Thermal Electrochemical, and Plasma Oxidation of Ti–50Zr, Cu–50Zr, Cu–50Ti, and Cu–33Ti–33Zr Alloys

The three main methods for oxidation of metallic substrates, thermal, anodic and plasma have been applied to a copper, titanium, and zirconium alloy and its corresponding binaries (Cu–33Ti–33Zr, Cu–50Ti, Cu–50Zr and Ti–50Zr). Polished polycrystalline samples of these alloys were examined before treatment, after vacuum thermal annealing at 100°C and heating in 20 mTorr oxygen at 100, 200, and 300°C. ISS depth profiles were taken of selected samples. The least-noble component oxidizes first, but at high temperatures and with plasma oxidation the noble component segregates to the surface. A comparison of the resulting structures on the ternary and binary alloys with different oxidation methods is used to explore the physico-chemical processes during oxidation. Results from these three methods are discussed in terms of physical/chemical parameters that influence the chemical nature and structure of the resulting oxides. The electrochemical processes that occur during the materials reaction with a chosen environment are used to discuss the physical and chemical mechanisms involved. Intrinsic (thermal and plasma oxidation) and extrinsic (electrochemical oxidation) electric fields are shown to influence the chemical and structural nature of the resulting oxide structures. The influence of transport phenomena is discussed.     

Structure,phase composition,and strengthening of cast Al–Ca–Mg–Sc alloys

The structure and phase composition of Al–Ca–Mg–Sc alloys containing 0.3 wt % Sc, up to 10 wt % Ca, and up to 10 wt % Mg have been investigated in the cast state and state after heat treatment. It has been shown that only binary phases Al₄Ca, Al₃Sc, and Al₃Mg₂ can be in equilibrium with the aluminum solid solution. It has been found that the maximum strengthening effect caused by the precipitation of Al₃Sc nanoparticles for all investigated alloys is attained after annealing at 300–350°C.     

Structure and properties of selected (Cr–Al–N,TiC–C,Cr–B–N) nanostructured tribological coatings

The paper will present the state-of-art in the process, structure and properties of nanostructured multifunctional tribological coatings used in different industrial applications that require high hardness, toughness, wear resistance and thermal stability. The optimization of these coating systems by means of tailoring the structure (graded, superlattice and nanocomposite systems), composition optimization, and energetic ion bombardment from substrate bias voltage control to provide improved mechanical and tribological properties will be assessed for a range of coating systems, including nanocrystalline graded Cr_1−xAl_xN coatings, superlattice CrN/AlN coatings and nanocomposite Cr–B–N and TiC/a-C coatings. The results showed that the superlattice CrN/AlN coating exhibited a super hardness of 45 GPa when the bilayer period Λ was about 3.0 nm. Improved toughness and wear resistance have been achieved in the CrN/AlN multilayer and graded CrAlN coatings as compared to the homogeneous CrAlN coating. For the TiC/a-C coatings, increasing the substrate bias increased the hardness of TiC/a-C coatings up to 34 GPa (at −150 V) but also led to a decrease in the coating toughness and wear resistance. The TiC/a-C coating deposited at a −50 V bias voltage exhibited an optimized high hardness of 28 GPa, a low coefficient of friction of 0.19 and a wear rate of 2.37 × 10⁻⁷ mm³ N⁻¹ m⁻¹. The Cr–B–N coating system consists of nanocrystalline CrB₂ embedded in an amorphous BN phase when the N content is low. With an increase in the N content, a decrease in the CrB₂ phase and an increase in the amorphous BN phase were identified. The resulting structure changes led to both decreases in the hardness and wear resistance of Cr–B–N coatings.     

Electrodeposition and properties of Zn,Zn–Ni,Zn–Fe and Zn–Fe–Ni alloys from acidic chloride–sulphate electrolytes

Abstract

Zn, Zn–Ni, Zn–Fe and Zn–Fe–Ni films have been deposited by electrochemical deposition technique onto steel plate substrates. The objective of this study was to characterise the corrosion properties of these alloys in saline solution for the application as new environmentally friendly sacrificial coatings in the protection of steel structures. The morphological and structural properties of the alloys were systematically studied using XRD and SEM techniques. Cyclic voltammetry of the individual metals was performed to help understand the electroplating process of the films. Grain sizes of the films were calculated using Scherrer's formula. Partial substitution of Zn to Fe and Ni leads to an improvement in the corrosion resistance. Compared with other zinc alloys, the Zn–Ni alloy deposit was the noblest.     

Theoretical Analysis of Anomalies in High-Temperature Oxidation of Fe–Cr, Fe–Ni, and Fe–Ni–Cr Alloys

The following anomalies are theoretically analyzed: weakening of the protective ability of dense Cr₂O₃ film during its long-term thermal exposure (because of iron oxidation under the film); lowering of the heat resistance of Fe–Cr and Fe–Ni–Cr alloys during the oxidation (800°C) with an increase in the chromium content over 40 at. %; improving of the protective ability of the films formed at Fe–Ni alloys because of nickel oxidation under the dense FeO film; and the internal oxidation of the Fe 30Ni alloys under the FeO films with the internal formation of FeO oxides and spinel of NiFe₂O₄ type. It is shown that these anomalies can be explained, and the composition of the most heat-resistant alloys calculated, if one takes into account that associates with significantly stronger interatomic bonds than those in ideal solutions can form in solid solutions and cause unlimited solubility of the metallic components in each other.     

Microstructure,mechanical properties,and corrosion resistance of Mg–9Li–3Al–1.6Y alloy

Mg–9Li–3Al–1.6Y alloys were prepared through mixture method. The microstructure, mechanical properties, and corrosion resistance of the as-cast and asextruded alloys were studied by optical microscopy(OM),scanning electronic microscopy(SEM), X-ray diffraction(XRD), mechanical properties testing, and electrochemical measurement. The as-cast Mg–9Li–3Al–1.6Y alloy with the average grain size of 325 lm is composed of b-Li matrix, block a-Mg, and granule Al_2Y phases. After extrusion, the grain size of the as-cast alloy is obviously refined and reaches to 75 lm; the strength and elongation of the extruded alloy are enhanced by 17.20 % and49.45 %, respectively, owing to their fine microstructure and reduction of casting defects. The as-extruded alloy shows better corrosion resistance compared to the as-cast one, which may be related to the low stored energy and dislocation density in the extruded alloy, also the homogenization treatment before extrusion.     

Evolution of Microstructure,Residual Stress,and Tensile Properties of Mg–Zn–Y–La–Zr Magnesium Alloy Processed by Extrusion

The microstructure, texture, residual stress, and tensile properties of Mg–6 Zn–2 Y–1 La–0.5 Zr(wt%) magnesium alloy were investigated before and after extrusion process, which performed at 300 °C and 400 °C. The microstructural characterizations indicated that the as-cast alloy was comprised of α-Mg, Mg–Zn, Mg–Zn–La, and Mg–Zn–Y phases. During homogenization at 400 °C for 24 h, most of the secondary phases exhibited partial dissolution. Extrusion process led to a remarkable grain refi nement due to dynamic recrystallization(DRX). The degree of DRX and the DRXed grain size increased with increasing extrusion temperature. The homogenized alloy did not show a preferential crystallographic orientation, whereas the extruded alloys showed strong basal texture. The extrusion process led to a signifi cant improvement on the compressive residual stress and mechanical properties. The alloy extruded at 300 °C exhibited the highest basal texture intensity, the compressive residual stress and hardness, and yield and tensile strengths among the studied alloys.     

A comparative study of microstructure,oxidation resistance,mechanical, and tribological properties of coatings in Mo–B–(N), Cr–B–(N) and Ti–B–(N) systems

M–B–(N) (M = Mo, Cr, Ti) coatings were obtained by the magnetron sputtering of MoB, CrB₂, TiB, and TiB₂ targets in argon and in gaseous mixtures of argon with nitrogen. The structure and composition of the coatings have been investigated using scanning electron microscopy, glow-discharge optical emission spectroscopy, and X-ray diffraction. The mechanical and tribological properties of the coatings have been determined by nanoindentation, scratch-testing, and ball-on-disk tribological tests. The experiments on estimating the oxidation resistance of coatings were carried out in a temperature range of 600–1000°С. A distinctive feature of TiB₂ coatings was their high hardness (61 GPa). The Cr–B–(N) coatings had high maximum oxidation resistance (900°С (CrB₂) and 1000°С (Cr–B–N)) and possessed high resistance to the diffusion of elements from the metallic substrate up to a temperature of 1000°С. The Mo–B–N coatings were significantly inferior to the Ti–B–(N) and Cr–B–(N) coatings in their mechanical properties and oxidation resistance, as well as had а tendency to oxidize in air atmosphere after long exposure at room temperature. All of the coatings with nitrogen possessed a low coefficient of friction (in a range of 0.3–0.5) and low relative wear ((0.8–1.2) × 10^–6 mm3 N^–1 m^–1.     

Density of thermal vacancies in γ-Ti–Al–M,M=Si,Cr, Nb,Mo, Ta or W

Modifications to alloy chemistry are often used to tailor the intrinsic flow behavior of structural materials. Models of creep in intermetallic alloys must account for the influence of chemistry on the available intrinsic creep mechanisms. As in simple metals the presence of vacancies strongly influences bulk diffusion processes in these materials. Limiting the density of constitutional and thermal vacancies by alloying may produce materials with enhanced creep properties. The energy of intrinsic and substitutional point defects in L1₀ TiAl is calculated within a first principles, local density functional theory framework. Relaxed structures and energies for vacancies, antisites and solid solutions are calculated using a plane-wave-pseudopotential method. Calculated defect energies are used within a canonical ensemble formalism to estimate the point defect densities as a function of temperature and composition. The density of vacancies is found to be sensitive to the underlying stoichiometry of TiAl. The dependence of the vacancy concentration for solid solutions of Si, Cr, Nb, Mo, Ta and W is also predicted.     

The Influence of H,W, H/E,H 3/E 2, Structure and Chemical Composition on the Resistance of Ti–B–(N), Mo–B–(N), Cr–B–(N), and Zr–B–(N) Coatings to Cyclic Impact Loading

Protection of Metals and Physical Chemistry of Surfaces - Coatings based on transition metal borides (Ti, Mo, Cr, Zr) were obtained by magnetron sputtering of ceramic targets in Ar and Ar–15%...     

Heat Resistance,High-Temperature Tribological Characteristics,and Electrochemical Behavior of Arc-PVD Nanostructural Multilayer Ti–Al–Si–N Coatings

The present paper has aimed at studying heat resistance, electrochemical behavior, and tribological characteristics at high temperatures of superhard (~48 ± 2 GPa), multilayered with a modulation period of 17–18 nm, and nanostructured (nc)AlN-(am)Si₃N₄/(nc)TiN coatings obtained with an ion-plasma vacuum arc. The heat resistance of the coatings studied in the temperature range of up to 800°C inclusive was mainly determined by the oxidation of their surface layers without the substrate intrusion. Having a high coefficient of friction from 0.6 at 20°C to 0.8–0.85 at elevated temperatures, the coatings are characterized by virtually no wear, which was confirmed by profilometry measurements of friction zones. The obtained results concerning electrochemical behavior indicate that the Ti–Al–Si–N coatings are highly efficient in the protection of a cutting tool from corrosion in both acidic and alkaline media.     

Mechanical and Magnetic Properties of New(Fe,Co,Ni)–B–Si–Ta Bulk Glassy Alloys

The alloying effects of the like-atom substitution of Ni and Co for Fe on the various properties of Fe_(70)B_(16.7)Si_(8.3)Ta_5 metallic glass are investigated in this present work. New Fe-based bulk glassy alloys, namely Fe_(60–x)Co_xNi_(10)B_(16.7)Si_(8.3)Ta_5(at.%;x = 10, 20 and 30) with critical diameters up to 1.5 mm, were made by means of copper mold casting.A new glass-forming ability indicator, viz., the enthalpy of supercooled liquid, has been introduced for assessment of the glass-forming abilities(GFAs) of these Fe-based multi-component alloys. Nano-indentation results indicate that the calculated elastic modulus and hardness of the bulk glassy alloys are lower than those of the Fe_(70)B_(16.7)Si_(8.3)Ta_5 alloy.Among these bulk glassy alloys, Fe_(70)B_(16.7)Si_(8.3)Ta_5 exhibits the large elastic modulus and hardness with values of 178 ± 1GPa and 12.9 ± 0.1 GPa, respectively. All the bulk glassy alloys exhibit good soft magnetic properties with high saturation magnetization Bs~0.75–1.04 T but low coercive force Hc~0.2–5.2 A/m.     

Effect of Precipitate State on Mechanical Properties,Corrosion Behavior,and Microstructures of Al–Zn–Mg–Cu Alloy

The mechanical properties, corrosion behavior and microstructures of the Al–Zn–Mg–Cu alloy under various ageing treatments were investigated comparatively. The results show that the tensile strength and corrosion resistance are strongly affected by the precipitate state. Massive fine intragranular precipitates contribute to high strength. Discontinuous coarse grain boundary precipitates containing high Cu content, as well as the narrow precipitate free zone, result in low corrosion susceptibility. After the non-isothermal ageing (NIA) treatment, the tensile strength of 577 MPa is equivalent to that of 579 MPa for the T6 temper. Meanwhile, the stress corrosion susceptibility r_tf and the maximum corrosion depth are 97.8% and 23.5 μm, which are comparable to those of 92.8% and 26.7 μm for the T73 temper. Moreover, the total ageing time of the NIA treatment is only 7.25 h, which is much less than that of 48.67 h for the retrogression and re-ageing condition.     

Zr–(Cu,Ag)–Al bulk metallic glasses

In this paper, we report the formation of a series Zr–(Cu,Ag)–Al bulk metallic glasses (BMGs) with diameters at least 20 mm and demonstrate the formation of about 25 g amorphous metallic ingots in a wide Zr–(Cu,Ag)–Al composition range using a conventional arc-melting machine. The origin of high glass-forming ability (GFA) of the Zr–(Cu,Ag)–Al alloy system has been investigated from the structural, thermodynamic and kinetic points of view. The high GFA of the Zr–(Cu,Ag)–Al system is attributed to denser local atomic packing and the smaller difference in Gibbs free energy between amorphous and crystalline phases. The thermal, mechanical and corrosion properties, as well as elastic constants for the newly developed Zr–(Cu,Ag)–Al BMGs, are also presented. These newly developed Ni-free Zr–(Cu,Ag)–Al BMGs exhibit excellent combined properties: strong GFA, high strength, high compressive plasticity, cheap and non-toxic raw materials and biocompatible property, as compared with other BMGs, leading to their potential industrial applications.     

Engineering Research Needs, 1965–1985

This study by the Engineering Research Committee of the Engineers Joint Council examines the future responsibilities of the engineering profession for the creative application of science and technology to meet the changing needs and wants of our society. It appraises a number of engineering research opportunities for which existing institutions and programs appear inadequate.     

Correlations among stress corrosion cracking,grain-boundary microchemistry,and Zn content in high Zn-containing Al–Zn–Mg–Cu alloys

The correlations among the corrosion behaviour, grain-boundary microchemistry, and Zn content in Al–Zn–Mg–Cu alloys were studied using stress corrosion cracking (SCC) and intergranular corrosion (IGC) tests, combined with scanning electron microscopy (SEM) and high-angle angular dark field scanning transmission electron microscopy (HAADF-STEM) microstructural examinations. The results showed that the tensile strength enhancement of high Zn-containing Al–Zn–Mg–Cu alloys was mainly attributed to the high density nano-scale matrix precipitates. The SCC plateau velocity for the alloy with 11.0 wt.% Zn was about an order of magnitude greater than that of the alloy with 7.9 wt.% Zn, which was mainly associated with Zn enrichment in grain boundary precipitates and wide precipitates-free zones. The SCC mechanisms of different Zn-containing alloys were discussed based on fracture features, grain-boundary microchemistry, and electrochemical properties.     

Microstructure,Microsegregation, and Mechanical Properties of Directional Solidified Mg–3.0Nd–1.5Gd Alloy

The microstructure, microsegregation, and mechanical properties of directional solidified Mg–3.0Nd–1.5Gd ternary alloys were experimentally studied. Experimental results showed that the solidification microstructure was composed of dendrite primary a(Mg) phase and interdendritic a(Mg) ? Mg12(Nd, Gd) eutectic and Mg5 Gd phase. The primary dendrite arm spacing k1 and secondary dendrite arm spacing k2 were found to be depended on the cooling rate R in the form k1= 8.0415 9 10-6R-0.279 and k2= 6.8883 9 10-6R-0.205, respectively, under the constant temperature gradient of40 K/mm and in the region of cooling rates from 0.4 to 4 K/s. The concentration profiles of Nd and Gd elements calculated by Scheil model were found to be deviated from the ones measured by EPMA to varying degrees, due to ignorance of the back diffusion of the solutes Nd and Gd within a(Mg) matrix. And microsegregation of Gd depended more on the growth rate, compared with Nd microsegregation. The directionally solidified experimental alloy exhibited higher strength than the non-directionally solidified alloy, and the tensile strength of the directionally solidified experimental alloy was improved,while the corresponding elongation decreased with the increase of growth rate.     

Alloyed W–(Co,Ni,Fe)–C phases for reaction sintering of hardmetals

It has been shown that W–Co–C phases could dissolve a substantial amount of metals such as V, Cr and Ta, which are known to positively influence the microstructure of hardmetals with respect to uniform grain size distribution and fine grain size. This offers a tool to circumvent the conventional doping of hardmetals with individual carbides. In the present study we used double- and triple-alloyed κ-W₉Co₃C₄ (i.e. κ-(W,V,Cr)₉Co₃C₄ and κ-(W,V,Cr,Ta)₉Co₃C₄) and applied a variety of sintering experiments to obtain WC–Co, WC–(Ti,Ta,Nb)C–Co and WC–(Ti,Ta,Nb)(C,N)–Co hardmetals. We also prepared κ-W₉Fe₃C₄, alloyed κ-W₉Ni₃C₄, and κ-W₉(Fe/Ni)₃C₄, and used the latter for sintering.     

Determination of the interface energies of spherical,cuboidal and octahedral face-centered cubic precipitates in Cu–Co,Cu–Co–Fe and Cu–Fe alloys

The coarsening theory of a spherical particle in a ternary alloy developed by Kuehmann and Voorhees (KV) has been generalized to any centro-symmetric particle. A classical thermodynamic analysis reveals that the generalized KV theory enables us to estimate the interface energy of a particle with a fixed shape, even if the shape of the particle is not controlled by minimization of the interface energy. Data on the coarsening of spherical, {0 0 1}-faceted cuboidal and {1 1 1}-faceted octahedral precipitates in a Cu–Co alloy, a Cu–Fe alloy, and three Cu–Co–Fe alloys with different Co and Fe contents during aging at 873–973 K have been collected by transmission electron microscopy and electrical resistivity. By applying the generalized KV theory to the experimental data, the energies of sphere, {0 0 1} and {1 1 1} interfaces have been determined. Their energies increase with increasing the Fe composition in the alloys.     

Comparison of high temperature shape memory behaviour for ZrCu-based,Ti–Ni–Zr and Ti–Ni–Hf alloys

New ZrCu-based high temperature shape memory alloys with M_s close to 500 K are under development. The shape memory behaviour of this material is compared to those of Ti–Ni–Zr and Ti–Ni–Hf alloys. The optimal compositions show a shape recovery of not less than 3% at temperatures above 470 K.