Oxidation and corrosion behaviour of laser-alloyed mild steel with chromium

The oxidation and corrosion of mild steel coated with chromium powder followed by laser treatment has been investigated. Chromium powder was deposited on mild steel surface using atmospheric plasma spraying. The chromium-coated surface was irradiated separately using a pulsed Nd:YAG laser and a continuous CO₂ laser. The oxidation tests were carried out in air at 700°C and anodic polarization tests in 1N H₂SO₄ solution. There was significant difference in the morphologies of the surface alloys formed using CO₂ laser and Nd:YAG laser. Samples treated with CO₂ laser showed better oxidation resistance whereas the surface alloys formed using Nd:YAG laser showed poor oxidation resistance. Anodic polarization tests carried out on samples laser-treated with CO₂ laser showed improved corrosion resistance.     

SURFACE ALLOYING OF MILD STEEL BY LASER MELTING OF AN ELECTROLESS NICKEL DEPOSIT CONTAINING CHROMIUM CARBIDES

It is possible to realize surface alloys by laser melting an electroless nickel layer containing chromium carbide particles predeposited on a mild steel substrate. By this way the surface alloy is expected to have not only a high nickel content but also an important chromium content in order to improve the corrosion resistance. The presence of chromium in solid solution results from the dissolution or melting of the carbide particles. Typical laser solidification microstructures are obtained. Dendrites consist of an austenitic Fe-Ni-Cr solid solution and interdendritic regions are constituted by an eutectic mixture containing the same austenitic solid solution and complex Fe, Ni, Cr carbides and phosphides. In comparison with a surface alloy obtained by laser melting of an electroless nickel layer without carbide particles, the corrosion resistance was slightly improved in saline aqueous solutions. The limited effect was due to the fact that the final chromium content in the present experimental conditions was not as high as that initially expected.     

Effect of laser surface melting on the corrosion resistance of chromium-plated 9Cr-1Mo ferritic steel in an acidic medium

9Cr-1 Mo ferritic steel forms an integral part of some of the nuclear power generating industries where it is used as the steam generating material. Its corrosion resistance could be further improved by employing a chromium coating over it. However, this chromium coating has been found to be unsatisfactory owing to the microcracks present in the coating. Laser surface melting (LSM) could be effectively used not only to remove these microcracks but also to form a better corrosion-resistant modified surface without affecting the bulk properties of the material. Studies were carried out on the laser surface melted chromium-plated 9Cr-1Mo steel. The specimens with chromium deposit thicknesses ranging from 30–70 m were prepared and then laser irradiated. Optical microscopic studies on the cross-sections of these specimens revealed an average laser-melted thickness of around 0.1–0.5 mm, depending upon the irradiation parameter used. Aqueous corrosion behaviour of these specimens was studied by anodic polarization in 1N H₂SO₄ medium. Anodic polarization experiments were carried out for specimens after repolishing the same specimen until the 9Cr-1Mo base metal was reached. The passive and peak current density values, range of passivity, peak and transpassive potentials, were determined at each stage of polishing, and these were compared with those of pure chromium metal as well as 9Cr-1Mo alloy in the same medium. Observation of these data indicates that the laser surface melting could be beneficial in raising the aqueous corrosion resistance of such chromium-coated steels, to a level comparable with that of the pure chromium metal.     

The solid state bonding of nickel,chromium and nichrome sheets to α-Al2O3

This paper describes experiments to measure the interfacial shear strengths of bonds formed between nickel, chromium and nichrome sheets hot pressed on to -Al₂O₃ single crystal plaques. Nickel developed bonds of 8×10³ psi (56 MN. m^–2) in shear when pressing was carried out under non-reducing conditions at 1100° C, 1 tsi (15 MN. m^–2) for 2 h: in the case of chromium, the effect of pressing temperature (1000 to 1300° C) pressing pressure (1/2 to 3 tsi [7.7 to 45 MN. m^–2]) and pressing time (1/2 to 7 h) on the bond was investigated. Nickel-chrome alloys produced from alternate nickel and chromium strips showed bond strengths up to 20×10³ psi (140 MN. m^–2) whilst commercial nickel-chrome (containing a silicon impurity) was not as effective in bonding to alumina. In material prepared from alternate strips of nickel and chromium, the degree of alloy homogenisation was investigated using microprobe analysis and suggestions made as to the mechanism of the interfacial reactions with alumina.     

Corrosion behaviour of a steel surface laser alloyed with chromium borides

The corrosion behaviour of a carbon steel surface laser alloyed with chromium borides was investigated using electrochemical and surface analytical methods. Chromium and boron were unevenly distributed in the laser-alloyed layer. The distribution of chromium controlled the anodic dissolution of the alloy. Iron was dissolved preferentially from the surface and a loose corrosion product layer enriched in chromium was formed during active dissolution in 0.1m H₂SO₄. The chromium boride inclusions on the surface promoted hydrogen evolution and controlled cathodic behaviour. In neutral and basic solutions, the corrosion behaviour of the laser-alloyed surface was very close to that of the matrix steel. The effects of the alloying elements on corrosion behaviour are discussed.     

Microstructure and wear of some high-tensile brasses

The relationship between microstructure, coefficient of friction and wear behaviour against mild steel has been examined for three commercially extruded high-tensile brasses, containing additions of manganese (3 wt%) and silicon (1 wt%). The alloys contained an approximately constant volume fraction of Mn₅Si₃ (6–7%) but the proportions of the and phases present were varied widely both by heat treatment and by changing the composition, particularly the aluminium content which lay in the range 0–3 wt%. A conventional pin-on-rotating-disc configuration with different loads and sliding speeds was used to determine the wear and the coefficient of friction. The effect of heat treatment on the wear behaviour of given alloys was complex, and depended on the volume fraction of the and phases, on their distribution in the microstructure, and on the ease with which the hard Mn₅Si₃ particles became detached from the phases in which they were located. The average coefficient of friction for the materials examined was 0.36±0.02 and showed little variation with composition and microstructure, but it was clear that the experimental data was being influenced by detachment of Mn₅Si₃ particles. Results for the three alloys examined are presented and discussed.     

Corrosion behaviour of some stainless steel alloys in molten alkali carbonates (I)

In the present work it is aimed to study the corrosion behaviour of two types of stainless steel alloys (one ferritic and two austenitic) in molten Li₂CO₃- Na₂CO₃- K₂CO₃ mixture. This mixture is of interest in corrosion studies because of its low melting point (397°C) and good electrical properties. In this investigation the following techniques of measurements are used: (i) open circuit-potential, (ii) galvanic current, (iii) impedance, (iv) atomic absorption spectroscopy for the determination of the amount of metals dissolved in the melt (v) corrosion tests, carried out on the oxide scales formed during the oxidation of stainless steel alloys in carbonate melt. In this melt the electrode Ag/AgCl was used as a reference electrode. In molten carbonates, the oxide ions originate by self-dissociation according to the equilibrium CO₃ ^2– CO₂ + O^2–. The oxide ions, O^2–, and carbonate ions, CO₃ ^2–, play an important role in the oxidation process of these alloys and their passivation in the carbonate melt. As previously mentioned in references it can be assumed that the oxide scales formed on the alloy surface consist mainly of LiCrO₂ and LiFeO₂. The cathodic path of the corrosion process may be the reduction of CO₂ and/or CO₃ ^2–. The resistance of alloys against corrosion in melt increases with the increase of temperature. This may be due to the increase of concentration of O^2– and CO₂, enhancing both the anodic and cathodic reactions. The activation energy was calculated and found to be 91.496, 23.412 and 37.956 kJ/mol for the alloys 1, 2 and 3 respectively. The above mentioned techniques of measurements showed that the oxide scales of the austenitic stainless steel alloys (2, 3) are more passive and protective than of ferritic stainless steel alloy (1). This means that the resistance against corrosion, in the carbonate melts, of austenitic stainless steel alloys is higher than that of ferritic one.     

The abrasive corrosion behavior of plasma-nitrided alloy steels in chloride environments

Both corrosion and abrasive corrosion behavior of plama-nitrided type 304 and 410 stainless steels and 4140 low alloy steel were investigated in 3% NaCl solution (pH = 6.8) by electrochemical corrosion measurements. Surface morphology and alloying elements after corrosion and abrasion corrosion tests were examined by scanning electron microscopy and energy dispersive analysis of X-rays. The results indicated that the plasma-nitrided SAE 4140 steel containing -(Fe,Cr)_{2 – 3}N and -(Fe,Cr)₄N surface nitrides which produce a thick and dense protective layer exhibited a significant decrease of corrosion currents by inhibition of the anodic dissolution of iron, whereas the plasma-nitrided type 304 and 410 stainless steels containing the segregation of chromium nitride CrN exhibited a extensive pitting corrosion by acceleration of the anodic dissolution of iron. It is concluded that the susceptibility to pitting is consistent with the degree of chromium segregation, and decreases as follows: 304 stainless steel > 410 stainless steel > 4140 steel. Also, the results of abrasive corrosion testing for the plasma-nitrided alloys are strongly related to the subtleties of the nitrided microstructures resulting in a pitting and spalling type of abrasive corrosion of type 304 and 410 stainless steels, and excellent abrasive corrosion resistance for SAE 4140 steel.     

Electrochemical behaviour of iron—chrome alloys in relation to pitting corrosion

The polarization behaviour and pitting corrosion of Fe-Cr alloys of 7, 13, 18, 24 wt% Cr were studied. Potentiodynamic and galvanostatic measurements were performed in the absence and presence of Cl^–. As the Cr content increases the active dissolution current densities decrease while the passive range and transpassive current densities increase. Polarization parameters gave for the passive transition of the alloys a Cr concentration of -13%. An increase of Cl^– concentration causes the progressive destruction of passivity. It interfered with O₂ evolution, and then destroyed the transpassive region. Still higher Cl^– concentrations initiated pitting corrosion as shown by the oscillations in potential of the galvanostatic polarization curves supported by visual observation. Results are discussed on the basis of competitive adsorption between the aggressive and inhibitor anions for the active sites on the alloys' surface.     

Chromium carbide laser-beam surface-alloying treatment on stainless steel

In order to improve the resistance to wear, oxidation and corrosion of a stainless steel die, chromium carbide surface-alloying treatment was carried out on a 12 % Cr stainless steel using a CO₂ laser. Cr₃C₂ powder slurry was coated on the stainless steel and then a 3 kW CO₂ laser beam was used to irradiate the specimen. The thickness of surface-alloyed layer was about 0.3 mm and the chromium concentration was about 40 % throughout the alloyed-region. Large amounts of Cr₃C₂ and Cr₇C₃ were also distributed in this alloyed layer. From the results of the isothermal oxidation test at 960 °C for 100 h, it was found that the surface-alloying treatment improved the oxidation resistance by about 100 times due to the distribution of chromium carbides and the increase in the chromium concentration. The results of the cyclic oxidation test revealed that the oxidation layer was very stable on the chromium carbide surface-alloyed region, while it scaled off very easily from the substrate region due to porous oxidation products. The microhardness was about 1100 H_v due to the dispersion and precipitation of chromium carbides in addition to the martensitic structure in the surface-alloyed region. The microhardness did not decrease much, despite heating at 960 °C for 100 h. The chromium carbide surface-alloying treatment improved the wear-resistance greatly, and the results of the wear-resistance test were very consistent with those of the microhardness test.     

Thermodynamic analysis of equilibria in Fe-Cr-C alloys and evaluation of their dusting stability in aggressive carboniferous atmospheres

Thermodynamic analysis of phase transformations and reactions in Fe-Cr-C alloys is carried out with allowance made for all possible states, both stable and metastable, in the temperature range of metal dusting in aggressive carboniferous atmospheres. The results are compared with data on the corrosion resistance of chromium steel pipes under oil refining conditions. It is shown that, at high temperatures, one of the equilibrium phases in this system is the cementite solid solution (Fe_1-y Cr_y)₃C. Below 930 K, this phase becomes unstable to the decomposition into mixtures containing other carbides, but the tendency for chromium to stabilize cementite persists. The metal dusting mechanism changes in the composition range 0.03 y 0.055 (2.8–5.1 wt % Cr). This conclusion is supported by the results of tests on chromium steel (15Kh5M and 15Kh2M1) pipes under oil refining conditions, which indicate that the introduction of chromium into Fe alloys can only inhibit the degradation of Fe-Cr-C alloys under metal dusting conditions, without fully preventing it.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 177–184.Original Russian Text Copyright © 2005 by Alshevskii, Baklanova, Zaitsev, Maltsev, Rodionova, Rybkin, Shaposhnikov.     

Mechanical behaviour of Zn–Fe alloy coated mild steel

Zinc alloy coatings containing various amounts of Fe were deposited by electrodeposition technique on a mild steel substrate. The concentration of Fe in the produced alloy coatings ranged from 0 to 14 wt.%, whereas the thickness of the coatings was about 50 μm. Structural and metallurgical characterization of the produced coatings was performed with the aid of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) techniques. This study aims in investigating the mechanical behaviour of Zn–Fe coated mild steel specimens, as no research investigation concerning the tensile behaviour of Zn alloy coated ferrous alloys has been reported in the past. The experimental results indicated that the ultimate tensile strength of the Zn–Fe coated mild steel was lower than the bare mild steel. In addition, the ductility of the Zn–Fe coated mild steel was found to decrease significantly with increasing Fe content in the coating.     

Evaluation of hot corrosion behaviour of HVOF sprayed NiCrAl coating on superalloys at 900 °C

In the present investigation, NiCrAl coating was deposited on Ni- and Fe-based superalloy substrates by using high velocity oxy-fuel (HVOF) process to study the hot corrosion behaviour in molten salt (Na₂SO₄–60% V₂O₅) environment at 900 °C under cyclic conditions. The mass gain measurements were performed after each cycle to establish the kinetics of corrosion using thermogravimetric technique. X-ray diffraction (XRD), scanning electron microscopy/energy dispersive spectroscopic analysis (SEM/EDS) and X-ray mapping techniques were used to analyse the corrosion products. The bare superalloys experienced higher weight gain. The NiCrAl-coated Superni 750 alloy (SN 750) provided a better protection among the coated superalloys investigated. The formation of oxides and spinels of nickel, chromium and aluminum may be contributing better resistance to hot corrosion.     

X-ray microanalysis and properties of multicomponent plasma-borided layers on steels

The structure and chemical composition of composite and multicomponent borided layers obtained by a new method that combines the chemical electroless and plasma boriding techniques are described. Quantitative X-ray microanalysis examinations show that on the surface of nickel–phosphorus coated steel borided at 923 K three boride phases of the type (Ni _x Fe_{1 – x} )₄B₃, (Ni _x Fe_{1 – x} )₂B and (Fe _x Ni_{1 – x} )B formed, whereas in the samples borided at 1123 K only two borides (Fe_{1 – x} Ni _x )B and (Fe_{1 – x} Ni _x )₂B are present. The shape and the distribution of the phases depends on the thickness of the Ni–P layer deposited on the steel substrate before boriding. The thicknesses of boride zones obtained on nickel coated steels are much greater than those obtained on the same steel without nickel coating. Also the diffusion zone between the Ni–P layer and the steel increases during boriding, which improves the adhesion of the layer to the substrate. The composite layers obtained show a high wear resistance, with their resistance to corrosion being markedly greater than that of uncoated and only borided steel.     

In situ laser surface coating of TiC metal-matrix composite layer

Surface alloys are of great interest for improving the mechanical and/or chemical properties of the near-surface region on metallic materials. A new method, in situ laser surface coating of metal-matrix composite, is described, by which to produce a surface composite layer. Using this process, -Ni-TiC _x composite surface layers were achieved on mild steel; they exhibited increased hardness, and in situ formed TiC_x particles, 0.5–0.8 m in size, were homogeneously distributed in the top half of the matrix layer.     

Crystallization and phase transformation behaviour of electroless nickel-phosphorus deposits with low and medium phosphorus contents under continuous heating

Electroless nickel-phosphorus deposits with 5–8 wt% P and 3–5 wt% P were analysed for the effects of continuous heating on the crystallization kinetics and phase transformation behaviour of the deposits. The as-deposited coatings consist of a mixture of amorphous and microcrystalline nickel phases, featuring in their X-ray diffraction patterns. Continuous heating processes to 300°C–800°C at 20°C/min were carried out on the deposits in a differential scanning calorimetric apparatus. The subsequent X-ray diffraction analyses show that the sequence of phase transformation process was: amorphous phase + microcrystalline nickel f.c.c. nickel + Ni₃P stable phases. Preferred orientation of nickel (200) plane developed in the deposits after the heating processes. Differential scanning calorimetry of the deposits indicates that the crystallization temperatures increased with decreasing phosphorus content, and increasing heating rate. Crystallization activation energies of the deposits (230 and 322 kJ/mol, respectively) were calculated using the peak temperatures of crystallization process, from the differential scanning calorimetric curves at the heating rates ranging from 5 to 50°C/min. It was found that the deposit with lower phosphorus content has higher activation energy.     

Dry sliding wear behaviour of Al–12Si–4Mg alloy with cerium addition

The purpose of this work is to understand the effect of cerium addition on wear resistance behaviour of as-cast alloys. Al–12Si–4 Mg alloys with 1–5 wt% cerium addition were prepared using the casting technique. A sliding wear test was carried out under applied loads of 10 N, 30 N and 50 N at a fixed sliding speed of 1 m/s using a pin-on-disc configuration. The wear test was conducted in dry conditions at room temperature of 25 °C. Detailed analysis of the microstructure, worn surface, collected debris and microhardness was undertaken in order to investigate the differences between the as-cast alloys with different levels of cerium addition. The addition of 1–5 wt% cerium was found to lead to the precipitation of intermetallic phases (Al–Ce), resulting a needle-like structures. Increasing cerium content up to 2 wt% improved both wear resistance and microhardness of as-cast alloys. Addition of more than 2 wt% cerium, however, led to a decrease in microhardness, resulting in lower wear resistance of the alloys. Moderate wear was observed at all loads, with specific wear rates (K′) ranging from 6.82 × 10⁻⁵ with 2 wt% Ce at applied load of 50 N to 21.48 × 10⁻⁵ mm³/N m without added Ce at an applied load of 10 N. Based on K′ ranges, the as-cast alloys exhibited moderate wear regimes, and the mechanism of wear is a combination of abrasion and adhesion. Alloy containing 2 wt% Ce, with the highest hardness and lowest K′ value, showed the greatest wear resistance.     

Corrosion inhibition in magnesium-aluminium-based alloys induced by rapid solidification processing

The effect of rapid solidification on the corrosion behaviour in aerated 0.001 M NaCl solution of Mg-Al alloys containing 9.6 to 23.4wt% AI has been investigated in comparison with chill-cast material. Polarization studies show that rapid solidification decreases corrosion current by up to two orders of magnitude corresponding to a corrosion rate of 6 to 11 mil y^–1. Increasing the aluminium content in solid solution by rapid solidification gave rise to a steep increase in pitting potential between 10 and 23 wt% Al and resulted in development of an anodic plateau at 30Acm^–2 attributable to magnesium depletion for the alloy surface and formation of a protective film. Chemical analysis of the electrolyte as a function of dissolution time for the rapidly solidified material indicated that initially only magnesium dissolved and that this dissolution of magnesium ceased within 2 to 5 min. The results indicate the formation of an aluminium-enriched interdiffusion zone at the surface underlying a more stable surface oxide than for ingot-processed Mg-Al-based alloys.     

The effect of nickel content on the fracture behaviour of Cu-Al-Niβ-phase alloys

The fracture behaviour of Cu-14 wt% Al alloys has been studied as a function of nickel content varying from 0 to 10 wt%. It was found that the presence of a brittle phase ₂ at the grain boundaries is responsible for intergranular fracture in low nickel alloys. Severe intergranular embrittlement exhibited by high nickel alloys in not associated with any precipitate at the grain boundaries. In fact when high nickel alloys are cooled slowly, a ductile phase () forms along the grain boundaries that resists the propagation of crack through grain boundaries and the fracture is transgranular.     

Production of cast aluminium-graphite particle composites using a pellet method

Copper- and nickel-coated graphite particles can be successfully introduced into aluminium-base alloy melts as pellets to produce cast aluminium-graphite particle composites. The pellets were made by pressing mixtures of nickel- or copper-coated graphite particles and aluminium powders together at pressures varying between 2 and 20 kg mm^–2. These pellets were dispersed in aluminium alloy melts by plunging and holding them in the melts using a refractory coated mild steel cone, until the pellets disintegrated and the powders were dispersed. The optimum pressure for the preparation of pellets was 2 to 5 kg mm^–2 and the optimum size and percentage of aluminium powder were 400 to 1000m and 35 wt% respectively. Under optimum conditions the recovery of the graphite particles in the castings was as high as 96%, these particles being pushed into the last freezing interdendritic regions. The tensile strength and the hardness of the graphite aluminium alloys made using the pellet method are comparable to those of similar composites made using gas injection or the vortex method. The pellet method however has the advantage of greater reproducibility and flexibility. Dispersion of graphite particles in the matrix of cast aluminium alloys using the pellet method increases their resistance to wear.Formerly with Indian Institute of Science, Bangalore, India.