Electrochemical corrosion parameters of as-cast Al-Fe alloys in a NaCl solution

The aim of this study is to evaluate the general electrochemical corrosion resistance of Al-Fe alloys in the range of hypoeutectic compositions, Al-0.5 wt.% Fe and Al-1.5 wt.% Fe alloy. EIS plots, potentiodynamic polarization curves and an equivalent circuit analysis were used to evaluate the electrochemical parameters in a 0.5 M NaCl solution at 25 °C. It is shown that for an Al-0.5 wt.% Fe alloy, coarse cells tend to improve the corrosion resistance mainly due to the reduction in cellular boundaries and for an Al-1.5 wt.% Fe alloy, an opposite trend has been detected.     

Effect of iron-containing intermetallic particles on the corrosion behaviour of aluminium

The effect of heat treatment on the corrosion behaviour of binary Al-Fe alloys containing iron at levels between 0.04 and 0.42 wt.% was investigated by electrochemical measurements in both acidic and alkaline chloride solutions. Comparing solution heat-treated and quenched materials with samples that had been subsequently annealed to promote precipitation of Al₃Fe intermetallic particles, it was found that annealing increases both the cathodic and anodic reactivity. The increased cathodic reactivity is believed to be directly related to the increased available surface area of the iron-containing intermetallic particles acting as preferential sites for oxygen reduction and hydrogen evolution. These particles also act as pit initiation sites. Heat treatment also causes depletion in the solute content of the matrix, increasing its anodic reactivity. When breakdown occurs, crystallographic pits are formed with {1 0 0} facets, and are observed to contain numerous intermetallic particles. Fine facetted filaments also radiate out from the periphery of pits. The results demonstrate that the corrosion of aluminium is thus influenced by the presence of low levels of iron, which is one of the main impurities, and its electrochemical behaviour can be controlled by heat treatment.     

Study on the Si penetration into Fe sheets using PVD method and its application in the fabrication of Fe-6.5 wt.% Si alloys

FeSi (12 wt.% Si) and Si were alternatively deposited on pure iron (Fe) substrates by direct current magnetron sputtering. Subsequent annealing in vacuum at 1150-1190 °C results in penetration of Si into the substrate. Cross-sectional microstructure and Si concentration were investigated by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The penetration mechanism is found to depend greatly on Si amount in the as-deposited films. When FeSi/Si/FeSi/Si/FeSi was deposited on the Fe substrate, the Si penetration is controlled by phase-boundary migration, while a diffusion-controlling penetration is observed in FeSi/Si/FeSi deposited samples. Fe-6.5 wt.% Si sheet with thickness of 0.35 mm is obtained through the deposition of FeSi/Si multilayer on a Fe-3 wt.% Si sheet together with subsequent annealing at 1180 °C for 2 h.     

Effects of heat-treatment on the extent of chromium depletion and caustic corrosion resistance of Alloy 690

To quantify the extent of chromium depletion, electrochemical potentiokinetic reactivation tests were performed on solution-annealed (1393 K) and solution-annealed followed by ageing at 973 K for 4 h or 16 h samples of austenitic Alloy 690. The electrochemical studies indicated very high equilibrium chromium concentration at the chromium carbide/matrix interface for the aged samples. A new electrochemical test parameter that is the ratio of peak activation to maximum passive current density (defined by I_a/I_f) was considered to express the extent of chromium depletion. The alloy, in three different heat-treated conditions, revealed unstable passivity in deaerated 5% and 10% NaOH solutions at 295 K. A comparatively higher passive current density of the aged samples in deaerated caustic environments than the annealed one could be attributed to reactivity of Cr-carbides with the caustic. Microscopic studies indicated that the TiN inclusion/matrix interface may provide a preferred site for pit initiation in caustic environments, which could be attributed to large degree of misfit between TiN inclusion and austenite matrix.     

The study of stress application and corrosion cracking on Ni-16 Cr-9 Fe (Alloy 600) C-ring samples by polychromatic X-ray microdiffraction

Microscopic strains associated with stress corrosion cracks have been investigated in stressed C-rings of Ni-16 Cr-9 Fe (Alloy 600) boiler tubing. Polychromatic X-ray microdiffraction was used to measure deviatoric strain tensors and the distribution of dislocations near cracks that had been propagated in electrochemically accelerated corrosion tests. An associated investigation of the C-ring-induced strains prior to corrosion showed significant tensile strain in the stress axis direction by the torsional closure of the alloy tube section in the C-ring test. Significant grain lattice rotation and pronounced plastic strain at some grain boundaries were noted. Stress-corrosion-cracking-generated intergranular cracks were produced in two Alloy 600 specimens after 6 h and 18 h tests. The diffraction patterns and resultant strain tensors were mapped around the cracked area to a 1 μm spatial resolution. The strain tensor transverse to the crack growth direction showed tensile strain at the intergranular region just ahead of the crack tip for both specimens. Both cracks were found to follow grain boundary pathways that had the lowest angle of misorientation. Dislocation distributions within each grain were qualitatively obtained from the shapes of the diffraction spots and the effect of “hard” and “soft” grains on the crack pathway was explored for both 6 h and 18 h specimens. The Schmid factor of one of the grains adjacent to the crack at the 6 h and 18 h initiation sites was found to be the lowest, compared to Schmid factors calculated for surface grains away from the initiation site, and also along the crack path into the bulk.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

The effect of manganese and chromium on surface oxidation products formed during batch annealing of low carbon steel strip

Surface oxides formed at ferrite grain boundaries of low carbon steels annealed at 700 °C in 5% hydrogen 95% nitrogen atmosphere were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Two different oxides (Fe,Mn)O and MnCr₂O₄ are observed at the grain boundaries and the former is five-fold coarser than the latter. It was found at the annealing temperature of 700 °C that the mean particle size of the (Fe,Mn)O depends on the manganese content, and the mean particle size and distribution of the MnCr₂O₄ dependent on chromium, but independent of manganese. It is unlikely the coarse (Fe,Mn)O precipitates pose any potential risks to the electrolytic tin coating quality as they will be removed by the pickling operation prior to tinning. The potential risks posed by the MnCr₂O₄ to the quality of the electrolytic tin coating of tinplate products can be minimized by restricting the chromium content of the steel.     

Surface spreading of intergranular corrosion on stainless steels

The spreading of intergranular corrosion was investigated using micrometer scale simulations and experimental verifications on sensitized stainless steel [UNS S30400]. The degree of sensitization, presence of a pit, and applied potential all affected spreading. The inputs used in the simulation were obtained from Fe-XCr(X = 10, 12, 14, 16 wt.%)-Mo-Ni alloys representing various grain boundary Cr depletion levels. Corroding grain boundaries and pits triggered corrosion of nearby sensitized boundaries due to Ohmic potential drop. Large connected clusters of corroding grain boundaries formed at high fractions of Cr-depleted grain boundaries. The metallurgical, electrochemical and geometric conditions for this behavior could be forecasted.     

Oxidation of a quaternary three-phase Cu-20Ni-20Cr-5Fe alloy at 700-900 °C in 1 atm of pure O2

The oxidation of a quaternary Cu-Ni-Cr-Fe alloy containing approximately 20 at.% Ni, 20 at.% Cr and 5 at.% Fe, balance Cu (Cu-20Ni-20Cr-5Fe), was studied at 700-900 °C in 1 atm of pure oxygen. The alloy is composed of a mixture of three phases, where the lightest α phase with the largest Cu content forms the matrix, while the other two, much richer in Cr, form a dispersion of isolated particles. At variance with the ternary three-phase Cu-20Ni-20Cr alloy examined previously, which was unable to form protective chromia scales over the alloy surface even after an extended period of oxidation, the present alloy formed complex external scales containing mixtures of the oxides of the various components plus a deep internal region containing a mixture of alloy and oxide phases. With time, a very irregular and thin but essentially continuous chromia layer formed at the bottom of the mixed internal oxidation region, producing a gradual decrease of the oxidation rate. Thus, the addition of 5 at.% Fe to Cu-20Ni-20Cr alloy is able to decrease the critical Cr content required to form the most stable oxide and promotes the formation of a continuous chromia scale under a lower Cr content in spite of the simultaneous presence of three different phases.     

The Effect of Grain Size and Dislocation Density on the Tensile Properties of Ni-SiC<Subscript>NP</Subscript> Composites During Annealing

The grain size refinement, enhancement of mechanical properties, and static recrystallization behavior of metallic nickel-silicon carbide nano-particle (Ni-3wt.%SiC_NP) composites, milled for times ranging from 8 to 48 h have been examined. One set of Ni-SiC_NP composite samples were annealed at 300 °C for 250 h, while the other set of samples were maintained at room temperature for control purposes (reference). The electron backscatter diffraction results indicate that the grain size of the annealed Ni-SiC_NP composite was refined due to grain restructuring during static recrystallization. The x-ray diffraction results indicate that low-temperature annealing effectively reduced the density of dislocations; this can be explained by the dislocation pile-up model. Additionally, the tensile tests indicated that the annealed Ni-SiC_NP composite had a significant increase in strength due to an increase of the Hall–Petch strengthening effect with a slight increase in the total elongation. The decrease of dislocation pile-up in the grain interiors and the increase in grain boundary sliding are assumed to be the main mechanisms at play. The relationship between the microstructural evolution and the variation of tensile properties is examined in this study.     

Effect of niobium on the corrosion behaviour of low alloy steel in sulfuric acid solution

This study examines the effect of niobium (Nb) addition on the electrochemical properties of low alloy steel using electrochemical techniques in a 10 wt.% sulfuric acid solution as well as surface analysis techniques. The potentiodynamic test reveals the passive behaviour of all specimens and a decrease in the passive currents with increasing Nb content. Electrochemical impedance spectroscopy (EIS) shows that the Nb-containing steels have higher passive and charge transfer resistance than the control samples. These results suggest that the interaction of elements improves the corrosion resistance of low alloy steel due to the formation of Nb, C, S, P, and Fe products on the surface.     

Annealing temperature effect on the corrosion parameters of autocatalytically produced Ni-P and Ni-P-Al2O3 coatings in artificial seawater

Ni-P and Ni-P-Al₂O₃ amorphous alloy coatings with 9.3 and 8.3 wt.% P respectively were obtained by autocatalytic deposition at 90 °C on carbon steel substrates. The effect of annealing temperature (100, 200, 300, 400 and 500 °C) upon the corrosion parameters of the coatings in artificial seawater with pH 5.0 and 8.1 at room temperature was evaluated by potentiodynamic polarisation and electrochemical impedance spectroscopy. It was found that deposits annealed at 400 and 500 °C presented an increase of the charge transfer resistance and negligible changes on samples annealed at lower temperature. Polarisation tests showed a charge transfer controlled anodic kinetics on both Ni-P and Ni-P-Al₂O₃ deposits and diffusion controlled cathodic reaction in artificial seawater at pH 5.0 and 8.1. The coatings did not present passive behaviour in the electrolytes and impedance measurements showed a single time constant for all cases with the lowest double layer capacitance (C_dl) for samples annealed at 400 and 500 °C. The best corrosion parameters were observed on Ni-P and Ni-P-Al₂O₃ coatings annealed at temperatures higher than 400 °C, which is the temperature where crystallisation of this kind of coatings takes place.     

Grain size effects on the SCC susceptibility of a nitrogen steel in hot NaCl solutions

The effect of grain size on the exhibited stress corrosion cracking (SCC) resistance of an austenitic stainless steel containing 0.97 wt.% nitrogen was investigated in this work. In order to vary the grain size, the as-received steel (AR) was heat treated (HT) at 550 and at 1100 °C for 1 h. Cert specimens of the AR and HT N-containing steels were then machined and tested in a Cortest machine using slow strain rates ranging from 7.95 × 10⁻⁶ s⁻¹ to 7.06 × 10⁻⁷ s⁻¹. The corrosion environment was hot water, as well as a 30% NaCl solution at 90 °C. In all the steel conditions, SCC was directly related to active pitting development. In all the cases, pits were found to preferentially form at Mn-Al inclusions, but were not able to grow too deep probably as a result of active repassivation reactions. It was found that the drop in the exhibited mechanical properties of the steels such as yield strength, UTS and % elongation was particularly enhanced for the coarse grained steel HT at 1100 °C. A SCC susceptibility index confirmed that this was indeed the case. Apparently, a drop in the yield strength tends to reduce the mechanical stability of the passive layer promoting its breakdown. Finally, quasi-cleavage and the lack of appreciable plastic deformation in some of the fracture surfaces indicated that the steel underwent some degree of embrittlement when exposed to these aqueous environments.     

Effect of secondary carbides addition on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-based cermets

(Ti, W, Mo, V)(C, N)-based cermets were prepared by mixing Mo₂C, WC and TaC with ultrafine (Ti, W, Mo, V)(C, N) powders, and then processed via a conventional P/M technique. The effect of Mo₂C, WC and TaC on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co systems was investigated. The Mo₂C content was varied from 0 to 10 wt.% and additive WC or TaC was added at a level of 5 wt.% with Mo₂C addition. The results show that the densification of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co cermets was improved significantly by the addition of Mo₂C. With the increase of Mo₂C content, there is a coarsening tendency in the microstructure of (Ti, 20W, 15Mo, 0.2V)(C, N)-8Ni-7Co system, but the refinement for (Ti, 15W, 5Mo, 0.2V)(C, N)-8Ni-7Co. TaC addition decreases the density of (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-8Ni-7Co cermet and thus weakens its bending strength. (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-5WC-8Ni-7Co cermet has optimal mechanical properties: bending strength of 1999 MPa, hardness (H_v) of 1677 MPa and toughness of 9.95 MPa m^1/2 respectively by adding WC, which is due to its ultrafine and weak core/rim structure.     

Corrosion behaviour of AIP NiCoCrAlYSiB coating in salt spray tests

NiCoCrAlYSiB coatings were deposited by arc ion plating (AIP) and annealed/pre-oxidised under various conditions. The corrosion behaviour of as-deposited and annealed/pre-oxidised coatings was studied by salt spray testing in a neutral mist of 5 wt% NaCl at 35 °C for 200 h. The results showed that the as-deposited NiCoCrAlYSiB coating behaved poorly while the annealed and pre-oxidised ones performed much better in salt spray tests. The dense microstructure in annealed coatings and formation of α-Al₂O₃ scales on the surface during pre-oxidation improved the corrosion resistance in salt spray test. The corrosion process was investigated from the aspects of corrosion products, and its electrochemical mechanism was proposed as well.     

Effect of tungsten content on microstructure and quasi-static tensile fracture characteristics of rapidly hot-extruded W-Ni-Fe alloys

Tungsten heavy alloys (WHAs) with three different compositions (90W-7Ni-3Fe, 93W-4.9Ni-2.1Fe and 95W-3.5Ni-1.5Fe, wt.%) were heavily deformed by one-pass rapid hot extrusion at 1100 °C with an extrusion speed of ~ 100 mm/s and an extrusion ratio of ~ 3.33:1. The influence of tungsten content on the microstructure and tensile fracture characteristics of the as-extruded alloys was investigated in detail. The results show that the tungsten particles in the as-extruded 95W have the largest shape factor compared to the as-extruded 90W and 93W alloys and this implies that the tungsten particles in the as-extruded 95W alloy were subjected to the heaviest plastic deformation. In addition, ultimate tensile strength (UTS) and hardness (HRC) are significantly improved after rapid hot extrusion. The as-extruded 95W alloy processes the highest strength (1455 MPa) and hardness (HRC40) but the lowest elongation (5%), followed by the as-extruded 93W (UTS1390MPa; HRC39; 7%) and 90W alloys (UTS1260MPa; HRC36; 10%). The fracture morphology shows the distinct fracture features between the as-sintered alloys and the as-extruded alloys. For the as-sintered alloys, the fracture modes are various while transgranular cleavage of tungsten particles is the main characteristic in the as-extruded alloy. Meanwhile, the fracture modes of the three as-extruded alloys vary slightly with the tungsten content. TEM bright field images indicate that many lath-like subgrains with the width of 150-500 nm are present in the three as-extruded alloys, particularly in the as-extruded 93W and 95W alloys. Furthermore, the dislocations are absent in the γ-(Ni, Fe) phase. This means that dynamic recovery-recrystallization process took place during rapid hot extrusion.     

Strength and ductility of 316L austenitic stainless steel strengthened by nano-scale twin bundles

By means of dynamic plastic deformation (DPD) with high strain rates, a bulk nanostructured 316L austenitic stainless steel consisting of nano-sized grains embedded with bundles of nanometer-thick deformation twins was synthesized. The average transverse grain size is ∼33 nm and the twin/matrix lamellar thickness is ∼20 nm. The nano-twin bundles constitute ∼24% in volume. The nanostructured samples exhibit a high tensile strength of ∼1400 MPa but a limited ductility with a uniform elongation of ∼2%. Subsequent thermal annealing of the as-DPD samples in a temperature range of 730-800 °C led to a single-phased austenite structure consisting of static recrystallized (SRX) micro-sized grains embedded with remaining nano-twin bundles and nano-grains. The annealed DPD samples exhibit an enhanced strength-ductility synergy and much more enhanced work-hardening rates than the as-deformed samples. Work-hardening rates of the annealed DPD samples can be even higher than that of the original CG sample. Tensile ductility was found to increase almost linearly with the volume fraction of SRX grains. A combination of 1.0 GPa tensile strength with an elongation-to-failure of ∼27% is achieved in the annealed DPD 316L stainless steel samples.     

Microstructure characterization and electrical conductivity of electroless nano Ni coated 8YSZ cermets

Using a common electroless bath, Ni-8YSZ (Ni-8 mol% yttria stabilized zirconia) composite nano powder have been synthesized without use of any expensive sensitizing agent. HRTEM micrographs indicated that the coating morphology of Ni nano particles on the 8YSZ showed a spotty, discontinuous distribution and the Ni nano particles appeared as a crystalline phase. The amount of Ni in the composite powders was varied from 36-51 wt.% by changing the substrate powder loading in the electroless bath. Bar type samples were prepared by uniaxial pressing and sintering at 1300 °C for 2 h with these coated powders. The cubic (c)-zirconia was found to partially dissociate into monoclinic (m)-zirconia on sintering with Ni content 41% or higher and also increases with the increase of Ni content. The microstructure of each Ni-YSZ cermet after reduction in a H₂ + Ar gas atmosphere showed dual scale porosity (micro and submicron porosity). The Ni-8YSZ cermet samples showed metallic electrical conduction behavior, proving the percolation capability of the synthesized nano composite.     

Cyclic oxidation of yttria dispersed austenitic stainless steels

Cyclic oxidation of austenitic steels (Fe-20Ni-14Cr-2.5Mo-2Mn-2.5Al-wt.%) dispersed with 0, 0.5 and 5 wt.% yttria was carried out at 800 °C in air. The scale surface and cross-section were characterized using X-ray diffraction, scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). Yttria additions improve the resistance to spallation. The increase in the resistance to spallation appears to be related to the presence of mixed oxides between yttria and base metal oxides.     

Spark plasma sintering consolidation of nanostructured TiC prepared by mechanical alloying

Spark plasma sintering technique was used for the consolidation of nanostructured titanium carbide synthesized by mechanical alloying in order to avoid any important grain growth of the compact materials. The TiC phase was obtained after about 2 h of mechanical alloying. Towards the end of the milling process (20 h), the nanocrystalline powders reached a critical size value of less than 5 nm. Some physical and mechanical properties of the consolidated carbide were reported as a function of the starting grain size powders obtained after different mechanical alloying durations. The crystalline grain size of the bulk samples was found to be increased to a maximum of 120 nm and 91 nm for carbides mechanically alloyed for 2 h and 20 h respectively. The Vickers hardness showed to be improved to about 2700 Hv for a maximum density of 95.1% of the bulk material.