electroplating process, can cause problems such as peel-off. Contamination of the electroplating solution by foreign materials can cause blurring and flecks in the final layer. Machinery or equipment that is not properly calibrated, or experiences wear and tear, can produce products that do not meet standards. Variations in temperature, time, or electric current in the electroplating process can produce inconsistent coatings. Carefully monitor and control process-parameters to ensure stability.

Amorphous High‐Entropy Alloy Interphase for Stable Lithium Metal Batteries

AbstractThe unstable anode/electrolyte interphase induces severe lithium dendrite growth hindering the practical application of lithium metal batteries. The lithium alloy interphase presents a promising strategy for regulating Li+ plating/stripping behavior. However, binary or ternary alloys are insufficient to address various challenges in lithium metal batteries and the high temperature required for alloy preparation hampers their direct applications on lithium metal surfaces. In this study, a high‐entropy alloy (HEA) interphase is developed on lithium metal surfaces via room‐temperature magnetron sputtering, showcasing multifunctional advantages in regulating Li+ plating/stripping behavior. The cocktail effect of the (HEA) facilitated the formation of a homogeneous amorphous interphase with abundant lithiophilic sites and magnetic properties, promoting uniform Li+ nucleation and deposition. Furthermore, the high mechanical strength and corrosion resistance of HEA provided physicochemical stability for the lithium anode interphase, consistently suppressing dendrite growth. Consequently, lithium metal anodes with HEA interphases exhibited robust cycling performance lasting over 4000 h at 2 mA cm−2. The LFP full battery demonstrated high‐capacity retention of 90% with an average Coulombic efficiency of 99.7%. Thus, the HEA interphases on lithium metal surfaces offer controllable regulation of Li+ deposition behavior through high‐entropy manipulation, opening novel strategies for stable lithium metal batteries.

From Ethylene Glycol to Glycolic Acid: Electrocatalytic Conversion on Pt-Group Metal Surfaces.

Ethylene glycol (EG) is one of the most attractive platform molecules derived from biomass and waste plastics. Thus, the selective electrooxidation of ethylene glycol (EGOR) into value-added chemicals (especially glycolic acid (GA)) can promote its recycling and upgrading. However, the understanding of the EG-to-GA process on Pt-group metal (PGM) electrodes is far limited now. It has been shown that the Pt and Pd electrodes could show considerable EGOR activity but not Rh and Ir electrodes. Meanwhile, EGOR mainly produces the glycolate, oxalate, and formate on Pt and Pd electrodes, whereas it can obtain minute amounts of glycolate and oxalate on Rh and Ir electrodes. Impressively, the selectivity of glycolate on Pt and Pd electrodes can be over 85% (apparent Faradaic efficiency) in alkaline media, although the stability should be further improved through interfacial tuning and/or engineering. This work might deepen the fundamental understanding of the EGOR process on the nature of PGM electrodes.

Biogenic corrosion inhibition through Bacillus coagulans on mild steel in mild acidic medium

In the present study, the corrosion inhibition properties of Bacillus coagulans against mild steel (MS) were studied employing electrochemical procedures to monitor the real-time corrosion rate, mechanism, development of efficient mitigation strategies, and material protection. Results of the study revealed that under acidic environments B. coagulans formed a protective biofilm on MS surface and caused marked reduction in corrosion and other forms of mutilation. Characterization and electrochemical procedures were performed to investigate the inhibitory effects of B. coagulans at different pH and at different temperatures on the corrosion rate and, to determine the mechanism of corrosion prevention. The film developed on surface of the MS by B. coagulans, was crack free, compact, and lipophilic in nature and was composed of amyloid fibers, carboxylic acid, and proteins that make electrochemical reactions that, accruing on the metal–solution interface difficult and substantial reduction in corrosion rates observed. The film adhered to the surface of metal substrates shows fitting with diverse adsorption isotherm indications, with physical adsorption being the predominant pattern observed in most cases. This suggests that the interaction between the biofilm and metal surfaces is primarily governed by physical forces. To conclude, B. coagulans exhibits protective action on MS against corrosion.

Mechanical and Corrosion Properties of Super Austenitic Stainless Steel Joint for Double‐Sided Synchronous TIP TIG Arc Butt Welding

Super austenitic stainless steel 254SMO (254SMO SASS) plates are joined by double‐sided double‐arc synchronous TIP TIG butt welding (DSSTTABW) using ER NiCrMo3 wire, and the micro‐structure, mechanical and corrosion properties of 254SMO SASS joints are investigated subsequently. Results show that solidification grain boundary and solidification sub‐grain boundary can be observed in fusion zone. A small amount of σ phase precipitates in the weld, while χ phase is found in the transition zone, but no solidification crack occurs in weld and heat affected zone (HAZ). 254SMO SASS joint has higher micro‐hardness and lower tensile strength and elongation compared to base metal. During transverse tensile process, 254SMO SASS joints fail in the weld zone in a ductile mode. Electrochemical corrosion performance tests indicate that 254SMO SASS joint achieve equivalent pitting corrosion resistance and similar passive mechanism to base metal in 3.5 wt% NaCl solution. The passivation film on the surface of both joint and base metal display as n‐p semi‐conductive character, but the film stability of 254SMO joint surface is slightly poorer compared to base material. The surface passivation film of 254SMO joint primarily consists of oxides of Fe, Cr, and Mo before potentiodynamic polarization, while hydroxides of Fe and Cr are also observed after polarization.

Copper‐cobalt bimetallic nanoparticles for the acceptorless dehydrogenation of alcohols: a combined experimental and theoretical study.

Bimetallic Cu and Co nanoparticles were prepared using the polyol process. The nature of the polyol was found to be decisive to control the distribution of the two metals within the particles, resulting in either core‐shell or quasi‐alloyed structures, as shown by chemical analysis at the single particle level. The particles can be prepared over the entire composition range with a very good control of the Cu/Co molar ratio. The introduction of Cu in the synthetic system allows decreasing significantly the mean size of the resulting particles. The two sets of particles were used as unsupported catalysts for the solvent‐free acceptorless dehydrogenation of octan‐2‐ol. Very good ketone yields were measured when using the quasi‐alloyed particles while lower activities were obtained with core‐shell structures. The Cu25Co75 quasi‐alloyed catalyst could be recycled at least ten times without a significant loss in catalytic activity and particle‐scale chemical analyses confirmed that the recovered particles are still alloyed with no observed demixing. The catalytic results are discussed in the light of different exposed metal surface areas and possible synergetic effects using theoretical predictions.

Revealing the nontrivial topological surface states of catalysts for effective photochemical carbon dioxide conversion

Topological semimetals with protected surface states mark a new paradigm of research beyond the early landmarks of band-structure engineering, allowing fabrication of efficient catalyst to harness the rich metallic surface states to activate specific chemical processes. Herein, we demonstrate a facile solid-phase method for in-situ doping of Ir at the Os sites in the Os3Sn7, an alloy with topological states, which significantly improves the photocatalytic performance for the reduction of CO2 to CO and CH4. Experimental evidence combined with theoretical calculations reveal that the nontrivial topological surface states greatly accelerate charge-separation/electron-enrichment and adsorption/activation of CO2 molecules, rendering highly efficient reaction channels to stimulate the formation of *COOH and *CO, as well CHO*. This work shows the promise of achieving high photocatalytic performances with synthesizing topological catalysts and provides hints on the design of novel topological catalysts with superior photoactivity towards the CO2 reduction reaction.

First-Principles Nonadiabatic Dynamics of Molecules at Metal Surfaces with Vibrationally Coupled Electron Transfer

First-Principles Nonadiabatic Dynamics of Molecules at Metal Surfaces with Vibrationally Coupled Electron Transfer

Investigation of corrosion inhibition and adsorption properties of quinoxaline derivatives on metal surfaces through DFT and Monte Carlo simulations

Investigation of corrosion inhibition and adsorption properties of quinoxaline derivatives on metal surfaces through DFT and Monte Carlo simulations

Interfacial structure and acidity of orthoclase (001) surface: understanding the effect of surface metal cation

Interfacial structure and acidity of orthoclase (001) surface: understanding the effect of surface metal cation

Estimation of Time-Since-Deposition of bloodstains on different surfaces using ATR-FTIR Spectroscopy and Chemometrics.

Blood is commonly discovered at crime scenes in various forms, including stains, dried residue, pools, and fingerprints on assorted surfaces. Estimating the age of bloodstains is a crucial aspect of reconstructing crime scenes. This research aimed to investigate how the nature of different surfaces affects the estimation of bloodstain age, utilizing a reliable and non-destructive approach. The study employed ATR-FTIR spectroscopy in conjunction with Chemometric techniques such as PCA (Principal Component Analysis) and OPLSR (Orthogonal Signal Correction Partial Least Square Regression Analysis) to analyze spectral data and develop regression models for estimating bloodstain age on cement, metal, and wooden surfaces for up to eleven days. The chemometric models for bloodstains on all three substrates demonstrated strong performance, with predictive Root Mean Square Error (RMSE) values ranging from 1.1 to 1.43 and R2 values from 0.84 to 0.89. Notably, the model developed for metal surfaces was found to be the most accurate with minimal prediction error. The findings of the study showed that the porosity of the substrates upon which bloodstains were found had a discernible influence on the age-related transformations observed in bloodstains; the majority of which occured within the spectral range of 2800cm- 1 to 3500cm- 1.

Effect of brazing process on microstructure evolution and mechanical properties of Ti6Al4V/ZrO2 joints after laser surface treatment

Ti6Al4V alloy and ZrO2 ceramic have similar application fields and complementary properties. Brazing connections can broaden the application range. When using sealing glass with good air tightness, good electrical insulation, and low connection temperature to connect, the solder is difficult to wet on the metal surface. The traditional method is to oxidize the surface of the alloy at a high temperature, but the film is not uniform and the treatment time is long. In this study, nanosecond laser surface treatment was used as a prewelding pretreatment method to form a micro-nano structure on the surface and perform oxidation treatment. It is particularly important to select the brazing process. After the laser parameters and processing times were determined, the effects of different welding temperatures and holding times on the properties of the joints were compared, and it was found that there were regular changes. Finally, it is concluded that the maximum shear strength is 46 MPa when the welding temperature is 650 °C and the holding time is 30 min. Under this process, the performance of the joint significantly improved under the dual effects of mechanical bonding and metallurgical bonding. This study provides a new idea for the connection of metal and ceramic and has reference value for the selection of the brazing process.

Engineering Partially Oxidized Gold via Oleylamine Modifier as a High-Performance Anode Catalyst in a Direct Borohydride Fuel Cell.

Direct borohydride fuel cell (DBFC) is considered a promising energy storage device due to its high theoretical cell voltage and energy density. For DBFC, an Au catalyst has been used as an anode for achieving an ideal eight-electron reaction. However, the poor activity of the Au catalyst for borohydride oxidation reaction (BOR) limits its large-scale application because of the weak BH4- adsorption. We found, by density functional theory calculations, that the adsorption of BH4- on the oxidized Au surface is stronger than that on the metallic Au surface, which can promote the process of the oxidation of BH4- to *BH3 during the BOR. Here, we reported an oleylamine-modified partially oxidized Au supported on carbon powder (AuC-OLA) with a stable oxidation state. The obtained catalyst delivered a high peak power density of 143 mW/cm2, which is 2 times higher than that of a commercial 40% AuC (Pretemek). The in situ Fourier transform infrared studies showed that the activity of AuC-OLA for BOR is ascribed to the enhanced adsorption for BH4- on the partially oxidized Au surface. These findings will promote the reasonable design of efficient Au electrocatalysts for DBFCs.

Complementary Multisite Turnover Catalysis toward Superefficient Bifunctional Seawater Splitting at Ampere-Level Current Density.

The utilization of seawater for hydrogen production via water splitting is increasingly recognized as a promising avenue for the future. The key dilemma for seawater electrolysis is the incompatibility of superior hydrogen- and oxygen-evolving activities at ampere-scale current densities for both cathodic and anodic catalysts, thus leading to large electric power consumption of overall seawater splitting. Here, in situ construction of Fe4N/Co3N/MoO2 heterostructure arrays anchoring on metallic nickel nitride surface with multilevel collaborative catalytic interfaces and abundant multifunctional metal sites is reported, which serves as a robust bifunctional catalyst for alkaline freshwater/seawater splitting at ampere-level current density. Operando Raman and X-ray photoelectron spectroscopic studies combined with density functional theory calculations corroborate that Mo and Co/Fe sites situated on the Fe4N/Co3N/MoO2 multilevel interfaces optimize the reaction pathway and coordination environment to enhance water adsorption/dissociation, hydrogen adsorption, and oxygen-containing intermediate adsorption, thus cooperatively expediting hydrogen/oxygen evolution reactions in base. Inspiringly, this electrocatalyst can substantially ameliorate overall freshwater/seawater splitting at 1000mA cm-2 with low cell voltages of 1.65/1.69V, along with superb long-term stability at 500-1500mA cm-2 for over 200 h, outperforming nearly all the ever-reported non-noble electrocatalysts for freshwater/seawater electrolysis. This work offers a viable approach to design high-performance bifunctional catalysts for seawater splitting.

Energy Barriers for the Spontaneous Magnetization Reversal of the Atomic Co Chains on Pt(664) Surface in the Model with Dzyaloshinskii–Moriya Interaction

The analytical approach has been developed in the framework of the continuous XY-model. This approach allows calculating the spontaneous magnetization reversal time of finite-length atomic chains on the metallic surface. The interaction of the magnetic moments of atoms is described by the classical Hamiltonian, which includes the Heisenberg exchange interaction, the Dzyaloshinskii–Moriya interaction, and the magnetic anisotropy energy. Using the Co/Pt(664) system as an example, it has been shown that the proposed method is in a good agreement with the results of the numerical simulation in the limit of short and long atomic chains. And for atomic chains of intermediate length, it can be used to estimate an upper bound on the spontaneous magnetization reversal time. We obtained the dependences of the spontaneous magnetization reversal time of finite-length Co chains the value of the exchange integral, parameters of the magnetic anisotropy, and also on the value of the projection of the Dzyaloshinskii vector onto the axis perpendicular to the plane containing the magnetic moments of the atoms. It is shown that the proposed method has a wide range of applicability both in terms of temperature and the values of the physical parameters characterizing the magnetic properties of the atomic chains.

Exploring deep fully convolutional neural networks for surface defect detection in complex geometries

AbstractIn this paper, we propose a machine learning approach for detecting superficial defects in metal surfaces using point cloud data. We compare the performance of two popular deep learning architectures, multilayer perceptron networks (MLPs) and fully convolutional networks (FCNs), with varying feature sets. Our results show that FCNs (F1=0.94) outperformed MLPs (F1=0.52) in terms of precision, recall, and F1-score. We found that transfer learning with pre-trained models can improve performance when the amount of available data is limited. Our study highlights the importance of considering the amount and quality of training data in developing machine learning models for defect detection in industrial settings with 3D images.