Secondary ion mass spectrometry and multireflection infrared analyses of conversion coatings on Fe–Cr–Al stainless steels for catalysis: study of thermal stability

Abstract

The thermal stability of three stainless steel conversion coatings for high temperature applications (e.g. photothermal conversion catalysis) are investigated. The thermal oxidation in air up to 1000°C of Fe–17Cr, Fe–18Cr–1·3Al, and Fe–22Cr–5Al coatings (all wt-%) are compared. This study has revealed a critical temperature below which the coating thickness is preserved; the critical temperature increases and the thermal oxidation of the conversion coating decreases with higher chromium and aluminium content. This is attributed to the difference in the substitution ratio of γ lacunar phase (additionally oxidised substituted magnetite), which is the main component of the conversion coatings. The thermal stability of this phase is higher when it is richer in chromium or aluminium. Higher contents of these elements raise the temperature of formation of chromite (FeCr₂O₄) and alumina, the occurrence of which causes thickening of the coating during thermal treatment.

MST/1891     

Synthesis and Physicochemical Properties of La–Ce–Ni–O and Sr–Ce–Ni–O Oxides

La_{2 – x} Ce _x NiO _y and Sr_{2 – x} Ce _x NiO _y materials were prepared, and their properties were studied. Nearly single-phase Sr_{2 – x} Ce _x NiO _y samples (tetragonal K₂NiF₄ structure) could be obtained at x= 0.25 and 0.3. The lattice parameters, weight change, relative length change, and electrical resistivity of Sr_1.7Ce_0.3NiO _y were measured from 20 to 1000°C. The oxygen content of this material, determined by hydrogen reduction and iodometric titration, was found to vary widely, depending on heat-treatment conditions. The room-temperature resistivity of Sr_1.7Ce_0.3NiO _y is (2–5) × 10^–2 cm. In the range 20–450°C, this material exhibits n-type conductivity. Its thermoelectric power varies from –12 V/K at 20°C to –34 V/K at 450°C. The temperature variation of resistivity for Sr_1.7Ce_0.3NiO₄ in the first heating–cooling cycle below 450°C is shown to depend on the thermal history of the sample. The resistivity reaches a maximum between 500 and 800°C. The structural and transport properties of the mixed oxide are shown to be correlated with its oxygen content.     

Processing and properties of Al–Li–SiCp composites

Al–Li–SiC_p composites were fabricated by a modified version of the conventional stir casting technique. Composites containing 8, 12 and 18 vol% SiC particles (40 mm) were fabricated. Hardness, tensile and compressive strengths of the unreinforced alloy and composites were determined. Ageing kinetics and effect of ageing on properties were also investigated. Additions of SiC particles increase the hardness, 0.2% proof stress, ultimate tensile strength and elastic modulus of Al–Li–8%SiC and Al–Li–12%SiC composites. In case of the composite reinforced with 18% SiC particles, although the elastic modulus increases the 0.2% proof stress and compressive strength were only marginally higher than the unreinforced alloy and lower than those of Al–Li–8%SiC and Al–Li–12%SiC composites. Clustering of SiC particles appears to be responsible for reduced the strength of Al–Li–18%SiC composite. The fracture surface of unreinforced 8090 Al-Li alloy (8090Al) shows a dimpled structure, indicating ductile mode of failure. Fracture in composites occurs by a mixed mode, giving rise to a bimodal distribution of dimples in the fracture surface. Cleavage of SiC particles was also observed in the fracture surface of composites. Composites show higher peak hardness and lower peak ageing time compared with unreinforced 8090Al alloy. Macroand microhardness increase significantly after peak ageing. Ageing also results in considerable improvement in strength of the unreinforced 8090Al alloy and its composites. This is attributed to formation of δ^' (Al₃Li) and S^' (Al₂CuMg) precipitates during ageing. Per cent elongation, however, decreases due to age hardening. Al–Li–12%SiC, which shows marginally lower UTS and compressive strength than the Al–Li–8%SiC composite in extruded condition, exhibits higher strength than Al–Li–8%SiC in peak-aged condition.     

Physicochemical Properties of Amorphous and Crystalline Fe–P–Mn and Fe–P–Mn–V Alloys

Annealing Fe–P–Mn and Fe–P–Mn–V soft-magnetic amorphous alloys prepared from ferrophosphorus waste leads to the formation of fine-particle crystalline phases. The associated structural hardening is more pronounced in alloys with stronger interatomic interactions. The dissolution of Mn and V inhibits the growth of Fe₃P particles, which become smaller than the -Fe particles.     

Synthesis and characterization of bismaleimide–polyetherimide–titania hybrid

Ternary hybrids of bismaleimide–polyetherimide–titania were synthesized by sol–gel reaction and characterized by Scanning Electron Microscope, Energy Dispersive X-ray Analysis, Thermogravimetric Analysis and Differential Scanning Calorimeter. Moreover, their mechanical properties were also measured.The results indicated that titania could be introduced into the blends of bismaleimide–polyetherimide(BMI/PEI) by sol–gel reaction. Although, the titania content in BMI-rich phase was higher than that in PEI-rich phase, the titania particles dispersed in the hybrids were almost uniform. The introduction of titania actually changed the ultimate phase structure of the PEI modified BMI system because of the chelate complex formation between o,o′-diallyl bisphenol A and dibutoxy bis(acetylacetonato) titanium (IV), which was proved by their ultraviolet spectra. If the content of titania was increased under a specific PEI content, the morphology of the bismaleimide–polyetherimide–titania hybrids remained unaffected apparently, while its mechanical properties were obviously improved.     

Effect of Al and C on structure and mechanical properties of Fe–Al–C alloys

Abstract

Effect of aluminium and carbon content on the microstructure and mechanical properties of Fe–Al–C alloys has been investigated. Alloys were prepared by combination of air induction melting with flux cover (AIMFC) and electroslag remelting (ESR). The ESR ingots were hot forged and hot rolled at 1373 K. As rolled alloys were examined using optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to understand the microstructure of these alloys. The ternary Fe–Al–C alloys containing 10·5 and 13 wt-%Al showed the presence of three phases: FeAl with disordered bcc structure, Fe₃Al with ordered DO₃ structure and Fe₃AlC_0·5 precipitates with L′1₂ structure. Addition of high concentration of carbon to these alloys resulted in excellent hot workability and superior tensile at room temperature as well as tensile and creep properties at 873 K. An increase in Al content from 9 to 13 wt-% in Fe–Al–C alloys containing the same levels of carbon has no significant influence on strength and creep properties at 873 K, however resulted in significant improvement in room temperature strength accompanied by a reduction in room temperature ductility.     

Characteristic times of oxygen mass transfer at the liquid metal–vapour interface

The interactions of liquid metals and alloys with the environment mostly depends on the thermodynamic properties of the liquid surface. In fact, the surface tension is strongly influenced by the presence in the surrounding atmosphere of reactive gases through solution, adsorption mechanisms and/or surface reactions. In particular, oxygen, which shows a high surface activity towards a large number of metallic systems, is the most important contaminant of liquid metals and alloys.Theoretical approaches for estimating the oxygen mass transfer at the liquid–vapour interface under inert atmosphere and vacuum have been developed already in order to relate the observed physical properties to the real surface composition data.In the present work a model of the interfacial transport of a liquid metal–oxygen system under Knudsen conditions that foresees the temporal evolution of the interfacial composition is presented. The diffusion characteristic times for reaching steady-state conditions are evaluated in order to define two system sizes depending on the different oxygen transport mechanisms in the liquid phase.An experimental study of the interface evolution is at present under way and preliminary results show a satisfactory agreement with theoretical studies.     

Investigation of corrosion and mechanical properties of Al–Cu–SiC–xNi composite alloys

In this study, dry sliding wear behavior and corrosion resistance of Al–Cu–SiC–xNi (x: 0, 0.5, 1, 1.5 wt.%) composites were investigated. Effect of nickel content on the microstructure and hardness of the alloys was also studied. Wear tests were conducted using a ball on disc wear test device. Corrosion behavior of Al–Cu–SiC–xNi composite alloys in 3.5% NaCl solution was investigated by using potentiodynamic polarization, impedance spectroscopy and cronoamperometric methods. The results showed that the hardness of the composite alloy increases with increasing nickel content. Maximum wear resistance is reported with the addition of 1 wt.%Ni. It was determined that corrosion resistance of Al–Cu–SiC composite alloys improved with increasing nickel content in the alloy.     

Investigation of solidification behavior and associate microstructures of Co–Cr–W and Co–Cr–Mo alloy systems using DSC technique

This article presents a study of solidification behavior and the corresponding microstructure of Co–Cr–W and Co–Cr–Mo alloy systems using the differential scanning calorimetry technique. The influence of main constituents on the solidification behavior and associate microstructures of these alloys are investigated. It is found that chemical composition influences significantly the solidification behavior of cobalt-based alloys. Solution-strengthened alloy has the highest solidification temperature and narrowest solidification range. Presence of carbon decreases the solidification temperature and increases the solidification range. Addition of boron greatly decreases the solidification temperature. Carbon content dominates the solidification behavior of cobalt-based alloys when the contents of the solution-strengthening elements Mo and Ni are within their saturation in the solution matrix. However, as these contents reach a certain level, formation of intermetallic compounds changes the solidification behavior of these alloys remarkably. Increase in the contents of solution-strengthening elements reduces the solid solution transformation temperature and the eutectic temperature when carbon content is constant.     

Formation and thermal stability of Ca–Mg–Zn and Ca–Mg–Zn–Cu bulk metallic glasses

Several Ca–Mg–Zn and Ca–Mg–Zn–Cu bulk metallic glasses were produced by copper mold casting method. The alloy compositions were selected using specific criteria recently identified by the authors. The glass transition temperature, crystallization temperature, temperature interval of the supercooled region, melting temperature as well as heats of crystallization, and melting are reported for these alloys.     

Oxidation and abrasive wear of Fe–Si and Fe–Al intermetallic alloys

In the present work, intermetallic alloys Fe–Si and Fe–Al (Fe₃Si–C–Cr and Fe₃Al-C), produced by induction melting, were evaluated regarding their oxidation and abrasive resistance. The tests performed were quasi-isothermal oxidation, cyclic oxidation, and dry sand/rubber wheel abrasion. As reference, the ASTM A297-HH grade stainless steel was tested in the same conditions. In the oxidation tests, the Fe–Al based alloy presented the lowest oxidation rate, and the Fe–Si based alloy achieved the best results in the abrasion test, showing better performance than the HH type stainless steel.     

Structural and physical properties of Ni–Tb–Fe–O system

A series of soft ferrites in the system Ni_1 ? xTb_xFe₂O₄ (0 ≤ x ≤ 0.2), was prepared by a standard ceramic technique. The influence of terbium content was investigated by means of X-ray diffraction, Fourier Transform Infrared (FTIR) spectroscopy and scanning electron microscopy. The X-ray diffraction analysis reveals that the samples have a cubic spinel (single phase) structure for 0 ≤ x ≤ 0.08; for x > 0.08 a small peak of orthorhombic phase (TbFeO₃) appears and becomes more conspicuous with increased terbium substitution. The lattice parameter changes in a non-linear way as a function of terbium content which may be attributed to differences in the ionic radii of the cations involved and the solubility limit of terbium ions. A gradual increase in the bulk density was observed with the increase of terbium concentration, from 5.13 g/cm³ to 5.69 g/cm³. FTIR absorption spectra of the Ni–Tb–Fe–O system were investigated in the wave number range 370–1500 cm^? 1. Each spectrum exhibited two main absorption bands, thereby confirming the spinel structure.     

“Averaging” method in problems of convective mass and heat transfer

An approximate method is proposed for the solution of nonlinear boundary problems of convective heat and mass transfer; the method is based on the procedure of averaging equations or boundary conditions.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 47, No. 2, pp. 205–215, August, 1984.     

Purification and high-resolution top-down mass spectrometric characterization of human salivary α-amylase

Human salivary α-amylase (HSAMY) is a major component of salivary secretions, possessing multiple important biological functions. Here we have established three methods to purify HSAMY in human saliva for comprehensive characterization of HSAMY by high-resolution top-down mass spectrometry (MS). Among the three purification methods, the affinity method based on the enzyme-substrate specific interaction between amylase and glycogen is preferred, providing the highest purity HSAMY with high reproducibility. Subsequently, we employed Fourier transform ion cyclotron resonance MS to analyze the purified HSAMY. The predominant form of α-amylase purified from saliva of various races and genders is nonglycosylated with the same molecular weight of 55,881.2, which is 1885.8 lower than the calculated value based on the DNA-predicted sequence. High-resolution MS revealed the truncation of the first 15 N-terminal amino acids (-1858.96) and the subsequent formation of pyroglutamic acid at the new N-terminus Gln (-17.03). More importantly, five disulfide bonds in HSAMY were identified (-10.08) and effectively localized by tandem MS in conjunction with complete and partial reduction by tris (2-carboxyethyl) phosphine. Overall, this study demonstrates that top-down MS combined with affinity purification and partial reduction is a powerful method for rapid purification and complete characterization of large proteins with complex and overlapping disulfide bond patterns.     

Microstructure and magnetic studies of Mg–Ni–Zn–Cu ferrites

Soft Mg–Ni–Zn–Cu spinel ferrites having general chemical formula Ni_xMg_0.5−xCu_0.1Zn_0.4Fe₂O₄ (where x = 0.1, 0.2, 0.3, 0.4 and 0.5) were prepared by standard double sintering ceramic method. The samples were characterized by X-ray diffraction at room temperature. The X-ray diffraction (XRD) study revealed that lattice parameter decreases with increase in Ni content, resulting in a reduction in lattice strain. The electrical and magnetic properties of the synthesized ferrites have been investigated as a function of temperature. The variation of initial permeability and AC susceptibility with temperature exhibits normal ferrimagnetic behavior. The variation of initial permeability with frequency is studied. The Curie temperature (T_C) in the present work was determined from initial permeability and AC susceptibility. The Curie temperature increases with Ni content.     

Dilatometric behavior and microstructure of sintered Fe–NbC and Fe–TaC composites

Fe-reinforced composites were manufactured by the addition of 10–20 wt.% NbC or TaC particles aiming at improved mechanical and wear behavior. Two varieties of Fe powders from Hoeganaes Corp. were used, Ancorsteel 1000B and 45P. Composites produced using the former variety included a small amount of Fe₃P to induce liquid-phase sintering whereas 45P powder was pre-alloyed with P by the manufacturer. The hardness of the matrix was adjusted adding carbon to the composite mixture. The powders were milled for different times and annealed prior to pressing. A dilatometric study was carried out under hydrogen to establish optimum sintering profiles. Relative densities up to 97% TD were achieved. Both microstructure and density of the sintered pellets were evaluated in order to establish correlations involving composition, processing parameters and microstructure of the composite.     

Bend formability and strength of Cu–Be–Co alloys

The effects of addition of 0.01 and 0.03 wt% Mg on the bend formability and strength of a Cu–1.8 wt% Be–0.21 wt% Co alloy aged at 320 °C for 30 min have been investigated metallographically. The addition of Mg to the Cu–Be–Co alloy enhances the bend formability and strength of the alloy. The enhancement of strength is caused by the increase in volume fraction of g_\textI^￠ \gamma_{\text{I}}^{\prime } precipitates in the Cu matrix. In bending of the alloys with and without 0.01 and 0.03 wt% Mg, a number of micro necks first arise along grain boundaries, and part of them grows, resulting in surface wrinkles, which finally lead to surface cracking. The cracking is initiated from voids formed by destruction of bar-like γ precipitates in discontinuous precipitation (DP) cells and propagates along grain boundaries. The addition of Mg decreases the width of DP cells, resulting in better bend formability. This arises because smaller stress concentration due to less inhomogeneous deformation develops in cells and, as a result, destruction of the γ precipitates in cells occurs less easily as the cell width decreases.     

Microstructure and solidification behavior of Cu–Ni–Si alloys

The microstructure and solidification behavior of Cu–Ni–Si alloys with four different Cu contents was studied systematically under near-equilibrium solidification conditions. The microstructures of these Cu–Ni–Si alloys were characterized by SEM and the phase composition was identified by XRD analysis. The phase transition during the solidification process was studied by DTA under an Ar atmosphere. The results show that the microstructure and solidification behavior is closely related to the composition of Cu–Ni–Si alloys. The microstructure of Cu–Ni–Si alloys with higher than 40% Cu content consists of primary phase α-Cu(Ni, Si) and eutectic phase (β₁-Ni₃Si + α-Cu(Ni,Si).When the Cu content is about 40%, only the eutectic phase (β₁-Ni₃Si + α-Cu(Ni,Si)) is present. DTA analysis shows there are three phase transitions during every cooling cycle of alloys with higher than 40% Cu content, but only one for 40% Cu content. Cu–Ni–Si alloy with 40% Cu solidifies by a eutectic reaction, but Cu–Ni–Si alloys with higher than 40% Cu content solidify as a hypoeutectic reaction.     

DSC and TEM characterizations of thermal stability of an Al–Cu–Mg–Ag alloy

Assessment of long-term stability of an aluminium alloy exposed to elevated temperatures is important in the design of lightweight aerospace structures. The manner in which differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) are used together in monitoring microstructural evolution, and thereby assess phase stabilities in an Al–5.1Cu–0.8 Mg–0.5 Ag–0.7 Mn–0.13 Zr (wt%) alloy, are described. DSC thermograms of the alloy, spanning room temperature to 400°C, revealed the presence of two endotherms and an exotherm. TEM investigation has identified these thermal events to be associated with , S, and precipitates. Quantitative TEM was used to measure diameter, thickness, number density, and volume fraction of the precipitates in the alloy exposed at 135°C for times as long as 3000 h. The quantitative TEM results are correlated with the DSC signatures relating to precipitation, dissolution, and coarsening reactions affecting the , S, and precipitates in the exposed alloy.     

Influence of titanium and nitrogen on hot ductility of C–Mn–Nb–Al steels

Abstract

The influence of small additions of titanium on the hot ductility of C–Mn–Nb–Al steels has been examined. Titanium and nitrogen levels varied in the ranges 0·014–0·045 and 0·004–0·011 wt-%, respectively, so that a wide range of Ti/N ratios could be studied. The tensile specimens were cast and cooled at average cooling rates of 25, 100, and 200 K min^-1 to test temperatures in the range 1100–800°C and strained to failure at a strain rate of 2 × 10^-3 s^-1. It was found that ductility in the titanium containing niobium steels improved with a decrease in the cooling rate, an increase in the size of the titanium containing precipitates, and a decrease in the volume fraction of precipitates. Coarser particles could be obtained by increasing the Ti/N ratio above the stoichiometric ratio for TiN and by testing at higher temperatures. However, ductility was generally poor for these titanium containing steels and it was equally poor when niobium was either present or absent. For steels with ～0·005 wt-%N ductility was very poor at the stoichiometric Ti/N ratio of 3·4 : 1. Ductility was better at the higher Ti/N ratios but only two of the titanium containing niobium steels gave better ductility than the titanium free niobium containing steels and then only at temperatures below about 950–900°C. One of these steels had the lowest titanium addition (0·014 wt-%), thus limiting the volume fraction of fine Ti containing particles and the other had the highest Ti/N ratio of 8 : 1. However, even for these two steels ductility was worse than for the titanium free steels in the higher temperature range. The commercial implications of these results are discussed.