Characterization and control of selective corrosion of α,β′-brass by acoustic emission

Acoustic emission (AE) associated with electrochemical measurements (electrochemical impedance spectroscopy and polarization curves) are used to study the selective corrosion of α,β′-brass in an ammonia buffer solution. AE reveals, in this work, three different populations of events during the corrosion of this alloy. The corrosion process was found to proceed via oxygen reduction following a diffusion-controlled mechanism and selective dissolution of α,β′-brass was controlled by the zinc atoms diffusion through oxide film. The diffusion coefficient obtained for zinc in α,β′-brass following Cottrell law is of the order of 9.28×10⁻¹² cm²/s. An equivalent circuit modelling the reactions taking place at the electrode/electrolyte interface was suggested. The analysis by X-ray diffraction of residual stresses, before and after corrosion, showed that the dezincification of metal produces two types of residual stresses: macro and microstresses. Their evolution correlates perfectly with the measured acoustic activity. These stresses are then the sources of AE. This shows the important potential of AE in the detection and the control of selective corrosion phenomena.     

Performance of thermal barrier coatings on γ‐TiAl

The current development of new generation gamma titanium aluminides is expected to result in alloy chemistries and microstructures capable of operating at temperatures in excess of 850 °C. Under these conditions, environmental and thermal protection becomes a concern since oxidation might eventually limit the maximum service temperatures achievable. Therefore protective coatings are necessary to exploit the full potential of gamma titanium aluminides at moderately elevated temperatures; however, as yet no coating system tested has proven sufficient performance for long‐term use in automotive and aerospace applications. Thermal barrier coatings (TBCs), typically applied to nickel‐based alloys, offer the potential to increase the service temperature of components by lowering the metal surface temperature in combination with cooling systems. The paper is focussed on development of thermal barrier coatings for gamma titanium aluminides. Different coatings were used for oxidation protection and bond coat application. Substrate specimens were either pre‐oxidized or coated with PVD‐Al₂O₃, TiAlCrYN, or diffusion aluminides. Yttria‐stabilized zirconia TBCs were deposited applying electron‐beam physical vapour deposition. Cyclic and quasi‐isothermal oxidation tests were carried out at 900 °C in air. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy. Zirconia top coats offer a promising thermal protection concept to be applied on γ‐TiAl components. However, high oxidation resistance has to be supplied by protective coatings. Diffusion layers of the TiAl₃ aluminide provided excellent environmental protection because of the formation of a continuous alumina scale. No spallation of the thermal barrier coatings was observed on aluminized specimens during 1000 1‐h cycles and 3000 h of cyclic and isothermal oxidation testing, respectively.     

Crystallographic and morphological relationships between β phase and the Widmanstätten and allotriomorphic α phase at special β grain boundaries in an α/β titanium alloy

In the present study, the relationship between the crystallographic orientations and growth directions of grain boundary-allotriomorphic-α (GB α) and secondary Widmanstätten α laths growing from the GB α at grain boundaries separating β grains with specific misorientations has been examined. These relationships have been determined using a variety of characterization techniques, including scanning electron microscopy, orientation imaging microscopy, transmission electron microscopy (TEM) and a dual-beam focused ion beam instrument to provide site-selected TEM foils. Two very interesting cases, one in which the two adjacent β grains are rotated mutually by approximately 10.5° about a common 1 1 0 direction and the other in which the two β grains are in a twin relationship, i.e. a 60° rotation about a common 1 1 1 direction, have been studied. It was discovered that the α laths growing into two adjacent β grains from the common grain boundary may have the same orientation in both grains, while they may have either large (88.8°) or small (28.8°) angular differences in growth directions in the two adjacent β grains, depending on the relative misorientation of the β grains. The growth directions of the α laths growing from such boundaries are explained on the basis of the Burgers orientation relationship between the Widmanstätten α and the β phases and the interfacial structure proposed previously by various workers.     

Improving the oxidation resistance of γ‐titanium aluminides by halogen treatment

Intermetallic alloys based on TiAl are candidates for several structural high temperature applications but their oxidation resistance is limited to temperatures below 800 °C. In this paper the results of high temperature oxidation and creep tests will be presented and discussed. The treatment with halogens improves the oxidation resistance of these alloys up to 1050 °C. A thin protective Al₂O₃‐layer is formed after treatment with halogens instead of the mixed TiO₂/Al₂O₃/TiN scale typically grown on these alloys. This alumina layer protects the component under isothermal and thermocyclic conditions. The protective effect is stable up to at least 8760 h. Creep tests of halogen treated materials at high temperatures showed no effect on the creep behaviour. Automotive turbocharger rotors were exposed at 1050 °C in air with and without fluorine‐treatment for demonstration of real parts.     

Oxide phase development upon high temperature oxidation of γ‐NiCrAl alloys

The amount of each oxide phase developed upon thermal oxidation of a γ‐Ni‐27Cr‐9Al (at.%) alloy at 1353 K and 1443 K and a partial oxygen pressure of 20 kPa is determined with in‐situ high temperature X‐ray Diffractometry (XRD). The XRD results are compared with microstructural observations from Scanning Electron Microscope (SEM) backscattered electron images, and model calculations using a coupled thermodynamic‐kinetic oxidation model. It is shown that for short oxidation times, the oxide scale consists of an outer layer of NiO on top of an intermediate layer of Cr₂O₃ and an inner zone of isolated α‐Al₂O₃ precipitates in the alloy. The amounts of Cr₂O₃ and NiO in the oxide scale attain their maximum values when successively continuous Cr₂O₃ and α‐Al₂O₃ layers are formed. Then a transition from very fast to slow parabolic growth kinetics occurs. During the slow parabolic growth, the total amount of non‐protective oxide phases (i.e. all oxide phases excluding α‐Al₂O₃) in the oxide scale maintain at an approximately constant value. The formation of NiCr₂O₄ and subsequently NiAl₂O₄ happens as a result of solid‐state reactions between the oxide phases within the oxide scale.     

Scale growth process at 1473 K on unmodified and yttrium‐ or chromium‐implanted β‐NiAl

Early oxidation of unmodified and yttrium‐implanted or chromium‐implanted β‐NiAl intermetallic compound at 1473 K was studied using a combination of two‐stage‐oxidation exposure with ¹⁸O₂ as a tracer, SIMS elemental distribution analysis (depth profiling and imaging modes) and photoluminescence spectroscopy analysis of the scale phase composition. It was found that phase transformation of transient aluminium oxides, represented by θ‐ Al₂O₃ into stable and protective α‐Al₂O₃ occurs locally and is affected by implanted additions: Yttrium retarded while chromium appeared to accelerate it. Typical patch‐ and/or web‐like scale morphology of the growing scales was observed.     

Coarsening of γ (Ni–Al solid solution) precipitates in a γ′ (Ni3Al) matrix; a striking contrast in behavior from normal γ/γ′ alloys

Coarsening of γ precipitates in a γ′ (Ni₃Al) matrix depends strongly on volume fraction, in dramatic contrast with coarsening of γ′ precipitates. Coalescence of γ precipitates is easy, unlike the resistance to coalescence of γ′ precipitates. We regard this as indirect proof that anti-phase relationships among γ′ precipitates inhibit coalescence.     

Microstructure and mechanical properties of a directionally solidified and aged intermetallic Ni–Al–Cr–Ti alloy with β-γ′-γ-α structure

Microstructure and mechanical properties were investigated in a directionally solidified (DS) Ni–21.7Al–7.5Cr–6.5Ti (at.%) alloy. The dendrites of the as-grown alloy were composed of β(B2)-matrix (NiAl), coarse γ′(L1₂)-particles (Ni₃Al), fine γ′-needles and spherical α(A2)-precipitates (Cr-based solid solution). The majority of fine γ′-precipitates was found to be twinned. The interdendritic region contained γ(A1)-matrix (Ni-based solid solution) separating ordered domains of γ′-phase and fine lath-shaped α-precipitates. Ageing in the temperature range 973–1373 K decreased the volume fraction of dendrites from about 50 vol.% measured in the as-grown material to about 38 vol.% in the material aged at 1373 K for 300 h. During ageing in the temperature range 973–1273 K the γ-phase transformed to the γ′-phase in the interdendritic region. This transformation was connected with precipitation of lath-shaped α-precipitates. Ageing at higher temperatures of 1373 and 1473 K resulted in stabilisation of the γ-phase and precipitation of spherical γ′-particles in the interdendritic region. Ageing at 973 K significantly increased the microhardness, hardness and decreased room-temperature tensile ductility. Neither ageing nor finer dendritic microstructure were found to be effective in increasing the ductility of the alloy. The measured tensile ductility up to 1.1% can be attributed to the effect of extrinsic toughening mechanisms operating in the β-phase such as blunting and bridging of cracks by the α- and γ′-precipitates.     

α‐Fe layer formation during metal dusting of iron in CO‐H2‐H2O gas mixtures

The formation of an α‐Fe layer between cementite and graphite was observed and investigated during metal dusting of iron in CO‐H₂‐H₂O gas mixtures at both 600°C and 700°C. The condition to form this phenomenon is determined by the gas composition which depends on temperature. The iron layer formation was observed for CO content less than 1 % at 600°C and less than 5 % at 700°C. With increasing CO contents, no α‐Fe layer was detected at the cementite/graphite interface by optical microscopy. In this case cementite directly contacts with the coke layer. The morphologies of the coke formed in the gas mixtures with low CO contents were also analysed. Three morphologies of graphite have been identified with 1 % CO at 600°C: filamentous carbon, bulk dense graphite with columnar structure, and graphite particle clusters with many fine iron containing particles embedded inside. At 700°C with 5 % CO the coke mainly consists of graphite particle clusters with some filamentous carbon at the early stage of reaction. Coke analysis by X‐ray diffraction shows that both α‐Fe and Fe₃C are present in the coke. The mechanism of α‐Fe accumulation between cementite and graphite is discussed in this paper.     

Preparation of nanometer δ- and β-bismuth trioxide by vacuum vapor-phase oxidation

1 Introduction Bismuth trioxide is an important function material. It exits in four polymorphs[1-4], i.e. the monoclinic α-phase, the tetragonal β-phase, the body-centered cubic(bcc) γ-phase and the face-centered cubic(fcc) δ-phase. Below 730 ℃, bism     

Features of feathery γ structure in a near-γ TiAl alloy

This work characterizes the feathery-like structures produced in a Ti–46.8Al–1.7Cr–1.8Nb (at.%) alloy during rapid continuous cooling from the α domain. Their morphology and crystallography are described using different microscopy and orientation mapping techniques. These feathery-like structures are divided into many small domains, characterized by low-angle misorientations (rotated less than 15°) between the domains. The domains comprise multiple parallel γ lamellae and rare traces of α₂. These lamellae follow the Blackburn orientation relationship and have a {1 1 1}_γ habit plane. Two types of γ-feathery structures were identified according to their location and crystallography. The grain-boundary γ-feathery structures originate from lamellar structures that grow into a neighboring grain. Alternatively, the internal γ-feathery structures are located in the interior of prior α grains and show an average misorientation of 36° around one $〈100{〉}_{{\mathrm{\gamma }}_{\text{L}}}$ axis of the lamellar structure in which it is embedded. This paper describes these two γ-feathery structures in detail and discusses their development in light of the mechanisms available in the literature, particularly sympathetic nucleation.     

Relation between the magnetic transition temperature and magnetic moment for manganese nitrides MnNγ (O <γ < 1)

The magnetic properties of Mn₆N₅ and Mn₃N₂ prepared by nitridation of -Mn powder in NH₃ flow were studied by the measurement of magnetic susceptibilities in the temperature range from 100 to 958 K. It was revealed that both Mn₆N₅ and Mn₃N₂ exhibited antiferromagnetism and that the magnetic transition of Mn₆N₅ and Mn₃N₂ was accompanied by phase transitions at about 655 and 925 K respectively. The magnetic transition temperature of MnN_γ with γ ranging between 0 and 1 is discussed on the basis of both the shortest Mn—Mn distance and the magnetic moment per Mn atom.     

Control of microstructure and orientation distribution in Ni–Al-based (β/γ′) two phase alloys by thermomechanical processing

Microstructure and orientation distribution of two phase Ni–Al(β)/Ni₃Al(γ′) alloys obtained by thermomechanical processing were examined using electron back-scatter diffraction pattern technique. Cylindrical specimens were hot-compressed in the β phase region and subsequently annealed in the (β/γ′) two phase region. After the hot deformation, equiaxed β grains surrounded by high angle boundaries were homogeneously formed due to dynamic recrystallisation under adequate condition. Moreover, strong 1 1 1 fibre texture parallel to the compressive axis developed in the β phase because of the lattice rotation during hot deformation. After annealing in the two phase region, γ′ phase transformed from β phase with 1 1 1_β fibre texture satisfying the Kurdjumov–Sachs relationship and resulting in the formation of 1 1 0_γ′ fibre texture. Film-shaped γ′ phase preferentially often precipitated along the β grain boundaries and a large number of (β/γ′) boundaries were partially coherent. This thermomechanical processing was effective in controlling the crystallography of γ′ along the β grain boundaries.     

Ball-milling in vacuum of α and σ phases of near-equiatomic FeCr alloys

The structural changes induced by ball-milling of near-equiatomic σ-FeCr and α-FeCr in vacuum were followed. Besides the α-phase, an amorphous phase appears when milling the σ-phase for times longer than 20 h. An amorphous phase forms too, but at a slower rate than the latter, when milling the α-phase. The partial amorphisation of σ-FeCr and α-FeCr ball-milled in vacuum is concluded to be a phenomenon of intrinsic origin. The amorphous phase crystallizes into a bcc Cr-rich phase and a bcc Fe-rich phase during short annealing steps.     

Long-range ordering kinetics and ordering energy in Ni3Al-based γ′ alloys

Chemical long-range order kinetics were studied for the Ll₂-ordered γ′-phase domains of the quasi-binary systems Ni₇₅AL_25−xM_x (M = Fe, Mn, Cr, 0 ≤ x ≤ 25), where the γ′-phase stability (ordering energy) rapidly decreases with increasing M-component concentration x.The sample γ′ homogeneity was tested by means of transmission electron microscopy. The ‘order-order’ relaxations measured by means of in-situ resistometry indicated that an increase in x caused a systematic decrease in the activation energy, E_A, of homogeneous long-range order kinetics.Discussing a possible influence of various parameters, it was concluded that the observed decrease in E_A was predominantly due to an effect of the ordering energy on the bulk vacancy diffusion in these Ll₂-ordered compounds.     

Incremental deformation and the forgeability of γ titanium aluminide

Hot die forging has been undertaken on cube shaped workpieces of cast two-phase γ titanium aluminide. The inhomogeneous as-cast microstructure causes non-uniform deformation and low ductility. Incremental deformation using hot dies aims to break down large α₂+γ lamellae in the structure by using an accumulation of small amounts of deformation with interspersed with periods for material recovery. The effect of various forms of incremental deformation, with or without subsequent isothermal forging, on microstructure is discussed. It is shown that the use of hot-die forging to refine microstructure is limited by chilling of the workpiece and loss in ductility.     

Improving the protective properties of La‐conversion coating on α‐brass surface by the combined use of La2O3 nanoparticles incorporation and electrodeposition

The La₂O₃ nanoparticles incorporation and electrodeposition were used together to prepare the La‐conversion coatings on α‐brass surface in a basal solution containing rare earth salt. The results showed that both techniques can improve the protective properties of coatings. A ‘critical nano‐La₂O₃ content’ and a ‘critical deposition potential’ were observed, under which the conversion coatings had the highest protective properties. Increased electrodeposition time improve the quality of conversion coatings. The La‐conversion coatings could provide important protection against α‐brass corrosion for considerable immersion periods in 3.5 wt% sodium chloride solution because it ennobled the corrosion potential and decreased the anodic current.     

1‐Methyl‐3‐pyridine‐2‐yl‐thiourea as inhibitor for acid corrosion of stainless steel

The inhibiting effect of 1‐methyl‐3‐pyridine‐2‐yl‐thiourea (MPT) on the corrosion of stainless steel in 0.5 M H₂SO₄ solution was investigated using weight loss and potentiostatic polarization techniques. The percentage inhibition efficiencies and surface coverage degrees increased with increasing additive concentration. Potentiostatic polarization studies revealed that MPT is of the mixed‐type inhibitor in 0.5 M H₂SO₄ solution. The adsorption of this inhibitor is also found to obey the Langmuir adsorption isotherm. From the adsorption isotherm, value of the ΔG_ads for the adsorption process was calculated. From the corrosion rate obtained at 25–55 °C E_a, ΔH_a and possible mechanism have been proposed. Scanning electron microscopy (SEM) was done from the surface of the exposed sample indicating uniform film on the surface.