Hardness has been considered the main factor controlling the abrasive wear of steels. However, microstructure also affects the wear behavior. Four steels with different microstructures were produced with a Gleeble 3800 thermomechanical simulator and tested for abrasive wear behavior. Different cooling rates and heat treatments were applied to obtain a surface hardness of approximately 450 HV. Mainly tempered martensite, pearlite and some bainite could be observed in the microstructures. Scratch testing with a CETR UMT-2 tribometer was conducted to produce wear tracks. The results revealed that each steel showed distinct wear behavior.

Thermally sprayed hardmetal coatings were produced to provide improved erosion wear compared to conventional cast GX4CrNi13-4 martensitic steel (CA6NM) used in hydro turbine components. Sprayed coatings and reference materials were tested with high-speed slurry pot tester using either fine or coarse quartz as the erosive media. Additional erosion tests were carried out with centrifugal dry erosion tester. Tungsten carbide based coatings provided the highest wear resistance due to the high hardness and even distribution of the fine carbide particles. The cast 13-4 steel samples experienced up to 180 times higher wear rates in fine quartz slurry and up to 36 times higher wear rates in coarse slurry compared to the sprayed coatings.

Using ab initio calculations we investigated the surface energies of paramagnetic Fe_{1 - c - n}Cr_cNi_n random alloys within the concentration range of 0.12 ≤ c ≤ 0.32 and 0.04 ≤ n ≤ 0.32. These alloys crystallize mainly in the face centred cubic (fcc) structure and constitute the main building blocks of austenitic stainless steels. It is shown that all alloys have the lowest surface energies along the most close packed crystal orientation, namely the fcc (111) surfaces. The amount of Ni seems to have little effect on the surface energy, while almost all composition-driven change may be attributed to the changes in the Cr content. Within the studied compositional range, the change of the surface energy with the composition is of the order of 10%. Trends of the surface energy can be related to the magnetic structure of surfaces. Using the total energy as a function of the concentration, we determine the effective chemical potentials in bulk and at the surface, which can be used to estimate the surface segregation energies.

In this paper, high-velocity oxy-fuel sprayed coatings from experimental Cr₃C₂-Ni powder produced by mechanically activated thermal synthesis and disintegrator milling are compared with coatings from commercial Cr₃C₂-NiCr powder under room- and elevated-temperature abrasive-erosive wear (AEW) conditions. In a room-temperature AEW test, the coating made from the experimental powder had wear rates that were 1.1-5.3 times higher than the coating from the commercial powder; this difference was the lowest at the highest impact velocity (80 m s⁻¹). Under AEW tests at elevated temperature (300 and 550 °C), the coating made from the experimental powder exhibited wear rates that were 1.2-2.8 times higher in comparison with that made from the commercial powder, but this difference was smaller under an oblique impact angle (30°) and higher temperature conditions. The reasons for the lower resistance against AEW of the coating made from the experimental powder were found to be its lower ability to resist plastic indentation and deformation as well as lower indentation fracture toughness at room temperature, weaker bonding between the matrix and reinforcement and probably lower mechanical properties as well as unfavourable residual stresses at elevated temperatures.

Binding affinities and stoichiometries of Na⁺ and Ca²⁺ ions to phospholipid bilayers are of paramount significance in the properties and functionality of cellular membranes. Current estimates of binding affinities and stoichiometries of cations are, however, inconsistent due to limitations in the available experimental and computational methods. In this work, we improve the description of the binding details of Na⁺ and Ca²⁺ ions to a 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) bilayer by implicitly including electronic polarization as a mean field correction, known as the electronic continuum correction (ECC). This is applied by scaling the partial charges of a selected state-of-the-art POPC lipid model for molecular dynamics simulations. Our improved ECC-POPC model reproduces not only the experimentally measured structural parameters for the ion-free membrane, but also the response of lipid headgroup to a strongly bound cationic amphiphile, as well as the binding affinities of Na⁺ and Ca²⁺ ions. With our new model, we observe on the one side negligible binding of Na⁺ ions to POPC bilayer, while on the other side stronger interactions of Ca²⁺ primarily with phosphate oxygens, which is in agreement with the previous interpretations of the experimental spectroscopic data. The present model results in Ca²⁺ ions forming complexes with one to three POPC molecules with almost equal probabilities, suggesting more complex binding stoichiometries than those from simple models used to interpret the NMR data previously. The results of this work pave the way to quantitative molecular simulations with realistic electrostatic interactions of complex biochemical systems at cellular membranes.

The carbonate ion plays a central role in the biochemical formation of the shells of aquatic life, which is an important path for carbon dioxide sequestration. Given the vital role of carbonate in this and other contexts, it is imperative to develop accurate models for such a high charge density ion. As a divalent ion, carbonate has a strong polarizing effect on surrounding water molecules. This raises the question whether it is possible to describe accurately such systems without including polarization. It has recently been suggested the lack of electronic polarization in nonpolarizable water models can be effectively compensated by introducing an electronic dielectric continuum, which is with respect to the forces between atoms equivalent to rescaling the ionic charges. Given how widely nonpolarizable models are used to model electrolyte solutions, establishing the experimental validity of this suggestion is imperative. Here, we examine a stringent test for such models: a comparison of the difference of the neutron scattering structure factors of K ₂CO₃ vs KNO₃ solutions and that predicted by molecular dynamics simulations for various models of the same systems. We compare standard nonpolarizable simulations in SPC/E water to analogous simulations with effective ion charges, as well as simulations in explicitly polarizable POL3 water (which, however, has only about half the experimental polarizability). It is found that the simulation with rescaled charges is in a very good agreement with the experimental data, which is significantly better than for the nonpolarizable simulation and even better than for the explicitly polarizable POL3 model.

Calcium is one of the biologically most important ions; however, its accurate description by classical molecular dynamics simulations is complicated by strong electrostatic and polarization interactions with surroundings due to its divalent nature. Here, we explore the recently suggested approach for effectively accounting for polarization effects via ionic charge rescaling and develop a new and accurate parametrization of the calcium dication. Comparison to neutron scattering and viscosity measurements demonstrates that our model allows for an accurate description of concentrated aqueous calcium chloride solutions. The present model should find broad use in efficient and accurate modeling of calcium in aqueous environments, such as those encountered in biological and technological applications.

In this paper, a comparison is made between calculated and measured displacements from a complete contact fretting test device. An experimental technique based on digital image correlation was used to measure the local displacement field at the contact interface. The material of the fretting specimen and pads was quenched and tempered steel. The effect of test device compliances and rigid body movement was minimized by measuring displacements very close to the contact interface. The measured displacements were successfully compared to the computed displacements of a corresponding finite element model. The relative slip amplitude in partial slip conditions, slip distribution across the contact, length of the slip region, and accumulated slip distribution, were compared. Relative slip decreases markedly with increasing normal load and friction coefficient. The friction coefficient was calibrated and determined as a function of loading cycles of fretting fatigue tests with two normal loads. The friction coefficient was found to increase at the beginning of tests and stabilize after about 1000 cycles, which is in agreement with general observations.

Rheology and FTIR spectroscopy are compared as methods to study the degree of photodegradation in polypropylene (PP) and polystyrene (PS) sheets. The materials are hot pressed, artificially photo-aged with fluorescent lights for 4-2048 h and then measured with a rotational rheometer and FTIR. Both materials show a tendency for chain scission which can be seen as a reduction in viscosity. Changes in PP can be observed with both methods after 256 h of irradiation. Changes in PS become significant in rheology after 64 h but in FTIR only after 1024 h of irradiation. Due to the different chemical nature of the materials, the degradation of PS is rather linear with exposure, whereas the degradation of PP is more exponential. Using the zero shear viscosities obtained through extrapolations of the Cole-Cole and Carreau-Yasuda models, relative molecular weights are estimated with the aid of the power-law relationship between these two. These results are compared with the carbonyl indices determined from the FTIR spectra. Rheology is found to be a viable alternative for FTIR in certain situations.

Abstract: A finite cluster method is applied to describe the energy transfer from the adsorbate vibrations to the electron-hole pair excitations. For CO stretch vibration on Cu(100) surface a value of 0.5 meV is found for the consequent damping (corresponding to the lifetime of 1.3·10 ^-12 s) in an agreement with a recently measured vibrational line width. The mechanism behind the electron-hole pair excitations is found to be charge oscillations between the molecular 2π ^* resonance and the substrate, caused by the molecular vibration. Cluster size effects have been found to be negligible.

Chemical analysis of solid-liquid interfaces under electrochemical conditions has recently become feasible due to the development of new synchrotron radiation techniques. Here we report the use of "tender" X-ray ambient-pressure X-ray photoelectron spectroscopy (APXPS) to characterize a thin film of Ni-Fe oxyhydroxide electrodeposited on Au as the working electrode at different applied potentials in 0.1 M KOH as the electrolyte. Our results show that the as-prepared 7 nm thick Ni-Fe (50% Fe) film contains Fe and Ni in both their metallic as well as oxidized states, and undergoes further oxidation when the sample is subjected to electrochemical oxidation-reduction cycles. Metallic Fe is oxidized to Fe³⁺ and metallic Ni to Ni^2+/3+. This work shows that it is possible to monitor the chemical nature of the Ni-Fe catalyst as a function of potential when the corresponding current densities are small. This allows for operando measurements just above the onset of OER; however, current densities as they are desired in photoelectrochemical devices (∼1-10 mA cm^-2) could not be achieved in this work, due to ohmic losses in the thin electrolyte film. We use a two-dimensional model to describe the spatial distribution of the electrochemical potential, current density, and pH as a function of the position above the electrolyte meniscus, to provide guidance toward enabling the acquisition of operando APXPS at high current density. The shifts in binding energy of water with applied potential predicted by the model are in good agreement with the experimental values.

Guanidinium carbonate was used in this study as a simple proxy for the biologically relevant arginine-carbonate interactions in water. Molecular dynamics (MD) simulations of guanidinium carbonate were performed with nonpolarizible water using two implementations of the ion force fields. In the first, the ions had full charges, while in the second, the ions had reduced charges in order to effectively account for electronic polarization effects of water. The results from the simulations were then compared to data from previous neutron scattering experiments. It was found that there were significant discrepancies between the full charge force field MD simulations and the experimental results due to excessive ion pairing and clustering in the former. In contrast, reducing the ionic charges yields a more regular solution with a simulated structure, which fits well the experimental data.

High wear and corrosion of parts lead to an increase in operating costs at thermal power plants. The present paper shows a possible solution to this problem through the arc spraying of protective coatings. Cored wires of the base alloying system Fe-Cr-C were used as a feedstock. Rise of wear- and heat-resistance of the coatings was achieved by additional alloying with Al, B, Ti, and Y. The wear and heat resistance of the coatings were tested via a two-body wear test accompanied by microhardness measurement and the gravimetric method, respectively. A high-temperature corrosion test was performed at 550 °C under KCl salt deposition. The porosity and adhesion strengths of the coatings were also evaluated. The microstructure was investigated with a scanning electron microscope (SEM) unit equipped with an energy dispersive X-ray (EDX) microanalyzer, and the phase composition was assessed by X-ray diffractometry. The test results showed the positive influence of additional alloying with Y on the coating properties. A comparison with commercial boiler materials showed that the coatings have the same level of heat resistance as austenite steels and are an order of magnitude higher than that of pearlite and martensite-ferrite steels. The coatings can be applied to wear- and heat-resistant applications at 20-700 °C.

Four aryl end-capped quaterthiophene derivatives were synthesized and their material properties were studied by computational, spectroscopic, electrochemical, and thermoanalytical methods. Compounds were applied as interfacial layers between the bulk heterojunction active layer and Ag anode in inverted organic solar cells. Results show that p-cyanophenyl end-capped quaterthiophene with hexyl side chains increases both the short circuit current density and power conversion efficiency notably compared to reference interlayer material, tris-(8-hydroxyquinoline)aluminum. The improved cell performance was attributed to the optimal positions of the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO) of this material, relative to those of the photoactive electron donor poly(3-hexylthiophene) and Ag anode, and evenly distributed LUMO. In addition, the use of these materials as an anode interfacial layer increases the absorption of the solar cell, which could contribute to the formation of excitons and additional current production by the cell.

In this study, the local electrochemical activity of untreated and passivated (natural or chemical passivation) zinc specimens was observed during immersion in a 0.1-M NaCl solution. The localized anodic activity during the exposure, measured with the scanning vibrating electrode technique, was linked to zinc dissolution by the pitting corrosion mechanism. It was correlated to specific corrosion products characterized by Fourier transmission infrared (FTIR) microscopy. FTIR molecule maps were produced from individual pitting corrosion sites (100–200 µm in width). With argon ion beam milling and latest energy-dispersive X-ray spectroscopy (EDS) technology, element maps with a high spatial resolution (≪100 nm) were recorded from abrasion- and beam-sensitive corrosion products, showing a residual layer structure. This study demonstrates the capability of FTIR mapping, cross-section polishing, and state-of-the-art scanning electron microscopy imaging, and EDS element mapping to produce high-resolution elemental, molecular, and visual information about pitting corrosion mechanisms on a hot-dip galvanized steel sample.

Material and spray process selection are the key factors in the tailoring of thermal sprayed coatings for demanding industrial applications. In this study, four commercial Cr₃C₂-based feedstock materials were sprayed with gas-fuelled high-velocity oxygen-fuel (HVOF) and modern high-velocity air-fuel (HVAF) spray processes. Two materials with standard Cr₃C₂–25NiCr composition (porous and dense), a Cr₃C₂–50NiCrMoNb and Cr₃C₂–37WC–18NiCoCr materials were sprayed in addition to the reference WC-10Co4Cr material. The Cr₃C₂–50NiCrMoNb had a higher content of the Ni-based metal matrix compared to standard Cr₃C₂–25NiCr composition for added corrosion resistance, while the Cr₃C₂–37WC–18NiCoCr material contained additional tungsten carbide (WC) particles to improve the wear resistance. In abrasion and dry particle erosion, the Cr₃C₂–50NiCrMoNb coatings showed a higher degree of plastic deformation and increased material loss, whereas the Cr₃C₂–37WC–18NiCoCr coating had wear resistance between the standard Cr₃C₂–25NiCr and reference WC-10Co4Cr coatings. In cavitation erosion, the lower carbide content of Cr₃C₂–50NiCrMoNb coatings turned out to improve the resistance against fatigue wear due to higher fracture toughness. Overall, the HVAF sprayed coatings had higher elastic modulus, higher fracture toughness, equal or higher abrasion and erosion resistance, and higher cavitation erosion resistance compared to the HVOF sprayed counterparts.

The research on high-velocity air-fuel (HVAF)-sprayed Cr₃C₂-based materials has mostly focused on conventional Cr₃C₂-25NiCr composition. In this paper, two alternative compositions (Cr₃C₂-50NiCrMoNb and Cr₃C₂-37WC-18NiCoCrFe) were sprayed with high-velocity oxy-fuel (HVOF) and HVAF spray processes to evaluate the material behavior during spraying and to provide characterization of the microstructures and mechanical properties of the coatings. For comparison, coatings from the Cr₃C₂-25NiCr composition were sprayed with both processes. Spray diagnostics were carried out to obtain average particle velocity and temperature for each material and process combinations. The measured average in-flight particle data were 1800 °C and 700 m/s for HVOF process, and 1450 °C and 900 m/s for HVAF process. Characterization of the coating microstructures was carried out by scanning electron microscopy and X-ray diffraction. In addition, the carbon content of the feedstock powders and sprayed coatings was measured with carbon analyzer. The results show that carbide rebounding or selective deposition of particles with higher metal matrix content is the dominating reason for carbide loss during HVAF spraying, while carbide dissolution is an additional source for the HVOF spraying. Higher particle velocities and controlled temperature measured for the HVAF process produced dense coatings with improved toughness and more homogenous coating structure.

An initial friction peak typically occurs in a dry self-mated quenched and tempered steel fretting contact in gross sliding conditions. The peak is related to adhesive friction and wear, which causes non-Coulomb friction. An early surface degradation including cracks may occur. To avoid such a peak, different media were studied using a flat-on-flat fretting test device with a large annular contact. All the media decreased the initial friction peak in comparison to the dry reference case, and in one series the peak was completely removed. The peak could often be delayed by lubrication. The steady-state coefficient of friction values mostly remained at similar levels to those of the dry contact, but decreased when oil was applied. Nevertheless, some surface damage occurred in every test, with varying amounts of wear.

Under conditions of oxidative stress, 4-hydroxy-2-nonenal (4-HNE) is commonly present in vivo. This highly reactive and cytotoxic compound is generated by oxidation of lipids in membranes and can be easily transferred from a membrane to both cytosol and the extracellular space. Employing time-dependent fluorescence shift (TDFS) method and molecular dynamics simulations, we found that 4-HNE is stabilized in the carbonyl region of a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayer. 4-HNE is thus able to react with cell membrane proteins and lipids. Stabilization in the membrane is, however, moderate and a transfer of 4-HNE to either extra- or intracellular space occurs on a microsecond time scale. These molecular-level details of 4-HNE behavior in the lipid membrane rationalize the experimentally observed reactivity of 4-HNE with proteins inside and outside the cell. Furthermore, these results support the view that 4-HNE may play an active role in cell signaling pathways.

Corrosion, wear and tribocorrosion behaviours of leaded tin bronze were examined in simulated seawater using alumina counterbody for tribological contact. Active dissolution of alloy and corrosion product development on surfaces were the dominant corrosion mechanisms. Tribological contact with counterbody removed majority of the products, thus contributing to active dissolution of freshly exposed surface. This wear-induced corrosion mechanism contributed to 45% and 60% of total material losses at the two highest potentials, 50 mV and 250 mV vs. Ag/AgCl. Pure wear of alloy occurred in the form of abrasive wear. At anodic potentials under tribological contact, corrosion raised the friction coefficient as compared to pure wear and increased wear of the alloy. These results are presented and discussed in this paper.

Block copolymer lithography based on block copolymer (BCP) self-assembly can be used to develop soft mask nanoscale templates for subsequent pattern transfer to generate substrate features. Self-assembly of lamellar polystyrene-b-polymethylmethacrylate BCP of varying molecular weights to generate silicon nanoscale features is reported here. It has also been demonstrated that the feature size can be controlled by a plasma over-etch process and discussed.

The "Eigen cation", H₃O⁺(H ₂O)₃, is the most prevalent protonated water structure in the liquid phase and the most stable gas-phase isomer of the H ⁺(H₂O)₄ cluster. Nevertheless, its 50 K argon predissociation vibrational spectrum contains unexplainable low frequency peak(s). We have simulated the IR spectra of 10 gas-phase H⁺(H ₂O)₄ isomers, that include zero to three argon ligands, using dipole autocorrelation functions from ab initio molecular dynamics with the CP2K software. We have also tested the effect of elevated temperature and dispersion correction. The Eigen isomers describe well the high frequency portion of the spectrum but do not agree with experiment below 2000 cm ^-1. Most notably, they completely lack the "proton transfer bands" observed at 1050 and 1750 cm^-1, which characterize Zundel-type (H₅O₂+) isomers. In contrast, linear isomers with a Zundel core, although not the lowest in energy, show very good agreement with experiment, particularly at low frequencies. Peak assignments made with partial velocity autocorrelation functions verify that the 1750 cm^-1 band does not originate with the Eigen isomer but is rather due to coupled proton transfer/water bend in the Zundel isomer.

A series of tetrahedral amorphous carbon structures with different microscopic mass densities was generated by calculations based on the density functional theory with a local density approximation and using a method of melting-cooling cycles. A detailed investigation of the properties of the simulated structures has been carried out. Particularly, the short-range order, nearest neighbour distances, fractions of sp¹, sp² and sp³ sites, average C-C-C bond angles and electronic density of states have been analyzed. The simulated structures and calculated properties are in good agreement with those obtained by others and with the experimental data. An unexpected observation is the presence of planar structures, which are typical for graphite, in the sample with low density. In addition, the nearest neighbour distance in the sample with mass density 3.54 g/cm³ is different from those reported previously. Possibilities to compare the density of states obtained from the simulations with the experimental results from scanning tunnelling spectroscopy and X-ray near edge spectrum are discussed.

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)-filled thermoplastic polyurethane-urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X-ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of -NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40341.

Density functional simulations have been performed for Au₇Cu₂₃ and Au₂₃Cu₇ clusters on MgO(100) supports to probe their catalytic activity for CO oxidation. The adsorption of reactants, O₂ and CO, and potential O₂ dissociation have been investigated in detail by tuning the location of vacancies (F-center, V-center) in MgO(100). The total charge on Au₇Cu₂₃ and Au₂₃Cu₇ is negative on all supports, regardless of the presence of vacancies, but the effect is significantly amplified on the F-center. Au₇Cu₂₃/MgO(100) and Au₂₃Cu₇/MgO(100) with an F-center are the only systems to bind O₂ more strongly than CO. In each case, O₂ can be effectively activated upon adsorption and dissociated to 2 × O atoms. The different reaction paths based on the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms for CO oxidation have been explored on the Au₇Cu₂₃ and Au₂₃Cu₇ clusters on F-centers, and the results are compared with the previous findings for Au₁₅Cu₁₅. Overall, the reaction barriers are small, but the changes in the Au:Cu ratio tune the reactant adsorption energies and sites considerably, showing also varying selectivity for CO and O₂. The microkinetic model built on the basis of the above results shows a pronounced CO₂ production rate at low temperature for the clusters on F-centers.

Cationic specificity which follows the Hofmeister series has been established for the catalytic efficiency of haloalkane dehalogenase LinB by a combination of molecular dynamics simulations and enzyme kinetic experiments. Simulations provided a detailed molecular picture of cation interactions with negatively charged residues on the protein surface, particularly at the tunnel mouth leading to the enzyme active site. On the basis of the binding affinities, cations were ordered as Na⁺ > K⁺ > Rb⁺ > Cs⁺. In agreement with this result, a steady-state kinetic analysis disclosed that the smaller alkali cations influence formation and productivity of enzyme-substrate complexes more efficiently than the larger ones. A subsequent systematic investigation of two LinB mutants with engineered charge in the cation-binding site revealed that the observed cation affinities are enhanced by increasing the number of negatively charged residues at the tunnel mouth, and vice versa, reduced by decreasing this number. However, the cation-specific effects are overwhelmed by strong electrostatic interactions in the former case. Interestingly, the substrate inhibition of the mutant LinB L177D in the presence of chloride salts was 7 times lower than that of LinB wild type in glycine buffer. Our work provides new insight into the mechanisms of specific cation effects on enzyme activity and suggests a potential strategy for suppression of substrate inhibition by the combination of protein and medium engineering.

This study encompasses a comprehensive account of the abrasive wear properties of carbide-free, ultrahigh-strength bainitic steels processed through ausforming at three different temperatures well below the recrystallization stop temperature followed by bainitic transformation at temperatures close to the M_s temperature. Five medium-carbon, high-silicon compositions were designed for the study by suitably varying the alloying levels of carbon, vanadium, niobium, molybdenum, and aluminum. While ausforming at lower temperatures enabled a large number of nucleation sites leading to significant refinement of bainitic laths, the decomposition of austenite at relatively low transformation temperatures was accelerated due to the presence of a high dislocation density, thus enabling completion of bainitic transformation in a reasonable length of time. The steels were characterized in respect of microstructural features and mechanical properties, besides evaluation of wear resistance through a high-stress abrasive wear testing method with natural granite abrasives. The microstructures comprised different fractions of bainitic ferrite and/or granular bainite (56–68%), martensite (0–25%), besides a significant fraction of retained austenite (20–34%) manifesting as pools and also interlath films, depending on the ausforming conditions and subsequent cooling paths. A tensile strength of 1900 MPa level was achieved with hardness exceeding 500 HV for the medium-temperature ausformed steel containing a high carbon content that also showed lowest mass loss in the wear test. The hardness-to-mass loss ratio appeared highly promising with some of the carbide-free bainitic steels on par with or better than the reference martensitic steel. The high work-hardening capability as a consequence of the strain-induced austenite to martensite transformation was considered as the main factor for the superior abrasive wear resistance of the carbide-free bainitic steels.

An atmospheric pressure aerosol-based wet thin film coating technique called the nFOG is characterized and applied in polymer film coatings. In the nFOG, a fog of droplets is formed by two air-assist atomizers oriented toward each other inside a deposition chamber. The droplets settle gravitationally and deposit on a substrate, forming a wet film. In this study, the continuous deposition mode of the nFOG is explored. We determined the size distribution of water droplets inside the chamber in a wide side range of 0.1–100 µm and on the substrate using aerosol measurement instruments and optical microscopy, respectively. The droplet size distribution was found to be bimodal with droplets of approximately 30–50 µm contributing the most to the mass of the formed wet film. The complementary measurement methods allow us to estimate the role of different droplet deposition mechanisms. The obtained results suggest that the deposition velocity of the droplets is lower than the calculated terminal settling velocity, likely due to the flow fields inside the chamber. Furthermore, the mass flux of the droplets onto the substrate is determined to be in the order of 1 g/m³s, corresponding to a wet film growth rate of 1 µm/s. Finally, the nFOG technique is demonstrated by preparing polymer films with thicknesses in the range of approximately 0.1–20 µm.

Fretting fatigue may lead to severe damage in machines. Adhesive material transfer spots in millimeter scale have previously been observed on fretted surfaces, which have been related to cracking. In this study, fretting-induced cracks formed in a large annular flat-on-flat contact are characterized. Optical and scanning electron microscopy of the fretting scar cross-section samples of self-mated quenched and tempered steel specimens revealed severe cracking and deformed microstructure. Two major cracks typically formed around an adhesion spot, which propagated at an oblique angle, regardless of the test parameters used. Millimeter-scale cracks were observed already within a few thousand loading cycles.

High-velocity impact wear can have a significant effect on the lifetime of thermally sprayed coatings in multiple applications, e.g., in the process and paper industries. Plasma-sprayed oxide coatings, such as Cr₂O₃- and TiO₂-based coatings, are often used in these industries in wear and corrosion applications. An experimental impact study was performed on thermally sprayed ceramic coatings using the High-Velocity Particle Impactor (HVPI) at oblique angles to investigate the damage, failure, and deformation of the coated structures. The impact site was characterized by profilometry, optical microscopy, and scanning electron microscopy (SEM). Furthermore, the connection between the microstructural details and impact behavior was studied in order to reveal the damage and failure characteristics at a more comprehensive level. Differences in the fracture behavior were found between the thermally sprayed Cr₂O₃ and TiO₂ coatings, and a concept of critical impact energy is presented here. The superior cohesion of the TiO₂ coating inhibited interlamellar cracking while the Cr₂O₃ coating suffered greater damage at high impact energies. The HVPI experiment has proven to be able to produce valuable information about the deformation behavior of coatings under high strain rates and could be utilized further in the development of wear-resistant coatings.

Thermal spraying using liquid feedstock can produce coatings with very fine microstructures either by utilizing submicron particles in the form of a suspension or through in situ synthesis leading, for example, to improved tribological properties. The focus of this work was to obtain a bimodal microstructure by using simultaneous hybrid powder-precursor HVOF spraying, where nanoscale features from liquid feedstock could be combined with the robustness and efficiency of spraying with powder feedstock. The nanostructure was achieved from YSZ and ZrO₂ solution-precursors, and a conventional Al₂O₃ spray powder was responsible for the structural features in the micron scale. The microstructures of the coatings revealed some clusters of unmelted nanosized YSZ/ZrO₂ embedded in a lamellar matrix of Al₂O₃. The phase compositions consisted of γ- and α-Al₂O₃ and cubic, tetragonal and monoclinic ZrO₂. Additionally, some alloying of the constituents was found. The mechanical strength of the coatings was not optimal due to the excessive amount of the nanostructured YSZ/ZrO₂ addition. An amount of 10 vol.% or 7 wt.% 8YSZ was estimated to result in a more desired mixing of constituents that would lead to an optimized coating architecture.

The fatigue life of thermally sprayed Al₂O₃- and Cr₂O₃-based coatings has been studied under low-energy (0.7–5 mJ) impact conditions. A threshold impact energy and amount of repetitions the coatings can endure with said energy before catastrophic failure was obtained. The catastrophic failure was determined to occur when the fracture mode of the coating switched from brittle cone cracking to quasi-plastic radial cracking. The results are examined relative to the microstructural features along with other properties of the coatings - hardness and cavitation resistance. The experiment provided a new approach for a straightforward comparison of the micro-scale impact fatigue life of thermally sprayed coatings unachievable with previous methods.

Cold gas spraying was used to make a coating from an equiatomic CrFeNiMn high-entropy alloy. This four-component alloy was chosen because it is Co-free, thus allowing application in nuclear industries as a possible replacement of currently used stainless steel coatings. The feedstock material was gas atomized powder with a particle size distribution from 20 to 45 μm. A number of parameters were tested, such as the powder feed rate and gas feed pressure, in order to obtain as dense a coating as possible with nitrogen as the process gas. Spraying was performed using a gas preheating temperature of 1000 °C, gas feed pressure ranging from 50 to 60 bar, and two powder feeding rates. The coating thicknesses ranging from 230 to 490 m and porosities ranging from 3% to 10% were obtained depending on the powder feed rate and gas feed pressure. The hardness of the cross-section of the coating was usually lower than that of the surface. The highest coating hardness obtained was above 300 HV_0.3 for both the surface and the cross-section. The as-atomized powder consisted of a face-centered cubic (FCC) phase with a minute amount of body-centered cubic (BCC) phase, which was no longer detectable in the coatings. The microstructure of the coating was highly stressed due to the high degree of deformation occurring in cold gas spraying. The deformation leads to strain hardening and induces a pronounced texture in the coating. The 111 planes tend to align along the coating surface, with deformation and texturing concentrating mainly on particle boundaries. A high-entropy alloy (HEA) coating was successfully sprayed for the first time using nitrogen as a process gas. The coating has the potential to replace stainless steel coatings in nuclear industry applications.

Process optimization and quality control are important issues in cold spraying and coating development. Because the cold spray processing is based on high kinetic energy by high particle velocities, online spray monitoring of particle inflight properties can be used as an assisting process tool. Particle velocities, their positions in the spray jet, and particle size measurements give valuable information about spraying conditions. This, in turn, improves reproducibility and reliability of coating production. This study focuses on cold spraying of Al6061 material and the connections between particle inflight properties and coating characteristics such as structures and mechanical properties. Furthermore, novel 2D velocity scan maps done with theHWCS2 online spray monitoring system are presented as an advantageous powder and spray condition controlling tool. Cold spray processing conditions were similar using different process parameters, confirmed with the online spray monitoring prior to coating production. Higher particle velocities led to higher particle deformation and thus, higher coating quality, denser structures, and improved adhesions. Also, deposition efficiency increased significantly by using higher particle velocities.

The present work describes the wear behaviour of nodular cast iron in rolling-sliding contact with steel wire ropes and steel wires in laboratory and in-service conditions. In each of the studied examples, the wear had proceeded through a surface fatigue process, in which inter-nodular crack propagation and simultaneous deformation in a thin sub-surface zone had resulted in the formation of ferrous scales consisting of material from the metal matrix of the cast iron. The scale layers of the wear surface were oriented towards the direction of the sliding component of the motion, and the spalling of the scales was identified as the dominating mechanism for material removal from the wear surface. The initiation behaviour of the inter-nodular cracks was analysed by crack measurements and statistical analysis of the depths and initiation angles of the cracks in relation to the wear surface. The initiation depths of the cracks increased with increasing contact pressure. Roller samples from in-service and from the component wear tests showed closely similar distributions of the crack depths and crack initiation angles. The sample from the twin-disc test showed aspects of cracking behaviour that were typical of both the rolling and the sliding direction of the roller samples.

The demanding environments typically encountered by the wear resistant steels create challenges for the materials selection, because the hardness grades of the steels alone do not reveal the true nature of their wear behavior. In this study, five commercial wear resistant steels were tested using three application oriented test methods with five different test variables for abrasion, impact-abrasion, and slurry erosion. All the used test methods produced high-stress conditions that crushed the used mineral abrasive, plastically deformed the sample surfaces, and led to the formation of adiabatic shear bands. When the results produced by the chosen methods were compared, the normalization of the wear losses by the wear area and test time revealed well the differences between the methods. The test methods ranked the steels similarly, but there were clear differences in the wear rates and wear mechanisms between the tests. In addition, the abrasive methods produced surface adiabatic shear bands, while subsurface shear bands were initiated by the more impacting methods. In the studied conditions, the work hardening ability of the steel had a clear influence on its wear resistance, which largely explains the marked differences in the wear rates of the studied commercial 500HB grade steels.

We have investigated the role of the nitrogen content, the growth parameters, and the annealing processes involved in molecular beam epitaxy of GaInNAs solar cells lattice-matched to GaAs. The nitrogen composition was varied between 1% and 5%. The influence of the growth temperature was assessed by performing photoluminescence, atomic force microscopy, X-ray diffraction, reflection high-energy electron diffraction, quantum efficiency and light-biased current-voltage measurements. The growth temperature ensuring the best cell parameters was found to be 440 C. At this temperature we were able to incorporate up to 4% of nitrogen and achieve a good material quality. Further increase of the N composition to 5% led to phase separation. For the lattice matched samples grown within the optimal temperature range, we have identified a clear (1×3) surface reconstruction. Using the optimized growth we have demonstrated a GaInNAs p-i-n solar cell structure containing 4% nitrogen, that exhibited a short-circuit current density as high as 33.8 mA/cm² in respect to effective area illuminated. These measurements have been performed under real sun AM1.5 (~1000 W/m²) illumination. © 2014 Elsevier B.V.

Mechanical recycling of multilayer plastic films from food packages was investigated. The multilayer films were manually separated from municipal solid waste, washed, grinded, and finally compounded at 0–100 wt% concentrations with virgin low-density polyethylene (PE-LD). Polyethylene grafted with maleic anhydride (PE-g-MA) compatibilizer was used in two of the compounds to replace 2 and 5 wt% of the PE-LD to study its effect as well. PE-g-MA is expected to improve the mechanical properties of the compounds by promoting the adhesion between incompatible polymer phases. The composition of the compounds was characterized with Fourier-transform infrared spectroscopy and differential scanning calorimetry and their properties were studied with tensile testing and rotational rheometer measurements. All tested compounds had relatively good mechanical properties and processability. This indicates that recycled multilayer films could replace at least part of the virgin PE-LD in applications where high-thermal stability or good visual appearance is not required. The PE-g-MA compatibilizer did not have a significant effect on the mechanical properties of the compounds.

We introduce a novel strategy to quantify the disorder of extended water-water hydrogen-bond (HB) networks sampled in particle-based computer simulations. The method relies on the conformational clustering of the HB connectivity states. We successfully applied it to unveil the fine relationship among the protein dynamical transition in hydrated powder, which marks the activation of protein flexibility at T_d ≈ 240 K, and the sudden increase in the configurational disorder of the water HB network enveloping the proteins. Our finding links, in the spirit of the Adam-Gibbs relationship, the diffusivity of protein atoms, as quantified by the hydrogen mean-square displacements, and the thermodynamic solvent configurational entropy.

In the present work, a strong filler-filler network of conductive carbon black was strategically established in an elastomer matrix, which leads to a unique combination of electrical and mechanical properties. The novelty of our composites was the development of a strong percolated morphology of nanostructured conducting carbon black particles by the incorporation of relatively large nonreinforcing spherical silica particles, inside the soft elastomer matrix. This technique allowed us to fabricate solution styrene butadiene rubber (S-SBR) composites with outstanding electrical conductivity of 40 S/m, tensile strength ∼10 MPa, and extensibility up to 200%. Furthermore, the electrical conductivity was strain-independent up to 50% elongation strain. The electrical conductivity was found to be unaltered after 2000 loading-unloading cycles. This is the first ever report of a robust elastomeric system with such high electrical conductivity where all the basic ingredients used were selected from well-known commercially available raw materials of rubber industry. This work directly manifests an industrially viable method for preparing high-performance elastic conductors that can be utilized in robust and flexible applications.

Synthetic zinc patina was grown on galvanized steel sheets in supercritical carbon dioxide atmosphere. Different patina compounds were dissolved and quantified using a stepwise immersion and dissolution procedure. The distinct patina components, namely anhydrous zinc carbonate (a dense layer adjacent to metallic zinc) and zinc hydroxy carbonate (nanowires on the surface), were dissolved in glycine solutions, followed by quantification of Zn²⁺ in the solutes by X-ray fluorescence. The zinc hydroxy carbonate nanowires were readily glycine soluble, and the anhydrous zinc carbonate showed scarce glycine solubility, which enabled their selective quantification. The amount of the remaining (anhydrous) zinc carbonate after glycine extraction was determined from the glycine-soluble zinc oxide after calcination (heat treatment for 10 minutes at 350°C). The results were verified by scanning electron microscopy imaging and Fourier transform infrared spectroscopy measurements.

Cysteine-tagged, genetically engineered avidin named ChiAvd-Cys and wild-type avidin form monolayers or bilayer structures when immobilised directly on gold. Non-specific binding can be reduced by a post-treatment of the avidin layers with a N-[tris(hydroxymethyl)methyl]-acrylamide (pTHMMAA) polymer. ChiAvd-Cys showed excellent activity when immobilised on gold. About 70% of the ChiAvd-Cys molecules were able to bind two biotinylated green fluorescent proteins (per avidin tetramer). Amino-biotinylated antibody F(ab′) ₂ fragments could be bound to every 4th and 8th ChiAvd-Cys and wild-type avidin molecule, respectively, whereas on average one thiol-biotinylated antibody Fab′-fragment was bound to every ChiAvd-Cys. Antigen binding to the thiol-biotinylated Fab′-fragment bound to the ChiAvd-Cys/pTHMMAA layer was almost twice compared to that of the amino-biotinylated F(ab′) ₂-fragments. The high antigen binding was due to a site-directed orientation of the thiol-biotinylated fragments. The ChiAvd-Cys/pTHMMAA layers offer high capacity that may be used to couple biotinylated compounds on biosensor surfaces.

Evaluation of wear mechanisms of thick thermal sprayed cermet coatings is a challenging endeavor given the numerous process-induced structural and chemical changes as well as presence of residual stresses. In an effort to understand the damage processes under contact load and their sensitivity to the process induced microstructural attributes, controlled scratch testing was used. Detailed assessment of the resultant damage zone provided repeatable cracking patterns that are categorized as (i) Localized collapsing of material, (ii) angular cracks, (iii) primary semi-circular and developed semi-circular cracks and (iv) splat delamination. A correlation was established by linking observed damage mechanisms to the process induced microstructural descriptions including role of spray particle conditions and residual stresses. Quantitative correlations between delamination load for cracking and the process induced variable including particle properties as described by the non-dimensional melting index concept as well as residual stresses were established. Melting index captures the combined effect of particles[U+05F3] thermal and kinetic history and thus coating porosity and the process induced decarburization. The results highlight the critical role of coating density and stress evolution during the coating formation. The research points to scratch testing as a powerful evaluation method to characterize contact response of thick thermal spray cermet coatings including operative mechanisms.

A molecular layer with low non-specific binding enabling determination of low concentrations of 3,4-methylenedioxymethamphetamine (MDMA) by the displacement of antibodies has been developed. Antibody Fab′-fragments at various concentrations have been site-directly immobilised on gold and intercalated with a hydrophilic non-ionic polymer that reduces non-specific binding. Bovine serum albumin conjugated with MDMA and various concentrations of anti-MDMA antibodies were bound to the layer. The amount of conjugates and antibodies bound was dependent on the amount of Fab′-fragments in the layer. Antibodies were also bound to the conjugates physisorbed directly onto the gold surface and in mixtures with the polymer or with a lipoamide. A high displacement of antibodies was observed by surface plasmon resonance (SPR) on interaction of MDMA with the different layers in buffer solution. No displacement could, however, be observed in saliva with the pure conjugate layer because of a high non-specific binding of proteins. When the conjugates were coupled to the surface through the antibody Fab-fragment/polymer layer, MDMA concentrations as low as 0.02 ng mL^-1 (0.14 nM) could easily be detected in buffer. In diluted saliva the lowest limit of detection was 0.4 ng mL^-1 enabling determination of drugs from saliva with a cut-off concentration of 2 ng mL^-1. The molecular layer of antibody Fab′-fragments and polymer thus shows great potential for binding conjugates and antibodies that can be displaced on the interaction with very low concentrations of small-sized molecules. A low non-specific binding is guaranteed by the presence of the hydrophilic polymer.

Two different analytical approaches—collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) and chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-TOF)—were applied to detect and identify the online gaseous KOH and HCl formed in the addressed high-temperature reactions. Samples of pure KCl, KCl+Cr, KCl+Fe, and KCl+316 L were studied at 550°C under dry and humid conditions with varying oxygen concentrations. The goal was to shed more light on the gas-phase chemistry during KCl-induced corrosion under conditions relevant to biomass combustion. CI-APi-TOF proved to be a valuable tool for high-temperature corrosion studies: HCl was identified to have formed during the reactions under humid conditions. On the contrary, despite the known sensitivity of CPFAAS, the formation of KOH could not be verified in any of the performed measurements.

High density polyethylene (rHDPE) is extruded 1 to 8 times, with and without detergent, to simulate the effects of impurities on the material and on the artificial ageing process. The mechanical properties, thermal stability, rheology, Fourier transform infrared spectroscopy (FTIR), and volatile organic compound (VOC) emissions are measured. According to the results, ageing of rHDPE increases tensile strength, reduces elongation, and enhances side chain branching of the material and thus causes rheological changes. The addition of detergent reduces changes in mechanical properties and rheological behavior but accelerates thermal degradation. VOC and FTIR measurements of the samples with detergent addition show generation of harmful 1,4-dioxane. The amount of total emission, as well as emissions of important perfumes limonene and 1R-α-pinene, decreases during multiple extrusion cycles. Heating of the plastics is found to be a major factor in the VOC emission reduction. Impurities have a notable effect on the artificial ageing results.

Dielectric properties (e.g., DC resistivity and dielectric breakdown strength) of insulating thermally sprayed ceramic coatings differ depending on the form of electrical stress, ambient conditions, and aging of the coating, however, the test arrangements may also have a remarkable effect on the properties. In this paper, the breakdown strength of high velocity oxygen fuel-sprayed alumina coating was studied using six different test arrangements at room conditions in order to study the effects of different test and electrode arrangements on the breakdown behavior. In general, it was shown that test arrangements have a considerable influence on the results. Based on the results, the recommended testing method is to use embedded electrodes between the voltage electrode and the coating at least in DC tests to ensure a good contact with the surface. With and without embedded electrodes, the DBS was 31.7 and 41.8 V/µm, respectively. Under AC excitation, a rather good contact with the sample surface is, anyhow, in most cases acquired by a rather high partial discharge activity and no embedded electrodes are necessarily needed (DBS 29.2 V/µm). However, immersion of the sample in oil should strongly be avoided because the oil penetrates quickly into the coating affecting the DBS (81.2 V/µm).

A novel adaptive compensation architecture for the frequency response mismatch of 2-channel time-interleaved ADC (TI-ADC) is proposed for developing high-performance self-adaptive systems. The proposed approach overcomes the existing methods in the sense that the TI-ADC mismatch identification can be performed without allocating a region where only the TI-ADC mismatch spurs are present. This is accomplished via mapping the TI-ADC problem into an I/Q mismatch problem which allows deploying complex statistical signal processing. As proof of concept, the compensation architecture is demonstrated and tested on a 16-bit TI-ADC measured hardware data.

8-Oxoguanine is one of the key products of indirect radiation damage to DNA by reactive oxygen species. Here, we describe ionization of this damaged nucleobase and the corresponding nucleoside and nucleotide in aqueous phase, modeled by the nonequilibrium polarizable continuum model, establishing their lowest vertical ionization energies of 6.8-7.0 eV. We thus confirm that 8-oxoguanine has even lower ionization energy than the parental guanine, which is the canonical nucleobase with the lowest ionization energy. Therefore, it can act as a trap for the cationic hole formed by ionizing radiation and thus protect DNA from further radiation damage. We also model using time-dependent density functional theory and measure by liquid jet photoelectron spectroscopy the valence photoelectron spectrum of 8-oxoguanine in water. We show that the calculated higher lying ionization states match well the experiment which, however, is not sensitive enough to capture the electron signal corresponding to the lowest ionization process due to the low solubility of 8-oxoguanine in water.

Novel high-hardness medium-carbon martensitic laboratory steel has been produced and tested for abrasive wear resistance. Different finish rolling temperatures (FRT) combined with either direct quenching (DQ) or interrupted quenching to 250 °C was applied to vary the content of retained austenite and hardness. The steel carbon content was set to 0.35 % to obtain a surface hardness of approximately 600 HB. Lowering the finish rolling temperature in the range 920-780 °C, i.e. into the non-recrystallization regime resulted in a more elongated prior austenite grain structure, which increased the hardness of the DQ variants without any significant loss of Charpy-V impact toughness. Although increasing the degree of autotempering by raising the quench stop temperature reduces the hardness of the martensitic microstructure, it was found that proper quenching stop temperature could be utilized to achieve balanced toughness and hardness properties. Impact-abrasive wear resistance as measured in impeller-tumbler tests with natural granite as the abrasive demonstrated that wear resistance increased with increasing surface hardness.

The photoinduced electron transfer processes were studied for hybrid systems consisting of self-assembled monolayer of zinc phthalocyanine (ZnPc) assembled on ZnO nanorods and a film of organic hole transporting material (HTM) atop. Polythiophene (P3HT) or Spiro-OMeTAD were used as HTM. The study was carried out by ultrafast transient absorption spectroscopy technique with selective excitation of ZnPc at 680 nm or P3HT at 500 nm. Data analysis revealed that photoexcitation of ZnPc in the structure ZnO|ZnPc|P3HT results in a fast (1.8 ps) electron transfer from ZnPc to ZnO, which is followed by a hole transfer from the ZnPc cation to P3HT roughly in 30 ps. However, in the case of ZnO|ZnPc|Spiro-OMeTAD structure, the primary reaction upon excitation of ZnPc is a fast (0.5 ps) hole transfer from ZnPc to Spiro-OMeTAD, and the second step is electron injection from the ZnPc anion to ZnO in roughly 120 ps. Thus, we demonstrate two structurally very similar hybrid architectures that implement two different mechanisms for photoinduced charge separation found in dye-sensitized or in organic solar cells.

The microstructures of two types of ZrO₂-7.5wt.% Y₂O₃ (YSZ) coatings fabricated by air plasma spraying (APS) but containing different amounts of columnar grains were investigated through scanning electron microscopy and electron backscatter diffraction analysis. Differences in the formation mechanisms of columnar and equiaxed grains were characterized using particles collected in a water container, from which it was found that these mechanisms are closely related to the melted state of the in-flight particles. Furthermore, it was found that the higher the columnar grain concentration of an as-sprayed coating, the higher its thermal shock resistance. This means that it is possible to improve the thermal shock resistance of APS YSZ coatings simply by introducing more columnar grains, as this increases their thermal conductivity. Using this knowledge, YSZ coatings with good thermal shock resistance and a thermal conductivity of 0.81W·(m·K)^-1 at 1100°C were successfully prepared.

More durable materials enable reducing the downtime and maintenance costs by decreasing the number of replaced core components in various industrial applications. In this study, the behavior of three wear-resistant quenched martensitic steel grades and the S355 structural steel was examined in controlled impact conditions. The materials' impact behavior was investigated by several methods including residual stress measurements and electron backscatter diffraction. For all studied materials, the size and depth of the impact marks correlate via a logarithmic function to the number of impacts mostly due to work hardening. The underlying deformation behavior of the material depends on the mechanical properties and microstructure of the material. At high impact counts, softer martensitic steel was found to behave differently when compared to the other tested materials as it underwent severe changes in its microstructure and exhibited marked hardening.

Thermally sprayed hard metal coatings are the industrial standard solution for numerous demanding applications to improve wear resistance. In the aim of improving coating quality by utilising finer particle size distributions, several approaches have been studied to control the spray temperature. The most viable solution is to use the modern high velocity air-fuel (HVAF) spray process, which has already proven to produce high-quality coatings with dense structures. In HVAF spray process, the particle heating and acceleration can be efficiently controlled by changing the nozzle geometry. In this study, fine WC-10Co4Cr and Cr₃C₂-25NiCr powders were sprayed with three nozzle geometries to investigate their effect on the particle temperature, velocity and coating microstructure. The study demonstrates that the particle melting and resulting carbide dissolution can be efficiently controlled by changing the nozzle geometry from cylindrical to convergent–divergent. Moreover, the average particle velocity was increased from 780 to over 900 m/s. The increase in particle velocity significantly improved the coating structure and density. Further evaluation was carried out to resolve the effect of particle in-flight parameters on coating structure and cavitation erosion resistance, which was significantly improved in the case of WC-10Co4Cr coatings with the increasing average particle velocity.

We consider the impact of phosphatidic acid (namely, 1,2-dioleoyl-sn-glycero-3-phosphate, DOPA) on the properties of a zwitterionic (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC) bilayer used as a model system for protein-free cell membranes. For this purpose, experimental measurements were performed using differential scanning calorimetry and the Langmuir monolayer technique at physiological pH. Moreover, atomistic-scale molecular dynamics (MD) simulations were performed to gain information on the mixed bilayer's molecular organization. The results of the monolayer studies clearly showed that the DPPC/DOPA mixtures are nonideal and the interactions between lipid species change from attractive, at low contents of DOPA, to repulsive, at higher contents of that component. In accordance with these results, the MD simulations demonstrated that both monoanionic and dianionic forms of DOPA have an ordering and condensing effect on the mixed bilayer at low concentrations. For the DOPA monoanions, this is the result of both (i) strong electrostatic interactions between the negatively charged oxygen of DOPA and the positively charged choline groups of DPPC and (ii) conformational changes of the lipid acyl chains, leading to their tight packing according to the so-called umbrella model, in which large headgroups of DPPC shield the hydrophobic part of DOPA (the conical shape lipid) from contact with water. In the case of the DOPA dianions, cation-mediated clustering was observed. Our results provide a detailed molecular-level description of the lipid organization inside the mixed zwitterionic/PA membranes, which is fully supported by the experimental data.

Prior austenite grain size has a marked effect on the hardenability, strength, and impact toughness properties of steels. This study was conducted in order to understand the effect of prior austenite grain size and morphology on the mechanical properties and abrasive wear performance of an ultra-high strength steel. A commercial quenched 500 HB grade wear-resistant steel was selected for the study: the steel was austenitized at two different temperatures and compared to the original, as-received quenched condition. The resulting mean prior austenite grain size was ranging from 14 μm to 34 μm. The decrease in grain size improved the low-temperature impact toughness properties. A high stress abrasive wear testing method with natural granite abrasives was utilized for the evaluation of abrasive wear resistance. The results suggest that decreasing the prior austenite grain size improves the abrasive wear resistance with similar hardness level martensitic steels. In addition, high-resolution electron backscatter diffraction measurements revealed formation of ultra-fine grain structures in the severely deformed regions of the wear surfaces.

Nitrile rubber/silica composites are prepared by a sol-gel process using tetraethoxysilane as precursor in the presence of γ- mercaptopropyltrimethoxysilane as a silane coupling agent. Here, we follow a novel processing route where the silica particles are generated inside the rubber matrix before compounding with vulcanizing ingredients. The effect of in situ generated silanized silica on the properties of the rubber composite has been evaluated by studying curing characteristics, morphology, mechanical and dynamic mechanical properties. Enhanced rubber-filler interaction of these composites is revealed from stress-strain studies and dynamic mechanical analysis. Excessive use of silane shows an adverse effect on mechanical properties of the composites. Due to finer dispersed state of the in situ silica and enhanced rubber-filler interaction, the mechanical properties and thermal stability of the composites are improved compared to corresponding ex situ processed composite.

Thermally sprayed Fe-based coatings have been extensively studied as future solution in order to replace more expensive, harmful and environmentally dangerous Ni- and WC-based coatings for several industrial applications where high corrosion and wear resistance are required. The aim of the present study is to investigate the effect of spraying parameters on the microstructure and the corrosion resistance of Fe-based coatings manufactured with the High Velocity Air Fuel (HVAF) thermal spray process. Six sets of thermal spraying parameters have been chosen and their effect on the overall quality of coatings was investigated. All HVAF coatings showed comparably dense microstructure with near-zero oxidation, proving the high quality of the deposition process. However, higher anti-corrosion and mechanical properties were achieved by increasing the spraying air pressure and decreasing the particle feeding rate without altering the thickness and the overall deposition rate. Powder feeding rate was reported to have a remarkable effect on microstructure and corrosion properties. Coatings with beneficial compressive residual stresses were successfully obtained by increasing air pressure during spraying which resulted in improved microstructural and corrosion properties.

Tempering is an essential part in the fabrication of ultra-high strength steels and it is also widely applied in the processing of wear-resistant steels. In this paper, the effects of different tempering temperatures on the impact-abrasive and abrasive wear properties of martensitic ultra-high strength steels were studied. A novel press-hardening steel with carbon content of 0.4 wt% was received in hot-rolled condition and further austenitized, water-quenched and tempered for 2 h at different temperatures (150–400 °C). Tensile strength values up to 2200MPa and hardness exceeding 650HV were measured. Wear testing was done with impact-abrasive impeller-tumbler and abrasive dry-pot application-oriented test methods simulating mining and mineral handling environments. A laboratory rolled 600HB steel and a commercial 500HB grade wear-resistant steel were included for comparison. The wear surfaces and cross-sections of the samples were thoroughly characterized. Both testing methods produced highly deformed surface layers and strong work-hardening. Wear performance was mainly controlled by the initial hardness of the steels, but differences were found in the highly work-hardened surfaces of the steels.

Wear resistant steels are commonly categorized by their hardness, and in the case of quenched wear resistant steels, their Brinell hardness grades are widely considered almost as standards. In this study, the abrasive wear performance of 15 commercially available 400 HB grade quenched wear resistant steels from all over the world were tested with granite gravel in high stress conditions. The aim was to evaluate the real wear performance of nominally similar steels. Also properties such as hardness, hardness profiles, microstructures and chemical compositions of the steels were studied and reasons for the differences in their wear performance further discussed. In terms of mass loss, over 50% differences were recorded in the abrasive wear performance of the studied steels. Variations in the chemical compositions were linked to the auto-tempered microstructures of the steels, and the microstructural characteristics were further linked to their ultimate wear behavior. © 2014 Elsevier B.V.

A green-to-blue triplet-triplet annihilation upconversion of 24.5% quantum yield was achieved at a remarkably low 600 μM annihilator concentration in a viscous polymer matrix. This was made possible by utilizing a ZnTPP-based photosensitizer with exceptionally long 11 ms phosphorescence lifetime. Higher 3 mM annihilator concentration resulted in lower 24% upconversion quantum yield.

This work encompasses a facile method for tailoring surface defects in electrospun TiO2 nanofibers by employing hydrogen plasma treatments. This amiable processing method was proven with SQUID, EPR, and XPS to be highly effective in generating oxygen vacancies, accompanied by the reduction of Ti4+ centers to Ti3+, resulting in the formation of black titania. The treatment temperature was found to affect the Ti3+/Ti4+ ratios and surface valence, while preserving the original 1D morphology of the titania fibers. Ab initio DFT calculations showed that a high concentration of oxygen vacancies is highly efficient in producing midgap states that enhance the system absorption over the whole visible range, as observed with UV/vis/NIR diffuse reflectance spectroscopy. Pristine TiO2 nanofibers produced a photocurrent density of similar to 0.02 mA/cm(2) at 1.23 V vs RHE, whereas the hydrogen plasma treatment resulted in up to a 10-fold increase in the photoelectrochemical performance.

Recent experimental and theoretical studies showed the preference of the hydronium ion for the vapor/water interface. To investigate the mechanism responsible for the surface propensity of this ion, we performed a series of novel quantum chemical simulations combined with the theory of solutions. The solvation free energy of the H₃O⁺ solute placed at the interface was obtained as -97.9 kcal/mol, being more stable by 3.6 kcal/mol than that of the solute embedded in the bulk. Further, we decomposed the solvation free energies into contributions from the water molecules residing in the oxygen and the hydrogen sides of the solute to clarify the origin of the surface preference. When the solute was displaced from the bulk to the interface, it was shown that the free energy contribution from the oxygen side is destabilized by ∼10 kcal/mol because of a reduction of the number of surrounding solvent water molecules. It was observed, however, that the free energy contribution due to the hydrogen side of the solute is unexpectedly stabilizing and surpasses the destabilization in the opposite side. We found that the stabilization in the hydrogen side originates from the solute-solvent interaction in the medium range beyond the nearest neighbor. It was also revealed that the free energy contribution due to the solute's electronic polarization amounts to about the half of the total free energy change associated with the solute displacement from the bulk to the interface.

Natural rubber (NR) is a versatile material possessing outstanding mechanical properties, which can be used in multiple applications including the rapidly developing dielectric elastomer generators (DEGs). One of the drawbacks of the existing DEGs is their low efficiency, which can be improved by lowering the dielectric and mechanical losses originating from the material. Therefore, the present research was focusing on assessing the ways to minimize the dielectric and mechanical losses of NR films rather than developing a DEG. In this article, the effect of natural proteins and the rubber stabilizers on energy dissipation of NR films was evaluated. Moreover, the effect of sample posttreatment (with water and acetone), curing and time after cure was discussed. As a result, deproteinized NR stabilized by ammonium caseinate outperformed unmodified NR due to reduced dielectric losses, mechanical hysteresis and stress relaxation. Moreover, the posttreatment methods were found to moderately reduce the material-relates losses.

A sol-gel transformation of liquid silica precursor to solid silica particles was carried out in a one-pot synthesis way, where a solution of styrene butadiene elastomer was present. The composites, thus produced, offered remarkable improvements of mechanical and dynamic mechanical performances compared to precipitated silica. The morphological analysis reveals that the alkoxy-based silica particles resemble a raspberry structure when the synthesis of the silica was carried out in the presence of polymer molecules and represent a much more open silica-network structure. However, in the absence of the polymer, the morphology of the silica particles is found to be different. It is envisaged that the special morphology of the in situ synthesized silica particles contributes to the superior reinforcement effects, which are associated with a strong silica-rubber interaction by rubber chains trapped inside the raspberry-like silica aggregates. Therefore, the interfaces are characterized in detail by low-field solid-state ¹H NMR spectroscopy, ²⁹Si solid-state NMR spectroscopy, and energy-dispersive X-ray spectroscopy. Low-field ¹H NMR-based double-quantum experiments provide a quantitative information about the cross-link density of the silica-filled rubber composites and about the influence of silane coupling agent on the chemical cross-link density of the network and correlates well with equilibrium swelling measurements. The special microstructure of the alkoxy-based silica was found to be associated with the interaction between alkoxy-based silica and rubber chains as a consequence of particle growth in the presence of rubber chains.

Two austenitic stainless steel grades, 316L and 904L, and three duplex stainless steel grades, LDX 2101, 2205, and 2507, were erosion–corrosion tested as impeller blade materials for hydrometallurgical applications. Samples were attached to the pressure and suction sides of an impeller and were tested in 50 g/l H₂SO₄ and 0.5 g/l Fe₂(SO₄)₃ for 72 h at 80°C and 95 °C in a small-scale reactor using quartz sand slurry. The results showed that under lower erosion intensity the ranking of the grades was similar to that in pure erosion. Under higher erosion intensity the ranking of the grades changed completely: lean alloys LDX 2101 and 316L suffered from the highest mass losses followed by 2205, 2507, and 904L. To clarify this behavior, the ability of the grades to repassivate was investigated with scratch tests. It was found that the ranking could be explained by the repassivation rates. The only exception was that 2507 showed a similar repassivation rate to 904L but its erosion–corrosion mass loss under higher erosion intensity was larger. One contributing factor to this was found to be the selective dissolution of the austenite phase of all the tested duplex grades. The prerequisites for the galvanic coupling between the phases that was responsible for the selective dissolution are discussed.