Composition Of Surface Layer Research Articles

Complex Modification of the Surface Layer of a High-Entropy Al-Cr-Fe-Co-Ni Alloy by Electron-Ion-Plasma Treatment

Using the technology of wire-arc additive manufacturing (WAAM – wire arc additive manufacture), a high-entropy alloy (HEA) of non-equiatomic composition Al, Cr, Fe, Co, Ni was manufactured. Using the methods of modern physical materials science, an analysis of the elemental and phase composition, defective substructure, mechanical and tribological properties of the HEA surface layer, formed as a result of complex modification, combining the deposition of a film (B + Cr) and irradiation with a pulsed electron beam in an argon medium, was carried out. In the initial state, the alloy has a simple cubic lattice with a lattice parameter of 0.28795 nm; the average grain size of the HEA is 12.3 µm. Chemical elements (at. %) 33.4 Al; 8.3 Cr, 17.1 Fe, 5.4 Co, 35.7 Ni, which form HEA, are distributed quasi-periodically. The irradiation regime was revealed (energy density of the electron beam ES = 20 J/cm2, pulse duration 200 µs, number of pulses 3 pulses, frequency 0.3 s more than 5 times), allowing to increase microhardness (almost 2 times) and wear resistance (more than 5 times), reduce the coefficient of friction by 1.3 times. Regardless of the value of ES, HEA is a single-phase material and has a simple cubic crystal lattice. High-speed crystallization of the surface layer leads to the formation of a subgrain structure (150–200) nm. It is shown that an increase in the strength and tribological properties of HEA is due to a significant (4.5 times) decrease in the average grain size, the formation of particles of chromium and aluminum oxyborides, and the incorporation of boron atoms into the crystal lattice of HEA.

Composition and Structure of Surface Layer in Composite Castings from Gray Cast Iron Formed Using Chromium-Ferroboron Master Alloys

Composition and Structure of Surface Layer in Composite Castings from Gray Cast Iron Formed Using Chromium-Ferroboron Master Alloys

The Use of Ashes in Surface Metal Matrix Composites Produced by Friction Stir Processing

The article presents an assessment of the possibility of using ashes from the combustion of coal and biomass as a reinforcing phase in metal matrix composites. The composite surface layer was produced by means of the FSP (friction stir processing) method, using an original hole solution with a shifted working zone of the pin. The composite matrix was AA7075 alloy. The obtained composite was subjected to microscopic observations, tribological tests, and hardness measurements. The microscopic examinations revealed favorable changes in the microstructure, in particular, strong refinement of the grains, uniform distribution of the reinforcing phase, and good bonding of the particles of this phase with the matrix material. Changes in the microstructure resulted in a significant increase in the hardness (from 36 to 41% depending on the type of reinforcing phase) and wear resistance (from 24.1 to 32.9%), despite partial dissolution of the intermetallic phases. It was found that the effect of strengthening the matrix and the uniformity of the distribution of the reinforcing phase depend on the physicochemical properties of the used powders, especially on the shape and size of the particles. The research shows that the use of ashes as a reinforcing phase in composites is fully justified.

Investigation of the Features of the Formation of Diffusion Layers During Nitrocementation of High-Chromium Steels in a Carbon Black Medium

The purpose of the work is to establish the regularities of the formation of the structure and phase composition of surface (modified) layers on 20X13 chromium stainless steel under intense saturation with carbon and nitrogen and, on this basis, to substantiate the possibility of surface hardening of parts made of high-chromium steels by nitrocementation.Methods. The studies were carried out on samples made of high–chromium steel 20X13, which were subjected to high-temperature nitrocementation in a paste-like medium including fine soot, sodium carbonate and potassium ferruginous oxide (paste-forming agent is an aqueous solution of carbomethylcellulose). The microstructure was studied using an optical metallographic microscope OLIMPUS OX 51 and a scanning electron microscope Qanta FEG-650 with an X-ray microanalysis system EDAX. The microhardness was determined on the Duramit-5 microhardometer, the phase composition on the XRD-7000S X-ray diffractometer.Results. Nitrocementation of high chromium steel 20X13 in the temperature range of 820–950°C provides the formation of diffusion layers on the surface, the structure of which is represented by three zones: a crust of solid carbonitrides on the surface, an eutectoid zone with a solid matrix and inclusions of carbonitrides under the crust and a transition zone including a solid solution enriched in carbon and nitrogen with grains of the base metal. The microhardness of the nitrocemented layers on 20X13 steel after quenching from 1050°C in oil and tempering at 600°C reaches Nm 750–800 on the surface and decreases smoothly enough in depth of the nitrocemented layer. The depth of nitrocemented layers with increased microhardness (more than 400 Nm), depending on the duration of treatment, can reach ~ 0.5 (860°C, 6 hours).Conclusion. Nitrocementation of high-chromium steel 20X13 at 820–880°C in an active carbon black paste with the addition of potassium ferrocarbon leads to an increase in the hardness of the surface layers by about 4 times the hardness of the base, which, combined with the high mechanical properties of the base, will significantly increase the service life of parts made of high-chromium stainless steels of type X13 operating under high contact conditions loads.

Damage caused by He and D plasma exposure in Mo/Zr-added W-Y2O3 composites

In the present study, we developed Mo- and Zr-added W-Y2O3 composites, and investigated their surface damage, including commercially available W induced by He and D as well as He and D mixture plasmas. Blistering was not observed in the D-plasma-irradiated W and W composites. The thickness of the damaged surface layer due to He plasma exposure of the W-Mo-Y2O3 composite was similar to that of W. However, the thickness of the damaged surface layer of the W-Y2O3 composite was half that of W. In addition, the thickness of the damaged surface layer of the W-Zr-Y2O3 composite was further improved by 5 times. Y2O3 nanoparticles, especially refined Zr-Y-O nanoparticles, act as He trap sites to suppress the formation and growth of He bubbles. Furthermore, the W-O-Y and W-O-Zr-Y nanoparticles increased the solubility of He and delayed He diffusion, hindering the formation of He bubbles.

Lack of Laminar Shear Stress Facilitates the Endothelial Uptake of Very Small Superparamagnetic Iron Oxide Nanoparticles by Modulating the Endothelial Surface Layer.

To study whether the absence of laminar shear stress (LSS) enables the uptake of very small superparamagnetic iron oxide nanoparticles (VSOP) in endothelial cells by altering the composition, size, and barrier function of the endothelial surface layer (ESL). A quantitative particle exclusion assay with living human umbilical endothelial cells using spinning disc confocal microscopy revealed that the dimension of the ESL was reduced in cells cultivated in the absence of LSS. By combining gene expression analysis, flow cytometry, high pressure freezing/freeze substitution immuno-transmission electron microscopy, and confocal laser scanning microscopy, we investigated changes in ESL composition. We found that increased expression of the hyaluronan receptor CD44 by absence of shear stress did not affect the uptake rate of VSOPs. We identified collagen as a previously neglected component of ESL that contributes to its barrier function. Experiments with inhibitor halofuginone and small interfering RNA (siRNA) demonstrated that suppression of collagen expression facilitates VSOP uptake in endothelial cells grown under LSS. The absence of laminar shear stress disturbs the barrier function of the ESL, facilitating membrane accessibility and endocytic uptake of VSOP. Collagen, a previously neglected component of ESL, contributes to its barrier function.

Impact of the Amphoteric Nature of a Chelating Surfactant on its Interaction with an Anionic Surfactant: A Surface Tension and Neutron Reflectivity Study of Binary Mixed Solutions.

2-Dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) is a chelating, amphoteric surfactant with a bulky headgroup containing eight pH-responsive groups. The hypothesis was that the amphoteric nature of the chelating surfactant would affect the interaction with another surfactant and, consequently, also the composition of mixed surface layers. Binary mixed monolayers of C12-DTPA and the anionic surfactant sodium dodecyl sulfate (SDS) were examined using neutron reflection and surface tension measurements. The experiments were conducted at pH 5, where the C12-DTPA monomers carried a net negative charge. Surface excess calculations at low total surfactant concentration revealed that the chelating surfactant dominated the surface composition. However, as the concentration was raised, the surface composition shifted toward an SDS-dominant state. This phenomenon was attributed to the increased ionic strength at increased concentrations, which altered the balance between competing entropic forces in the system. Interaction parameters for mixed monolayer formation were calculated, following a framework based on regular solution theory. In accordance with the hypothesis, the chelating surfactant's ability to modulate its charge and mitigate repulsive interactions in the surface layer resulted in favorable interactions between the anionic SDS and negatively charged C12-DTPA monomers. These interactions were found to be concentration-dependent, which was consistent with the observed shift in the surface layer composition.

Effect of Cooling Rate on Microstructure of In Situ TiC-Reinforced Composite Surface Layers Synthesized on Ductile Cast Iron by Laser Alloying.

The microstructure of the in situ TiC-reinforced composite surface layers developed during laser surface alloying of a ductile cast iron substrate with titanium was related to the solidification conditions in the molten pool. The solidification conditions were estimated using infrared thermography. It was found that the cooling rates of the melt up to about 700 °C/s enable the complete reaction between carbon and the entire amount of titanium introduced into the molten pool. In turn, the cooling rate of about 280 °C/s for the melt containing 8.0 wt% Ti allows the TiC particles to grow in the dendritic form with well-developed secondary arms and a total size of up to 30 µm. For a constant Ti content, the cooling rate of the melt had no effect on the TiC fraction. The increase in the cooling rate elevated the retained austenite fraction in the matrix material, lowering its hardness.

Electrochemical activity of electroless Ni-P coatings in the hydrogen evolution reaction

The purpose of this study was investigation of the electrochemical activity of Ni-P coatings, differing in phosphorus content and structure, in the hydrogen evolution reaction (HER) and the identification of the reasons for their high activity in the reaction being studied. The coatings were deposited from an electroless nickel plating solution, the phosphorus content in the coatings (from 4.8 to 8.0 wt. %) varied by changing the pH of the solution. It was found that during cathodic polarization in 0.5 M H2SO4 additional surface activation occurs as a result of dissolution of the surface layer of the coating, removal of phosphorus from the surface layer, and development of the electrode surface. Of all the coatings studied coatings containing 4.8% phosphorus were most susceptible to cathodic activation. Coatings with a phosphorus content of 8.0% were least susceptible to cathodic activation. The similar electrochemical activity of the studied coatings (taking into account the roughness factor) in HER indicates that, as a result of cathodic polarization, the composition of the thin surface layer on which the cathodic reaction occurs is approximately the same, regardless of the initial phosphorus content

An Experimental Investigation on the Pool Boiling Heat Transfer of R-134a on Microporous Cu-MWCNT Composite Surfaces

Multiwalled carbon nanotubes (MWCNTs) exhibit outstanding physical properties, including high thermal conductivity, excellent mechanical strength, and low electrical resistivity, which make them suitable candidates for a variety of applications. The work presented in this paper focuses on the pool boiling performance of refrigerant R-134a on microporous Cu-MWCNT composite surface layers. A two-stage electrodeposition technique was used to fabricate Cu-MWCNT composite coatings. In order to achieve variation in the surface properties of the Cu-MWCNT composite surface layer, electrodeposition was carried out at various bath temperatures (25 °C, 30 °C, 35 °C, and 40 °C). All surfaces coated with the Cu-MWCNT composite demonstrated superior boiling performance compared to the uncoated surface. Heat transfer coefficient (HTC) values for Cu-MWCNT composite surface layers, prepared at bath temperatures of 25 °C, 30 °C, 35 °C, and 40 °C, exhibited improvements of up to 1.75, 1.88, 2.06, and 2.22, respectively, in comparison to the plain Cu surface.

How Relevant Are SEI Studies from Half Cell Samples to Understand Aging Mechanisms in Potassium Batteries? An in-Depth Photoelectron Spectroscopy Study

Owing to a shared common technological basis, monovalent K-ion battery (KIB) systems follow in the footsteps of Li-ion batteries (LIBs) with the aim to develop a broader portfolio of available battery technologies and to put them on a more sustainable material basis. For example, both cations intercalate into a graphite host structure, which can be used in combination with carbonate-based electrolytes as negative electrode. Especially in half cells, the degradation of graphite electrodes in KIBs is significantly accelerated in comparison to LIBs. Previous surface studies demonstrated that the formation of a durable and protective solid electrolyte interphase (SEI), that is paramount for long cycle life in alkali-ion batteries, is a major bottleneck for KIBs because of less benign SEI properties[1][2].Recently reported crosstalk phenomena in half cell configurations due to the highly reactive potassium counter electrode make the analysis of surface layers a particular challenge [2][3]. In this presentation, a detailed characterization of the SEI formation on graphite was performed in both half and full cell configurations by in-house and synchrotron-based photoelectron spectroscopy (PES) in order to demonstrate fundamental differences in surface layer composition under the influence of a reactive counter electrode. While it is generally acknowledged that PES results show differences in SEI composition and thickness between both configurations, our results clearly demonstrate that in case of KIBs the changes become severe. This challenges interpretations of SEI layer properties made in half cells, as they are distinctly different from those in full cells. More importantly, this also affects interpretations on the major electrolyte degradation pathways in these systems. Using PES depth profiling and complementing results with gas chromatography, as well as DFT calculations, delivers new insights on the irreversible processes in KIBs. Reference s : [1] Naylor, et al., ACS Appl. Mater. Interfaces. 11 (2019) 45636–45645.[2] Allgayer et al., ACS Appl. Energy Mater. 5 (2022) 1136–1148.[3] Hosaka et al., ACS Energy Lett. 6 (2021) 3643–3649.

Surface composition driven rippling of oblique Ar+ irradiated SiC/Si(111) thin films

Oblique ion beam patterned and structured thin films hold promise as an advanced material for applications to photonics, micro- to nano-electronics, electro-optical and electrochemical devices fabrication. Herein, for the first time, we report the fabrication of patterned and structured SiC thin films over Si(111) by obliquely incident Ar+ beam. We show that at a short time scale, carbon clusters possessing nano-dimensional size evolve while ripple structures with direction parallel to the ion beam projection emerge at later time scales. The roughness evolution plot follows exponential and power law scaling at low and high bombarding time (in terms of ion fluence). The underlying mechanism is the altered surface layer composition due to the non-stoichiometric sputtering of silicon and carbon. The optical bands corresponding to silicon carbide (3.27–4.23 eV) & silicon (1.15–1.45 eV) co-exist for lower argon ion fluences while optical bands of silicon (1.15- 1.45 eV) remains and silicon carbide vanishes for higher argon ion fluences. Our experimental findings demonstrated the fabrication of ripple patterns over radiation tolerant, thermally and physically stable SiC by large area irradiation and capability to tailor the temporal characteristics of these evolved structures.

Cryogenic heavy ion RBS-ERDA depth profiling of ion implanted PET films

The analysis of thin films using heavy ions offers some specific advantages over traditional light ion beam analysis techniques. In this work, polyethylene terephthalate (PET) substrate was implanted with 150 keV Ag+-ions at low temperature at fluences of 1.00 x 1016 and 5.00 x 1016 ions/cm2. A newly constructed low temperature chamber equipped with heavy ion Rutherford Backscattering Spectrometry (HI-RBS) and Elastic Recoil Detection Analysis (HI-ERDA) detectors was used for sample characterisation, using 14 MeV 28Si4+-ions at an irradiation fluence of about 2.40 x 1013 ions/cm2. The analyses were carried out at room temperature and with the sample holder cooled to liquid nitrogen temperature. Silicon beam irradiation effects on the PET were then compared at room- and low-temperature measurements. Significant hydrogen loss of about 64 % relative to pristine PET was observed for room-temperature measurements, whereas for low-temperature analyses the hydrogen loss was about 12 %. The significant release of hydrogen atoms from the surface region of the PET was accompanied by a drastic change in the surface layer composition. For room-temperature measurements, there was surface enhancement of the carbon content by about 31 %, while for low-temperature measurements the accumulation was about 9 % compared to the nominal 45 % content in pristine PET.

Electron-beam nitriding of carbon steel alloy in the forevacuum pressure range

We have explored the ion nitriding of AISI 5135 carbon steel alloy. Nitriding was performed in the plasma formed by an electron beam at the forevacuum pressure of 5 Pa. The beam was generated using a forevacuum-pressure plasma-cathode electron source. We report the results of SEM and X-ray diffraction pattern analysis of the surface of nitrided samples, as well as results of measured micro hardness, surface wear rate, coefficient of friction, roughness, and nitrogen penetration depth. We find that the sample temperature during nitriding affects the surface morphology and phase composition of surface layers. A threefold increase in surface micro hardness was achieved. The surface micro hardness increases with increasing nitriding duration. Samples nitrided at temperatures up to 500°С for a time of no less than 2 h show the greatest abrasive wear resistance. The nitrogen penetration depth is greater than 200 μm for all experimental conditions, with maximum of 450 μm.

Adsorption of Glucose Molecules on Stainless Steel Enables Ni‐Rich Passivation Film

AbstractStainless steel (SS) is well known for its remarkable versatility. Besides the importance of passivation film for durability and stability of SS, the composition and morphology of passive surface layer have to be precisely modified to create an alloy that is optimal for specific purposes. Herein, we report on the electrochemical preparation of nickel‐enriched passive film which is accomplished by the preferential adsorption of glucose on nickel species among constituents of SS. The presence of nickel‐rich surface and the exposure of nickel on the outmost surface layer participating in surface reactions are verified by monitoring redox couple of Ni2+/Ni3+ as well as elemental analyses (TEM‐Energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy). Reversible interchange of nickel‐rich into iron‐rich surface and vice versa is possible by adding or removing glucose. We find that molecules having more than tri‐dentate of hydroxy groups (e. g. glycerol) is required for the formation of Ni‐rich surface (chelate effect).

Corrosion and Wear-Resistant Composite Zirconium Nitride Layers Produced on the AZ91D Magnesium Alloy in Hybrid Process Using Hydrothermal Treatment

The aim of the study was to investigate the possibility of an effective improvement in performance properties, including corrosion and wear resistance of magnesium AZ91D alloy using a surface engineering solution based on zirconium nitride composite surface layers produced on AZ91D alloy in a hybrid process using hydrothermal final sealing. Research results show that the formation of a composite ZrN-Zr-Al-type zirconium nitride layer on zirconium and aluminum sublayers results in a significant increase in resistance to corrosion and wear. The decrease in chemical activity of the sealed zirconium nitride composite layer on AZ91D, expressed by the displacement of the corrosion potential in the potentiodynamic test, reaches an outstanding value of ΔEcorr = 865 mV. The results of the SIMS chemical composition analysis of the layers indicate that the sealing of the composite layer occurs at the level of the aluminum sublayer. The composite layer reduces wear in the Amsler roll on block test by more than an order of magnitude. The possibility of effective sealing of zirconium nitride layers on the AZ91D alloy demonstrated in this study, radically increases the corrosion resistance and combined with the simultaneous mechanical durability of the layers, is of key importance from the point of view of new perspectives for application in practice.

Direct Evidence of Dynamic Metal Support Interactions in Co/TiO2 Catalysts by Near-Ambient Pressure X-ray Photoelectron Spectroscopy.

The interaction between metal particles and the oxide support, the so-called metal-support interaction, plays a critical role in the performance of heterogenous catalysts. Probing the dynamic evolution of these interactions under reactive gas atmospheres is crucial to comprehending the structure-performance relationship and eventually designing new catalysts with enhanced properties. Cobalt supported on TiO2 (Co/TiO2) is an industrially relevant catalyst applied in Fischer-Tropsch synthesis. Although it is widely acknowledged that Co/TiO2 is restructured during the reaction process, little is known about the impact of the specific gas phase environment at the material's surface. The combination of soft and hard X-ray photoemission spectroscopies are used to investigate in situ Co particles supported on pure and NaBH4-modified TiO2 under H2, O2, and CO2:H2 gas atmospheres. The combination of soft and hard X-ray photoemission methods, which allows for simultaneous probing of the chemical composition of surface and subsurface layers, is one of the study's unique features. It is shown that under H2, cobalt particles are encapsulated below a stoichiometric TiO2 layer. This arrangement is preserved under CO2 hydrogenation conditions (i.e., CO2:H2), but changes rapidly upon exposure to O2. The pretreatment of the TiO2 support with NaBH4 affects the surface mobility and prevents TiO2 spillover onto Co particles.

Research on the permanent deformation mechanism and dynamic meso-mechanical response of porous asphalt mixture composite structure using the discrete element method

This study proposed a heterogeneous 3D virtual rutting model to investigate the rutting evolution mechanism and the dynamic meso-mechanical response of a porous asphalt mixture composite structure. The 3D virtual rutting test model incorporated a three-phase asphalt mastic-aggregate-airvoids system with grain size distribution and genuine aggregate morphology. Innovative algorithms were developed for cyclic rolling loading to reflect repetitive wheel loading. In contrast to the indoor rutting tests, the 3D virtual rutting tests exhibited greater rutting deformation and weaker dynamic stability in the range of 3.16%–10.17% and 2.65%–11.77%, respectively. Shear forces were predominant in the virtual rutting tests. As the porous asphalt mixture composite structure's surface layer thickness increased, the shear contact force increased and the maximum parallel-bond (PB) contact force diminished. The 3D virtual rutting test model was demonstrated to be feasible for simulating rutting deformation and dynamic meso-structural responses in porous asphalt mixtures with cyclic rolling loading algorithms.

Distinctive performance evolution of surface layer in TC4 alloy oxidized at high temperature: Softening or hardening?

The characteristics of metal surface layer at high-temperature significantly affect the service performance of TC4 titanium alloy components, so that the evolution mechanism of mechanical properties of metal surface layer under high-temperature oxidation conditions is an important scientific issue. In the present work, the mechanical behavior and the relevant mechanism of metal surface oxidized at the temperatures of 500 ℃, 700 ℃, and 900 ℃ for different times have been systematically investigated. The experimental results show that with the increase of temperature, the oxidation kinetics curve of the alloy changes from parabolic law to linear law, and the oxidation reaction changes from diffusion control to interfacial reaction control. Furthermore, as the temperature increases from 500 °C to 900 °C, the feature of oxide scale changes from the single-layer structure to the multi-layer alternating structure, and the thickness of oxide scales and depth of alpha case increased with increasing temperature. The surface oxide scale is mainly composed of low valent oxides such as Ti3O and Ti6O during low-temperature oxidation as well as short-term high temperature oxidation. After long-term high temperature oxidation, the oxide scale is mainly composed of high valent oxides such as TiO2, Al2O3, and TiVO4. Simultaneously, significant changes occur in the composition, microstructure and properties of metal surface layer. In general, the microstructure and mechanical properties of the surface-layer metal are strongly dependent upon the competitive influence of the outward diffusion of Al and the inward diffusion of O. In the temperature range of 500–900ºC, when the temperature is relatively low, the softening effect caused by the outward diffusion of Al is stronger than the strengthening effect caused by the inward diffusion of O, and a surface softening effect thus occurs. On the contrary, when the temperature is high, the strengthening effect caused by the inward diffusion of O is stronger than the softening effect caused by the outward diffusion of Al, and a surface strengthening effect accordingly happens.

The Effects of High-Energy Composite Surface Layer Modification on the Impact Performance of the H13 Steel Cutter Ring for Shield Tunneling Machine

The service life of the cutter ring of the shield tunneling machine affects the efficiency and cost of its tunneling. However, traditional heat treatment processes cannot simultaneously optimize both impact toughness and surface hardness, often leading to cracks or excessive wear of the cutter ring, greatly reducing their service life. According to the above situation, this paper applies high-energy composite modification treatment to H13 steel samples commonly used for the cutter ring of the hob and analyzes the impact toughness, hardness, microstructure, residual stress, and morphology characteristics of fracture of the samples under different high-energy composite modification processes. The study also investigates the effects of high-energy composite modification processes on the hardness and impact toughness of the samples. The experimental results show that the high-energy composite modification process enables the specimens to have good impact toughness and surface hardness simultaneously. The H13 steel sample has the best performance after carburizing, quenching, and laser shock modification, with a maximum surface hardness of 1017.5HV0.2 and an impact toughness of 15.64 J/cm2. Laser shock modification improves the surface residual compressive stress and hardness of H13 steel samples and also improves their impact toughness.