Comparative investigation of oxidation resistance and thermal stability of nanostructured Ti–B–N and Ti–Si–B–N coatings

Nanostructured Ti–B–N and Ti–Si–B–N coatings were deposited on silicon substrate by ion implantation assisted magnetron sputtering technique. To evaluate the oxidation resistance and thermal stability the coatings were annealed on air and in vacuum at 700–900°C. As-deposited and thermal-treated coatings were investigated by transmission electron microscope, selected area electron and x-ray diffraction, atomic force microscopy, Raman and glow discharge optical emission spectroscopy. Nanoindentaion tests were also performed. Obtained results show that Si alloying significantly improves the thermal stability of Ti–B–N coatings and increases their oxidation resistance up to 900°C. It was shown that formation of protective amorphous SiO₂ top-layer on the coating surface plays important role in the increasing of the oxidation resistance.     

Effect of minor Zr and Sc on microstructures and mechanical properties of Al–Mg–Si–Cu–Cr–V alloys

The effects of minor contents of Zr and Sc on the microstructures and mechanical properties of Al–Mg–Si–Cu–Cr–V alloy were studied. The results show that the effects of minor Zr and Sc on the as-cast grain refinement in the ingots, the improvement in the strength of the as-extruded alloys and the restriction of high angle grain boundaries in the aged alloys can be sorted as Al₃Sc>Al₃(Zr,Sc)>Al₃Zr. None of them could stop the nucleation of recrystallization, but Al₃(Zr,Sc) phase is a more effective inhibitor of dislocation movement compared to Al₃Sc in the aged alloys. Compared with the mechanical properties of the aged alloy added only 0.15% Sc, the joint addition of Zr and Sc to the alloy leads to a very slight decrease in strength with even no cost of ductility. Taking both the production cost and the little bad influence on mechanical properties into consideration, an optimal content of Zr and Sc in the Al–Mg–Si–Cu–Cr–V alloy to substitute 0.15% Sc is 0.13% Zr+0.03% Sc.     

Microstrucure and strengthening of Al–Li–Cu–Mg alloys and MMCs: I. Analysis and Modelling of Microstructural changes

A complete and detailed analysis of the microstructural development during ageing in an 8090 (Al–2.3Li–1.2Cu–1Mg–0.1Zr) alloy, an 8090/20 wt% SiC_p MMC, an Al–1.5Li–Cu–Mg MMC and an Al–Cu–Mg MMC (all with similar Cu and Mg contents) has been performed. Volume fractions of all precipitates relevant for precipitation strengthening of the alloys (δ′ phase, S′ phase and GPB zones) have been determined using a recently derived method based on differential scanning calorimetry (DSC). The volume fractions have subsequently been successfully fitted using a novel model for transformation kinetics. The sizes of these precipitates have been analysed using newly derived expressions consistent with the latter model. As a result of dislocation generation around misfitting SiC particles the volume fractions of both GPB zones and S′ phase depend strongly on the presence of these particles. Also the amount of Li present in the alloys influences the volume fractions of the phases significantly. The sizes of S′ are similar for the four alloys.     

Influence of Gd and B on solidification behaviour and weldability of Ni–Cr–Mo alloy

Abstract

The influence of Gd and B on the solidification behaviour and weldability of Ni–Cr–Mo alloy UNS N06455 has been investigated by Varestraint testing, differential thermal analysis and microstructural characterisation. These alloys are currently being developed as structural materials for nuclear criticality control in applications requiring transportation and disposition of spent nuclear fuel owned by the US Department of Energy. The Gd containing alloys were observed to solidify in a manner similar to a binary eutectic system. Solidification initiated with a primary L→y reaction and terminated at ~1258°C with a eutectic type L→y+Ni₅Gd reaction. The solidification cracking susceptibility of the Gd containing alloys reached a maximum at ~1 wt-%Gd and decreased with both higher and lower Gd additions. Low cracking susceptibility at Gd concentrations below ~1 wt-% was attributed to a relatively small amount of terminal liquid that existed over much of the crack susceptible solid+liquid zone. Low cracking susceptibility at Gd concentrations above ~1 wt-% was attributed to a reduced solidification temperature range and backfilling of solidification cracks. The addition of B above the 230 ppm level leads to the formation of an additional eutectic type reaction at ~1200°C and the secondary phase within the eutectic type constituent was tentatively identified as Mo₃B₂. The B containing alloys exhibited a three step solidification reaction sequence consisting of primary L→y solidification, followed by the eutectic type L→y+Ni₅Gd reaction, followed by the terminal eutectic type L→y+Mo₃B₂ reaction. Boron additions had a strong, deleterious influence on solidification cracking susceptibility. The high cracking susceptibility was attributed to extension of the crack susceptible solid+liquid zone induced by the additional eutectic type L→y+Mo₃B₂ reaction and extensive wetting of the grain boundaries by the solute rich liquid. Simple heat flow equations were combined with solidification theory to develop a relation between the fraction liquid f _L and distance x within the solid+liquid zone. Information on the phenomenology of crack formation in the Varestraint test were coupled with the calculated f _L–x curves and were shown to provide useful insight into composition–solidification–weldability relations.     

Structure and properties of cast and splat-quenched high-entropy Al–Cu–Fe–Ni–Si alloys

The effect of the composition and cooling rate of the melt on the microhardness, phase composition, and fine-structure parameters of as-cast and splat-quenched (SQ) high-entropy (HE) Al–Cu–Fe–Ni–Si alloys was studied. The quenching was performed by conventional splat-cooling technique. The cooling rate was estimated to be ~10⁶ K/s. Components of the studied HE alloys were selected taking into account both criteria for designing and estimating their phase composition, which are available in the literature and based on the calculations of the entropy and enthalpy of mixing, and the difference between atomic radii of components as well. According to X-ray diffraction data, the majority of studied Al–Cu–Fe–Ni–Si compositions are two-phase HE alloys, the structure of which consists of disordered solid solutions with bcc and fcc structures. At the same time, the Al_0.5CuFeNi alloy is single-phase in terms of X-ray diffraction and has an fcc structure. The studied alloys in the as-cast state have a dendritic structure, whereas, after splat quenching, the uniform small-grained structure is formed. It was found that, as the volume fraction of bcc solid solution in the studied HE alloys increases, the microhardness increases; the as-cast HE Al–Cu–Fe–Ni–Si alloys are characterized by higher microhardness compared to that of splat-quenched alloys. This is likely due to the more equilibrium multiphase state of as-cast alloys.     

Effect of halide anions and temperature on initiation of pitting in Cr–Mn–N and Cr–Ni steels

Abstract

The pitting corrosion of Cr₁₈Mn₁₂N and Cr₁₈Ni₉ steels in halide solutions (F^?, Cl^?, Br^? and I^?) has been investigated. The study involved cyclic potentiodynamic polarisation tests with subsequent examination of the specimens by both optical and scanning electron microscopy. Values of the critical concentrations of halide ions, [X^?]_cr, beyond which pitting occurs, as well as breakdown potentials for pitting in chloride solution, have been established. In addition, the effect of the temperature over the range of 5–80°C on the critical chloride ion concentration [Cl^?]_cr has been investigated and it has been found that temperature has a negligible effect beyond 40°C.     

Microstructures and mechanical properties of homogenization and isothermal aging Mg–Gd–Er–Zn–Zr alloy

The effects of homogenization and isothermal aging treatment on the mechanical properties of Mg–12Gd–2Er–1Zn–0.6Zr(wt%) alloy were investigated. The precipitated long-period stacking order(LPSO) structure and the aging precipitation sequence of the conditioned alloys were observed and analyzed, respectively. The results indicate that the 14H-LPSO structure occurs after the homogenization treatment and the b0 phase forms after the isothermal aging process. These two independent processes could be controlled by the precipitation temperature range. The significant increase in the elongation of the as-cast alloy after homogenization treatment is attributed to the disappearance of the coarse primary Mg5(Gd, Er, Zn) phase and the presence of the 14H-LPSO structure. The precipitation sequence of the investigated alloy is a-Mg(SSS)/b00(D019)/b0(cbco)/b.Furthermore, the yield tensile strength(YTS) and ultimate tensile strength(UTS) values of the isothermal aging alloy have a great improvement, which could be attributed to the high density of the precipitated b0 phase.     

Preparation and characterisation of melt-spun Al–Cu–Fe quasicrystals

Three Al–Cu–Fe alloys with compositions of Al_60–65Cu_20–27.5Fe_12.5–15 were prepared by conventional casting and further processed by melt-spinning. The structures formed were examined to get an insight into the interrelated effects of synthesis, processing and microstructure of Al–Cu–Fe alloys. The study aimed at answering the questions such as whether the production of single-phase quasicrystalline ribbons is possible by the melt-spinning process and what is the role of the degree of undercooling in the development of microstructure in melt-spun ribbons.The icosahedral ψ-Al₆₅Cu₂₀Fe₁₅ phase forms by a peritectic reaction between the primary β-AlFe phase and the liquid, as the temperature decreases. At the later stages of cooling, the monoclinic λ-Al₁₃Fe₄ phase and the tetragonal θ-Al₂Cu phase are formed in the cast alloys, as a result of peritectic reactions. In the rapidly solidified alloys, the formation of the tetragonal θ-Al₂Cu phase and, in the case of alloy Al₆₀Cu₂₅Fe₁₅, the monoclinic λ-Al₁₃Fe₄ phase is avoided, apparently due to high degree of undercooling. Thus, the production of single-phase quasicrystalline ribbons is not possible by the melt-spinning process, at least by using the cooling rate of 5–7×10⁴ °C/s. In addition to phase selection, the degree on undercooling influences, for example, the composition of the ψ-Al₆₅Cu₂₀Fe₁₅ phase and the grain morphology in melt-spun ribbons.     

Interrelation of wettability–microstructure–tensile strength of lead-free Sn–Ag and Sn–Bi solder alloys

A comparative investigation on the wettability and tensile strength of a Sn–2Ag, a Sn–40Bi and the traditional eutectic Sn–Pb solder alloys was carried out. The wettability is represented by thickness of covered layer (TCL) and spread area (SA) while the mechanical behaviour by the ultimate tensile strength (UTS). It is shown that the TCL of studied alloys decreased with the increase in the dipping temperature. It is also shown that TCL and SA have opposite behaviour with respect to the cooling rate. The Sn–Bi solder alloy has lower SA when compared with those of the Sn–Ag solder when similar cooling rates are considered. The Sn–Bi solder exhibits the best UTS/SA combination for dendritic spacings between 25 and 27?µm, associated with cooling rates ～2°C?s^?1, 2× lower than those of the Sn–Ag alloy. Besides, the Sn–Bi alloy has shown SA >70～80% associated with higher UTS (～80?MPa) as compared with the other alloys examined.     

Microstructure and properties of aging Cu–Cr–Zr alloy

The crystallography and morphology of precipitate particles in a Cu matrix were studied using an aged Cu–Cr–Zr alloy by transmission electron microscopy(TEM) and high-resolution transmission electron microscopy(HRTEM). The tensile strength and electrical conductivity of this alloy after various aging processes were tested. The results show that two kinds of crystallographic structure associated with chromium-rich phases, fcc and bcc structure, exist in the peak-aging of the alloy. The orientation relationship between bcc Cr precipitate and the matrix exhibits Nishiyama–Wasserman orientation relationship. Two kinds of Zr-rich phases(Cu4Zr and Cu5Zr)can be identified and the habit plane is parallel to {111}Cu plane during the aging. The increase in strength is ascribed to the precipitation of Cr- and Zr-rich phase.     

Influence of heat treatment on the structure and magnetic properties of amorphous Co–Ni–Fe–Cr–Si–B alloy and its thermal stability

The causes of changes in the magnetic properties of an amorphous Co–Ni–Fe–Cr–Si–B alloy obtained by melt spinning in the form of a thin ribbon subjected to heat treatment and subsequent action of temperatures corresponding to various conditions of its exploitation have been analyzed. We have established the regimes of heat treatment that provide for the highest values of the maximum magnetic permeability of the alloy and the shielding factor of a magnetic shield made from the alloy. We have analyzed changes in the magnetic properties, shielding properties, and total magnetization distribution in an alloy ribbon at a temperature well below the crystallization temperature. We have found the temperature ranges that determine the practical application of this alloy.     

The characterization of structure,thermal stability and magnetic properties of Fe–Co–B–Si–Nb bulk amorphous and nanocrystalline alloys

Recently bulk amorphous alloys have attracted great attention due to their excellent magnetic properties. The glass-forming ability of bulk amorphous alloys depends on the temperature difference (ΔT_x) between glass transition temperature (T_g) and crystallization temperature (T_x). The increase of ΔT_x causes a decrease of the critical cooling rate (V_c) and growth of the maximum casting thickness of bulk amorphous alloys. The aim of the present paper is to characterize the structure, the thermal stability and magnetic properties of Fe₃₆Co₃₆B₁₉Si₅Nb₄ bulk amorphous alloys using XRD, Mössbauer spectroscopy, DSC and VSM methods. Additionally the magnetic permeability μ_i (at force H ≈ 0.5 A/m and frequency f ≈ 1 kHz) and the intensity of disaccommodation of magnetic permeability Δμ/μ(t₁) (Δμ = μ(t₁ = 30 s) ? μ(t₂ = 1800 s)), have been measured, where μ is the initial magnetic permeability measured at time t after demagnetisation, the Curie temperature T_C and coercive force H_c of rods are also determined with the use of a magnetic balance and coercivemeter, respectively.Fe–Co–B–Si–Nb bulk amorphous alloys were produced by pressure die casting with the maximum diameters of 1 mm, 2 mm and 3 mm.The glass transition temperature (T_g) of studied amorphous alloys increases from 807 K for a rod with a diameter of 1 mm to 811 K concerning a sample with a diameter of 3 mm. The crystallization temperature (T_x) has the value of 838 K and 839 K for rods with the diameters of 1 mm and 3 mm, respectively. The supercooled liquid region (ΔT_x = T_x ? T_g) has the value of about 30 K. These values are presumed to be the origin for the achievement of a good glass-forming ability of the Fe–Co–B–Si–Nb bulk amorphous alloy. The investigated amorphous alloys in the form of rods have good soft magnetic properties (e.g. M_s = 1.18–1.24 T). The changes of crystallization temperatures and magnetic properties as a function of the diameter of the rods (time of solidification) have been stated.     

Environmental Resistance of Mo–Si–B Alloys and Coatings

For high temperature application beyond the range of Ni-base superalloys, multiphase Mo–Si–B alloys with compositions, that yield the ternary intermetallic Mo₅SiB₂ (T₂) phase as a key microstructure constituent together with the Mo and Mo₃Si phases, offer an attractive balance of high melting temperature, oxidation resistance and mechanical properties. The investigation of reaction kinetics involving the T₂ phase enables the analysis of oxidation in terms of diffusion pathways and the design of effective coatings. From this basis kinetic biasing is used together with pack cementation to develop multilayered coatings and in situ diffusion barriers with self-healing characteristics for enhanced oxidation resistance. While a combustion environment contains water vapor that can accelerate attack of silica based coatings, the current pack cementation coatings provide oxidation resistance in water vapor up to at least 1500 °C. An exposure to hot ionized gas species generated in an arc jet confirms the robust coating performance in extreme environments.     

Preparation and Characterization of Amorphous W–B–C Alloy and Solid Solutions of C in Tungsten Borides

Mixtures of W and B_(13) C_2 powders were mechanically milled and subsequently annealed at 900–1200 °C. It is found that amorphous W–B–C alloy formed as the mixtures were milled for 20–80 h. After annealing the 80 h-milled mixtures at 900–950 °C, solid solutions of C and/or B in tungsten [W(B, C)], C in tungsten boride [W_2 B(C) or WB(C)]formed by the crystallization of amorphous W–B–C. The formation temperature of W_2 B(C) and WB(C) is lower than that of W_2 B and WB reported previously. As the 80 h-milled mixtures were annealed at 1200 °C, W reacted with amorphous W–B–C completely to form WB and W_2B_5 or W_2B_5 instead of the solid solutions of C in tungsten borides, which is determined by the mole ratio of W to B_(13) C_2. The formation mechanisms of the W_2 B(C) and WB(C) solid solutions as well as phase transition rules of the mixtures at annealing temperature and mole ratio were also investigated using first-principle calculation.     

Effects of extrusion and heat treatments on microstructure and mechanical properties of Mg–8Zn–1Al–0.5Cu–0.5Mn alloy

The effects of extrusion and heat treatments on the microstructure and mechanical properties of Mg–8Zn–1Al–0.5Cu– 0.5Mn magnesium alloy were investigated. Bimodal microstructure is formed in this alloy when it is extruded at 230 and 260 °C, and complete DRX occurs at the extruding temperature of 290 °C. The basal texture of as-extruded alloys is reduced gradually with increasing extrusion temperature due to the larger volume fraction of recrystallized structure at higher temperatures. For the alloy extruded at 290 °C, four different heat treatments routes were investigated. After solution + aging treatments, the grains sizes become larger. Finer and far more densely dispersed precipitates are found in the alloy with solution + double-aging treatments compared with alloy with solution + single-aging treatment. Tensile properties are enhanced remarkably by solution + double-aging treatment with the yield strength, tensile strength and elongation being 298 MPa, 348 MPa and 18%, respectively. This is attributed to the combined effects of fine dynamically recrystallized grains and the uniformly distributed finer precipitates.     

Microstructure and mechanical performance of brazed joints of Cf/SiC composite and Ti alloy using Ag–Cu–Ti–W

Abstract

C_f/SiC composite was brazed to Ti alloy using interlayer of Ag–Cu–Ti–W mixed powder. The effects of W content and brazing parameters on the microstructure and properties of the brazed joints were investigated. The results show that W grains mainly distribute in Ag phase in the brazing layer and provide the effects of reinforcement and lowering residual thermal stress on the joint. The room temperature and 500°C shear strengths of the joints performed at 500°C for 30 min with Ag–Cu–Ti–50W (vol.-%) are remarkably higher than the optimal strengths of the joints brazed with Ag–Cu–Ti.     

Microstructure and tensile properties of orthorhombic Ti–Al–Nb–Ta alloys

Microstructure and tensile properties of orthorhombic Ti–Al–Nb–Ta alloys have been studied. In order to optimize ductility and strength of the orthorhombic alloys with the nominal compositions of Ti–22Al–23Nb–3Ta and Ti–22Al–20Nb–7Ta, various thermomechanical processing steps were implemented as part of the processing route. With a special heat treatment before rolling to obtain a fine and homogeneous rolled microstructure, the rolled microstructure resulted in a good combination of high tensile yield strength and good ductility of the alloys through available solution and age treatments. The duplex microstructure with equiaxed α₂/O particles and fine O phase laths in a B2 matrix, deforming in α₂+B2+O phase field and treating in O+B2 phase field, possesses the highest tensile properties. The R.T. yield strength and ductility of the Ti–22Al–20Nb–7Ta alloy are 1200 MPa, and 9.8% respectively. The yield strength and ductility values of 970 MPa and 14% were also maintained at elevated temperature (650°C).     

On solidification shrinkage of copper–lead and copper–tin–lead alloys

Abstract

Solidification shrinkage is an important concept in achieving sound castings. In the present work solidification shrinkage was studied in copper–lead and copper–lead–tin alloys. A series of solidification experiments was performed under different cooling rates using a dilatometer which was developed for melting and solidification purposes. The volume change was measured during primary solidification and the monotectic reaction. In order to explain the volume-changing results, the sample macrostructures were studied to evaluate gas and shrinkage cavities which were formed during the solidification. Furthermore, the volume fraction of the primary phase during solidification was evaluated in the samples that were quenched from different temperatures below the liquidus temperature. A shrinkage model was used to explain the volume changes during solidification.     

Motion of dislocations and interfaces during deformation of martensitic Cu–Al–Ni crystals

Investigations of the ultrasonic strain amplitude-dependent internal friction (ADIF) and of the influence of ultrasonic vibrations on the macroplastic strain (the acoustoplastic effect) have been performed in situ during deformation of quenched Cu–Al–Ni single crystals in the β′₁ martensitic phase. The effect of the macroscopic plastic strain rate on the ADIF and acoustoplastic effect as well as the kinetics of the acoustoplastic effect has been studied. The results of in situ ADIF measurements are compared with data on the ADIF temperature dependence. Observed regularities are attributed to differences in the mechanisms of the macroplastic deformation of the martensitic phase, related to the motion of intervariant interfaces, and of the reversible anelastic strain, which, at ultrasonic frequencies and moderate strain amplitudes, is largely due to the oscillatory motion of the partial dislocations. The conclusion has been drawn that the dynamics of partial dislocations at temperatures of 210–300 K is to a great extent determined by their interaction with atmospheres of mobile pinners with saturated density. Simultaneous measurements of the ADIF and acoustoplastic effect allows the conclusion that, for high oscillatory strain amplitudes, the breakthrough of partial dislocations beyond the mobile atmospheres of pinners initiates the step-like accumulation of the macroplastic strain due to the motion of intervariant boundaries.