Chemical analysis of powdered metallurgical slags by X-ray fluorescence spectrometry

Slag composition determines the physical and chemical properties as well as the application performance of molten oxide mixtures. Therefore, it is necessary to establish a routine instrumental technique to produce accurate and precise analytical results for better process and production control. In the present paper, a multi-component analysis technique of powdered metallurgical slag samples by X-ray Fluorescence Spectrometer (XRFS) has been demonstrated. This technique provides rapid and accurate results, with minimum sample preparation. It eliminates the requirement for a fused disc, using briquetted samples protected by a layer of Borax(R). While the use of theoretical alpha coefficients has allowed accurate calibrations to be made using fewer standard samples, the application of pseudo-Voight function to curve fitting makes it possible to resolve overlapped peaks in X-ray spectra that cannot be physically separated. The analytical results of both certified reference materials and industrial slag samples measured using the present technique are comparable to those of the same samples obtained by conventional fused disc measurements.

Galvanic corrosion of magnesium alloy AZ91D in contact with an aluminium alloy, steel and zinc

An investigation was carried out into the galvanic corrosion of magnesium alloy AZ91D in contact with zinc, aluminium alloy A380 and 4150 steel. Specially designed test panels were used to measure galvanic currents under salt spray conditions. It was found that the distributions of the galvanic current densities on AZ91D and on the cathodes were different. An insulating spacer between the AZ91D anode and the cathodes could not eliminate galvanic corrosion. Steel was the worst cathode and aluminium the least aggressive to AZ91D. Corrosion products from the anode and cathodes appeared to be able to affect the galvanic corrosion process through an alkalisation, passivation, poisoning effect or shortcut effect. (C) 2003 Elsevier Ltd. All rights reserved.

Effect of curve fitting parameters on quantitative analysis of Fe0.94O and Fe2O3 using XPS

The XPS peaks of Fe 3p for Fe2+ and Fe3+ in FeO and Fe2O3, respectively, have been measured and the effects of curve fitting parameters on interpretation of the data have been analysed. Firstly, the peak fit parameters, i.e. (1) the number of peaks to be deconvoluted, (2) the range of the peak for back ground subtraction, (3) straight line (Li) or the Shirley (Sh) background subtraction method, (4) GL ratio (the ratio of Gaussian and Lorentzian contribution to the peak shape) and (5) asymmetry factor (AS), are manually selected. Secondly, the standard peak fit parameters were systematically investigated. The peak shape was fitted to a Voigt function by changing the peak position, the peak height and the full width at half maximum (FWHM) to minimize the chi(2). The recommended peak positions and peak parameters for Fe2+ and Fe3+ in iron oxides have been determined. (c) 2006 Elsevier B.V. All rights reserved.

Effect of sample geometry on regression rate of the melting interface for carbon steel burned in oxygen

Promoted-ignition testing on carbon steel rods of varying cross-sectional area and shape was performed in high pressure oxygen to assess the effect of sample geometry on the regression rate of the melting interface. Cylindrical and rectangular geometries and three different cross sections were tested and the regression rates of the cylinders were compared to the regression rates of the rectangular samples at test pressures around 6.9 MPa. Tests were recorded and video analysis used to determine the regression rate of the melting interface by a new method based on a drop cycle which was found to provide a good basis for statistical analysis and provide excellent agreement to the standard averaging methods used. Both geometries tested showed the typical trend of decreasing regression rate of the melting interface with increasing cross-sectional area; however, it was shown that the effect of geometry is more significant as the sample's cross sections become larger. Discussion is provided regarding the use of 3.2-mm square rods rather than 3.2-mm cylindrical rods within the standard ASTM test and any effect this may have on the observed regression rate of the melting interface.

Implications of restructuring and privatisation for competitiveness and perfomance:two Brazilian steel companies

The thesis examines the effects of the privatisation process on productivity, competitiveness and performance in two major Brazilian steel companies, which were privatised in between 1991 and 1993. The case study method was adopted in this research due to its strengths as a useful technique allowing in-depth examination of the privatisation process, the context in which it happened and its effects on the companies. The thesis has developed a company analysis framework consisting of three components: management, competitiveness/productivity and performance and examined the evidence on the companies within this framework.The research indicates that there is no straightforward relationship between privatisation, competitiveness and performance. There were many significant differences in the management and technological capabilities, products and performance of the two companies, and these have largely influenced the effects of privatisation on each company. Company Alpha's strengths in technological and management capabilities and high value added products explain strong productivity and financial performance during and after privatisation. Company Beta's performance was weak before the privatisation and remained weak immediately after. Before the privatisation, weaknesses in management, commodity type low value added products and shortage of funds for investment were the major problems. These were compounded by greater government interference. Despite major restructuring, the poor performance has continued after privatisation largely because the company has not been able to improve its productivity sufficiently to be cost competitive in commodity type markets. Both companies state that their strategies have changed significantly. They claim to be more responsive to market conditions and customers and are attempting to develop closer links with major customers. It is not possible to assess the consequences of these changes in the short time that has elapsed since privatisation but Alpha appears to be more effective in developing a coherent strategy because of its strengths. Both companies accelerated their programme of organisational restructuring and reducing the number of their employees during the privatisation process to improve productivity and performance. Alpha has attained standards comparable to major international steel companies. Beta has had to make much bigger organisational changes and cuts in its labour force but its productivity levels still remain low in comparison with Alpha and international competitors.

Oxidational wear of low alloy steel in gases other than air

A pin on disc wear machine has been used to study the oxidational wear of low alloy steel in a series of experiments which were carried out under dry wear sliding conditions at range of loads from 11.28 to 49.05 N and three sliding speeds of 2 m/s, 3.5 m/s and 5 m/s, in atmosphere of air, Ar, CO2, 100% O2, 20% O2-80% Ar and 2% O2-98% Ar. Also, the experiments were conducted to study frictional force, surface and contact temperatures and surface parameters of the wearing pins. The wear debris was examined using x-ray diffraction technique for the identification of compounds produced by the wear process. Scanning electron microscopy was employed to study the topographical features of worn pins and to measure the thickness of the oxide films. Microhardness tests were carried out to investigate the influence of the sub-surface microhardness in tribological conditions. Under all loads, speeds and atmospheres parabolic oxidation growth was observed on worn surfaces, although such growth is dependent on the concentration of oxygen in the atmospheres employed. These atmospheres are shown to influence wear rate and coefficient of friction with change in applied load. The nature of the atmosphere also has influence on surface and contact temperatures as determined from heat flow analysis. Unlubricated wear debris was found to be a mixture of αFe2O3, Fe3O4 and FeO oxide. A model has been proposed for tribo-oxide growth demonstrating the importance of diffusion rate and oxygen partial pressure, in the oxidation processes and thus in determination of wear rates.

Nonmetallic inclusion modification and its effect on the final properties of a linepipe steel

Five linepipe type steels were produced in order to study the effect of calcium and magnesium injection on their final properties. Two of these steels were at the extremes of the sulphide range i.e. 0.003 and 0.017% sulphur with no injection attempted; thereby, providing standards to compare with the injected steels. The oxygen level varied from 21 to 63 p.p.m. The cast ingots were controlled-rolled and isothermally rolled in order to study the deformation characteristics of the residual non-metallic inclusions. The structure and cleanliness of these steels was evaluated metallographically using the light microscope, SEM, and image analysis and the results related to their Charpy toughness and HIC resistance. Increasing sulphur levels decreased final properties of the steel. In the untreated state, with as little as 0.003% sulphur, test orientation was highly influential. Modification of sulphur bearing steels was achieved with low modifying element to sulphur ratios provided that the oxygen content was very low. Injection of calcium into steel caused interaction with oxide and sulphide inclusions which was biased toward oxide reduction relative to sulphur removal. Magnesium again reduced oxides and appeared to be linked with aluminia containing inclusions in the final product. It produced improved toughness values relative to a similar sulphur containing calcium treated steel. The results of this work could be extended to establish the mechanism of inclusion modification with magnesium additions to sulphur bearing steels.

Damage analysis of bridge structures using vibrational techniques

Much research is currently centred on the detection of damage in structures using vibrational data. The work presented here examined several areas of interest in support of a practical technique for identifying and locating damage within bridge structures using apparent changes in their vibrational response to known excitation. The proposed goals of such a technique included the need for the measurement system to be operated on site by a minimum number of staff and that the procedure should be as non-invasive to the bridge traffic-flow as possible. Initially the research investigated changes in the vibrational bending characteristics of two series of large-scale model bridge-beams in the laboratory and these included ordinary-reinforced and post-tensioned, prestressed designs. Each beam was progressively damaged at predetermined positions and its vibrational response to impact excitation was analysed. For the load-regime utilised the results suggested that the infuced damage manifested itself as a function of the span of a beam rather than a localised area. A power-law relating apparent damage with the applied loading and prestress levels was then proposed, together with a qualitative vibrational measure of structural damage. In parallel with the laboratory experiments a series of tests were undertaken at the sites of a number of highway bridges. The bridges selected had differing types of construction and geometric design including composite-concrete, concrete slab-and-beam, concrete-slab with supporting steel-troughing constructions together with regular-rectangular, skewed and heavily-skewed geometries. Initial investigations were made of the feasibility and reliability of various methods of structure excitation including traffic and impulse methods. It was found that localised impact using a sledge-hammer was ideal for the purposes of this work and that a cartridge `bolt-gun' could be used in some specific cases.

The transition from severe to mild wear in law alloy steel

The wear rates of sliding surfaces are significantly reduced if mild oxidational wear can be encouraged. It is hence of prime importance in the interest of component life and material conservation to understand the factors necessary to promote mild, oxidational wear, The present work investigates the fundamental mechanism of the running-in wear of BS EN 31!EN 8 steel couples. under various conditions of load. speed and test duration. Unidirectional sliding experiments were carried out on a pin-on~disc wear machine where frictional force, wear rate, temperature and contact resistance were continuously monitored during each test. Physical methods of analysis (x-ray, scanning electron microscopy etc.) were used to examine the wear debris and worn samples. The wear rate versus load curves revealed mild wear transitions, which under long duration of running, categorized mild wear into four distinct regions.α-Fe20s. Fe304, FeO and an oxide mixture were the predominant oxides in four regions of oxidational wear which were identified above the Welsh T2 transition. The wear curves were strongly effected by the speed and test duration. A surface model was used to calculate the surface parameters, and the results were found to be comparable with the experimentally observed parameters. Oxidation was responsible for the transition from severe to mild wear at a load corresponding to the Welsh T2 transition. In the running-in period sufficient energy input and surface hardness enabled oxide growth rate to increase and eventually exceeded the rate of removal, where mild wear ensued. A model was developed to predict the wear volume up to the transition. Remarkable agreement was found between the theoretical prediction and the experimentally-measured values. The oxidational mechanjsm responsible for transitjon to mild wear under equilibrium conditions was related to the formation of thick homogenous oxide plateaux on subsurface hardened layers, FeO was the oxide formed initially at the onset of mild wear but oxide type changed.during the total running period to give an equilibrium oxide whose nature depended on the loads applied.

Defects in steel investment castings

A general investigation was performed, in an industrial environment, of the major types of defect specific to investment castings in steel. As a result of this work three types of metallurgical defect were selected for further study. In the first of these, defects in austenitic stainless steel castings were found to result from deoxidation by-products. As a result of metallographic investigation and the statistical analysis of experimental data, evidence was found to support the hypothesis that the other two classes of defects - in martensite stainless and low alloy steels -both resulted from internal or grain boundary oxidation of the chromium alloy constituent This was often found to be followed by reaction between the metal oxides and the ceramic mould material. On the basis of this study, proposals are made for a more fundamental investigation of the mechanisms involved and interim suggestions are given for methods of ameliorating the effect in an industrial situation.

The effect of elevated temperature on the wear of stainless steel in contact with tungsten carbide

The bearings in the air motors of modern jet aircraft engines must operate dry in hostile conditions at temperatures up to 500° C, where the thrust races in the actuators operate at temperatures up to 300° C. One of the few metallurgical combinations which can function efficiently under these conditions is martensitic stainless steel on tungsten carbide. The work described was initiated to isolate the wear mechanisms of two such steels in contact with tungsten carbide at temperatures up to 500° C. Experiments were carried out on angular contact bearings similar to these used in service, where both rolling and sliding is present and also for pure sliding conditions using a pin-on-disc apparatus. Wear measurements of the bearings were obtained with wear rates, friction and surface temperatures from the pin-on-disc machine for a series of loads and speeds. Extensive X-ray diffraction analysis was carried out on the wear debris, with also S.E.M. analysis and hardness tests on the worn surfaces along with profilometry measurements of the disc. The oxidational parameters of the steel were obtained from measurements of oxide growth rates by ellipsometry. Three distinct mechanisms of wear were established and the latter two were found to be present in both configurations. These involve an oxidational-abrasive mechanism at loads below 40 N with pin surface temperatures up to about 300 °C, with the mechanism changing to severe wear for higher loads. As the temperature increases a third wear mechanism appears due to transfer of relatively soft oxide films to the steel surface reducing the wear rate. Theoretical K factors were derived and compared with experimental values which were found to be in good agreement for the severe wear mechanism. The pin-on-disc experiments may be useful as a screening test for material selection, without the considerable cost of producing the angular contact bearings.

Global optimisation of cold-formed steel sections

In this thesis, standard algorithms are used to carry out the optimisation of cold-formed steel purlins such as zed, channel and sigma sections, which are assumed to be simply supported and subjected to a gravity load. For zed, channel and sigma section, the local buckling, distortional buckling and lateral-torsional buckling are considered respectively herein. Currently, the local buckling is based on the BS 5950-5:1998 and EN 1993-1-3:2006. The distortional buckling is calculated by the direct strength method employing the elastic distortional buckling which is calculated by three available approaches such as Hancock (1995), Schafer and Pekoz (1998), Yu (2005). In the optimisation program, the lateral-torsional buckling based on BS 5950-5:1998, AISI and analytical model of Li (2004) are investigated. For the optimisation program, the programming codes are written for optimisation of channel, zed and sigma beam. The full study has been coded into a computer-based analysis program (MATLAB).

Microstructural analysis of surface and interface zones in concrete

Several of OPC paste and concrete specimens, with different mix proportions, were cast against CPF and impermeable formwork (IF) and the profiles of pore structure, microhardness and scratch hardness of the cover zone were established. The chloride ingress and the depth of carbonation of the surface zone of concrete cast against CPF and IF were investigated. The main mechanisms controlling the ECR processes and the factors affecting such treatment were critically reviewed. Subsequently, as a means of restoring passivation of steel embedded in carbonated concrete, such HCP specimens were subjected to ECR. The influence of ECR on the chemistry of the pore solution and the microstructure of the surface and the steel/cement past interface zones were also studied. The main findings of this investigation were as follows: (a) The thickness of the microstructure gradient of cover concrete is significantly decreased with increasing period of water curing but is relatively unaffected by curing temperature, w/e ratio and the use of cement replacement materials. (b) The scratch hardness technique was shown to be potentially useful for characterising the microstructure and microhardness gradients of the surface zone. (c) A relationship between the microstructure gradient and mass transport properties of the surface zone was established. (d) The use of CPF resulted in a significant reduction in porosity of both the cement paste matrix and the aggregate/cement paste transition zone, and a marked improvement in the resistance of the surface zone to carbonation and the ingress of chloride ions. (e) The ECR treatment resulted in a marked densification of the pore structure and in changes to the pore solution chemistry and the cement phases of near-surface and steel/cement paste transition zones. This effect was more pronounced with current density, period of treatment and particularly with the use of sodium phosphate as an electrolyte.

Elastic-plastic analysis of complete building structures

In this Thesis, details of a proposed method for the elastic-plastic failure load analysis of complete building structures are given. In order to handle the problem, a computer programme in Atlas Autocode is produced. The structures consist of a number of parallel shear walls and intermediate frames connected by floor slabs. The results of an experimental investigation are given to verify the theoretical results and to demonstrate various factors that may influence the behaviour of these structures. Large full scale practical structures are also analysed by the proposed method and suggestions are made for achieving design economy as well as for extending research in various aspects of this field. The existing programme for elastic-plastic analysis of large frames is modified to allow for the effect of composite action of structural members, i.e. reinforced concrete floor slabs and the supporting steel beams. This modified programme is used to analyse some framed type structures with composite action as well as those which incorporate plates and shear walls. The results obtained are studied to ascertain the influence of composite action and other factors on the load carrying capacity of both bare frames and complete building structures. The theoretical failure load presented in this thesis does not predict the overall failure load of the structure nor does it predict the partial failure load of the shear walls and slabs but it merely predicts the partial failure load of a single frame and assumes that the loss of stiffess of such a frame renders the overall structure unusable. For most structures the analysis proposed in this thesis is likely to break down prematurely due to the failure of the slab and shear wall system and this factor must be taken into account in any future work on such structures. The experimental work reported in this thesis is acknowledged to be unsatisfactory as a verification of the limited theory proposed. In particular perspex was not found to be a suitable material for testing at high loads, micro-concrete may be more suitable.