Elemental partitioning and microstructural development in duplex stainless steel weld metal

A thermodynamic analysis which is capable of estimating the austenite/ferrite equilibria in duplex stainless steels has been carried out using the sublattice thermodynamic model. The partitioning of alloying elements between the austenite and ferrite phases has been calculated as a function of temperature. The results showed that chromium partitioning was not influenced significantly by the temperature. The molybdenum, on the other hand, was found to partition preferentially into ferrite phase as the temperature decreases. A strong partitioning of nickel into the austenite was observed to decrease gradually with increasing temperature. Among the alloying elements, average nitrogen concentration was found to have the most profound effect on the phase balance and the partitioning of nitrogen into the austenite. The partitioning coefficient of nitrogen (the ratio of the mole fraction of nitrogen in the austenite to that in the ferrite) was found to be as high as 7.0 around 1300 K. Consequently, the volume fraction of austenite was influenced by relatively small additions of nitrogen. The results are compared with the experimentally observed data in a duplex stainless steel weld metal in conjunction with the solid state δ → δ + γ phase transformation. Particular attention was given to the morphological instability of grain boundary austenite allotriomorphs. A compariso between the experimental results and calculations indicated that the instability associated with irregular austenite perturbations results from the high degree of undercooling. The results suggest that the model can be used successfully to understand the development of the microstructure in duplex stainless steel weld metals.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

Intragranular nucleation of austenite

The mechanism of intragranular nucleation of austenite in a duplex stainless steel (Fe-23.1 Cr-6.1 Ni-3.1 Mo-O.165 N-0.017 C, wt.%) weld metal and heat-affected zone (HAZ) has been examined. In the weld metal the acicular austenite is found to nucleate intragranularly on inclusions and subsequent plates form sympathetically resulting in a fine interlocked microstructure. Austenite plates adopt the Kurdjumov-Sachs orientation relationship with the ferrite matrix and grow with diffusion-controlled mechanism as evident from partitioning of substitutional alloying elements. At least one set of fine intrinsic dislocations on the austenite/ferrite interphase interfaces is observed suggesting that the boundaries are semi-coherent. The high cooling rates involved in the HAZ result in a supersaturated ferrite matrix where precipitation of intragranular austenite occurs as a result of reheating associated with subsequent passes. Austenite particles in the HAZ nucleate preferentially away from gain boundary austenite allotriomorphs indicating that intragranular precipitation is favoured by the supersaturated matrix.

Cracking in the welding of cupro-nickel alloys

The problem of variation in weld crack susceptibility caused by small variations in alloy and impurity elements for the 70-30 cupro-nickel alloy has been investigated. Both wrought and cast versions of the alloy have been studied, the main techniques employed being the Varestraint test and weld thermal simulation. In the wrought alloys, cracking has been found to occur mainly in the weld metal, whilst in the cast alloys cracking is extensive in both weld metal and heat affected zone. The previously reported effects of certain impurities (P,S,Si) in increasing cracking have been confirmed, and it has also been shown that Ti and Zr may both have a crack promoting effect at levels commonly found in cupro-nickels, whilst C can interact with several of the other elements investigated to produce a beneficial effect. The testing carried out using the weld thermal simulator has shown that a relationship does exist between hot ductility and weld cracking. In particular, the absence of the peak in ductility in the range 1100°C-900°C on cooling from a temperature near to the solidus is indicative of a highly crack susceptible alloy. Principal practical implications of the investigation concern the relationship of weld metal cracking to alloy composition, especially the level of certain impurities. It would appear that the upper limits permitted by the alloy specifications are unrealistically high. The introduction of lower impurity limits would alleviate the current problems of variability in resistance to cracking during welding.

Ultrasonic inspection of austenitic stainless steel weldments

Ultrasonic waves interact in a complex manner with the metallurgical structure of austenitic weldments resulting in ambiguity when interpreting reflections and at times in misinterpretation of defect positions. In this work, current knowledge of the structure of austenitic welds is outlined, and the influence of this structure on the propagation of ultrasonic waves is reviewed. Using an established and highly accurate technique, data on velocity variations as a function of the angle between the direction of soundwave propagation and the axes of preferred grain orientation existing in such welds, are experimentally obtained. These results and existing theory are used to provide quantitative evidence of (i) anisotropy factors in austenitic welds, (ii) beam skewing effects for different wave modes and polarizations, and (iii) the extent of acoustic impedance mismatch between parent and weld metals. The existence of "false" indications is demonstrated, and suggestions are made into their nature. The effectiveness of conventional transverse wave techniques for inspecting artificial and real defects existing in austenitic weldments is experimentally investigated, the limitations are demonstrated, and possible solutions are proposed. The possibilities offered by the use of longitudinal angle probes for ultrasonic inspection of real and artificial defects existing in austenitic weldments are experimentally investigated, and parameters such as probe angle, frequency and scanning position are evaluated. Detailed work has been carried out on the interaction of ultrasound with fatigue and corrosion-fatigue cracks in the weld metal and the heat affected zones (HAZs) of 316 and 347 types of austenitic weldments, together with the influence of elastic compressive stresses, defect topography and defect geometry. Practical applications of all results are discussed, and more effective means of ultrasonic inspection of austenitic weldments are suggested.

Gas-metal reactions and porosity in the inert gas arc welding of copper

A study has been made of the effects of welding and material variables on the occurrence of porosity in tungsten inert gas arc welding of copper. The experiments were based on a statistical design and variables included, welding current, welding speed, arc atmosphere composition, inert gas flow rate, weld preparation, and base material. The extent of weld metal porosity was assessed by density measurement and its morphology by X-ray radiography and metallography. In conjunction with this the copper-steam reaction has been investigated under conditions of controlled atmosphere arc melting. The welding experiments have shown that the extent of steam porosity is increased by increased water vapour content of the arc atmosphere, increased oxygen content of the base material and decreased welding speed. The arc melting experiments have shown that the steam reaction occurs in the body of the weld pool and proceeds to an apparent equi1ibrium state appropriate to to its temperature, the hydrogen and oxygen being supplied by the dissociation of water vapour in the arc atmosphere. It has been shown conclusively that nitrogen porosity can occur in the tungsten inert gas arc welding of copper and that this porosity can be eliminated by using filler wires containing small amounts of aluminum and titanium. Since it has been shown to be much more difficult to produce sound butt welds than melt runs it has been concluded that the porosity associated with joint fit up is due to nitrogen entrained into tho arc atmosphere. Clearly atmospheric entrainment would also, to a much lesser extent, involve water vapour. From a practical welding point of view it has thus been postulated that use of a filler wire containing small amounts of aluminum and/or titanium would eliminate both forms of porosity since these elements are both strongJy deoxidising and denitriding.

Lithium-aluminium casting alloys and their associated metal-mould reactions

Aluminium - lithium alloys are specialist alloys used exclusively by the aerospace industry. They have properties that are favourable to the production of modern military aircraft. The addition of approximately 2.5 percent lithium to aluminium increases the strength characteristics of the new alloys by 10 percent. The same addition has the added advantage of decreasing the density of the resulting alloy by a similar percentage. The disadvantages associated with this alloy are primarily price and castability. The addition of 2.5 weight percent lithium to aluminium results in a price increase of 100% explaining the aerospace exclusivity. The processability of the alloys is restricted to ingot casting and wrought treatment but for complex components precision casting is required. Casting the alloys into sand and investment moulds creates a metal - mould reaction, the consequences of which are intolerable in the production of military hardware. The primary object of this project was to investigate and characterise the reactions occurring between the newly poured metal and surface of the mould and to propose a method of counteracting the metal - mould reaction. The constituents of standard sand and investment moulds were pyrolised with lithium metal in order to simplify the complex in-mould reaction and the products were studied by the solid state techniques of powder X-Ray diffraction and magic angle spinning nuclear magnetic resonance spectroscopy. The results of this study showed that the order of reaction was: Organic reagents> > Silicate reagents> Non silicate reagents Alphaset and Betaset were the two organic binders used to prepare the sand moulds throughout this project. Studies were carried out to characterise these resins in order to determine the factors involved in their reaction with lithium. Analysis revealed that during the curing process the phenolic hydroxide groups are not reacted out and that a redox reaction takes place between these hydroxides and the lithium in the molten alloys. Casting experiments carried out to assess the protection afforded by various hydroxide protecting agents showed that modern effective, protecting chemicals such as bis-trimethyl silyl acetamide and hexamethyldisilazane did not inhibit the metal - mould reaction to a sufficiently high standard and that tri-methylchlorosilane was consistently the best performer. Tri-methyl chlorosilane has a simple functionalizing mechanism compared to other hydroxide protecting reagents and this factor is responsible for its superior inhibiting qualities. Comparative studies of 6Li and 7Li N.M.R. spectra (M.A.S. and `off angle') establish that, for solid state (and even solution) analytical purposes 6Li is the preferred nucleus. 6Li M.A.S.N.M.R. spectra were obtained for thermally treated laponite clay. At temperatures below 800oC both dehydrated and rehydrated samples were considered. The data are consistent with mobility of lithium ions from the trioctahedral clay sites at 600oC. The superior resolution achievable in 6Li M.A.S.N.M.R. is demonstrated in the analysis of a microwave prepared lithium exchanged clay where 6Li spectroscopy revelaed two lithium sites in comparison to 7Li M.A.S.N.M.R. which gave only a single lithium resonance.

The formation and impact of hazard control policy:a study of the regulation of white lead paint in Britain

Government regulation of industrial hazards is examined in the context of the economic and technical processes of industrial development. Technical problems and costs of control are considered as factors in both the formation and impact of regulation. This thesis focuses on an historical case-study of the regulation of the hazard to painting workers from the use of lead pigments in paint. A regulatory strategy based on the prohibition of lead paints gained initial acceptance within the British state in 1911, but was subsequently rejected in favour of a strategy that allowed continued use of lead paint subject to hygiene precautions. The development of paint technology and its determinants, including concern about health hazards, are analysed, focusing on the innovation and diffusion into the paint industry of the major white pigments: white lead (PbC03 .PB(OH)2)and its substitutes. The process of regulatory development is examined, and the protracted and polarised regulatory d~bate contrasted to the prevailing 'consensual' methods of workplace regulation. The rejection of prohibition is analysed in terms of the different political and technical resources of those groups in conflict over this policy. This highlights the problems of consensus formation around such a strategy, and demonstrates certain constraints on state regulatory activity, particularly regarding industrial development. Member-states of the International Labour Organisation agreed to introduce partial prohibition of lead paint in 1921. Whether this was implemented is related to the economic importance of lead and non-lead metal and pigment industries to a nation. An analysis is made of the control of lead poisoning. The rate of control is related to the economic and technological trajectory of the regulated industry. Technical and organisational characteristics are considered as well as regulatory factors which range from voluntary compliance and informal pressures to direct legal requirements. The implications of this case-study for the analysis of the development and impacts of regulation are assessed.

Synthesis and magnetic properties of Fe-Mn-Cr multinuclear complexes with 4-amino-1,2,4-triazole and oxalate ligands

A multinuclear Fe-Mn-Cr complex with 4-amino-1,2,4-triazole (NH2trz) and oxalate (ox) ligands has been synthesized successfully. The formula of the [Fe(NH2trz)3][ClO4][MnCr(ox)3].4H2O complex has been obtained based on the metal and C, H, N contents. The presence of water molecules, metal-ligand bonding and bridge ligand in the multinuclear complex has been confirmed by its infrared spectrum. The compound crystallizes in the hexagonal system with cell parameters of a = b = 18.695 Å and c = 57.351 Å. The compound shows a gradual spin crossover for iron(II) in the [Fe(NH2trz)3]2+ with transition temperature (T1/2) of 205 K. The antiferromagnetic interaction between Cr(III) and Mn(II) ions in the [MnCr(ox)3]n n- network is observed from the Weiss constant (θ) of –2.3 K.

High-pressure XPS of crotyl alcohol selective oxidation over metallic and oxidized Pd(111)

Here, we report on the first application of high-pressure XPS (HP-XPS) to the surface catalyzed selective oxidation of a hydrocarbon over palladium, wherein the reactivity of metal and oxide surfaces in directing the oxidative dehydrogenation of crotyl alcohol (CrOH) to crotonaldehyde (CrHCO) is evaluated. Crotonaldehyde formation is disfavored over Pd(111) under all reaction conditions, with only crotyl alcohol decomposition observed. In contrast, 2D Pd5O4 and 3D PdO overlayers are able to selectively oxidize crotyl alcohol (1 mTorr) to crotonaldehyde in the presence of co-fed oxygen (140 mTorr) at temperatures as low as 40 °C. However, 2D Pd5O4 ultrathin films are unstable toward reduction by the alcohol at ambient temperature, whereas the 3D PdO oxide is able to sustain catalytic crotonaldehyde production even up to 150 °C. Co-fed oxygen is essential to stabilize palladium surface oxides toward in situ reduction by crotyl alcohol, with stability increasing with oxide film dimensionality.

The tribology of laminated magnetic recording heads

This thesis investigates the mechanisms that lead to pole tip recession (PTR) in laminated magnetic recording heads (also known as "sandwich heads"). These heads provide a platform for the utilisation of advanced soft magnetic thin films in practical recording heads suitable for high frequency helical scan tape recording systems. PTR results from a differential wear of the magnetic pole piece from the tape-bearing surface of the head. It results in a spacing loss of the playback or read signal of 54.6dB per recording wavelength separation of the poles from the tape. PTR depends on the material combination used in the head, on the tape type and the climate - temperature and relative humidity (r.h.). Five head materials were studied: two non-magnetic substrate materials- sintered multi granular CaTi03 and composite CaTi03/ZrTi04/Ti02 and three soft magnetic materials- amorphous CoNbZr, and nanocrystalline FeNbSiN and FeTaN. Single material dummy heads were constructed and their wear rates measured when cycling them in a Hi-8 camcorder against commercially available metal particulate (MP) and metal evaporated (ME) tapes in three different climates: 25°C/20%r.h., 25°C/80%r.h. and 40°C/80%r.h. X-ray photoelectron spectroscopy (XPS) was used to examine changes the head surface chemistry. Atomic force microscopy (AFM) was used to examine changes in head and tape surface topography. PTR versus cycling time of laminated heads of CaTi03/ZrTiO4/Ti02 and FeTaN construction was measured using AFM. The principal wear mechanism observed for all head materials was microabrasion caused by the mating body - the tape surface. The variation in wear rate with climate and tape type was due to a variation in severity in this mechanism, except for tape cycling at 40°C in which gross damage was observed to be occurring to the head surface. Two subsidiary wear mechanisms were found: third body scratching (all materials) and grain pullout (both ceramics and FeNbSiN). No chemical wear was observed, though tribochemical reactions were observed on the metal head surfaces. PTR was found to be caused by two mechanisms - the first differential microabrasion of the metal and substrate materials and which was characterised by a low (~10nm) equilibrium value. The second was by deep ploughing by third body debris particles, thought mainly to be grain pullout particles. This level of PTR caused by this mechanism was often more severe, and of a non-equilibrium nature. It was observed more for ME tape, especially at 40°C/80%r.h. and 25°c/20%r.h. Two other phenomena on the laminated head pole piece were observed and commented upon: staining and ripple texturing.

The automation of resonant thermometer probe measurements

An ultrasonic thermometer has been developed for high temperature measurement over a wide temperature range. It is particularly suitable for use in measuring nuclear fuel rod centerline temperatures in advanced liquid metal and high flux nuclear reactors. The thermometer which was designed to determine fuel temperature up to the fuel melting point, utilizes the temperature dependence of the ultrasonic propagation velocity (related to the elastic modulus} in a thin rod sensor as the temperature transducing mechanism. A pulse excitation technique has been used, where the mechanical resonator at the remote end of the acoustic·line is madto vibrate. Its natural frequency is proportional to the ultrasonic velocity in the material. This is measured by the electronic instrumentation and enables a frequency­ temperature or period-temperature calibration to be obtained. A completely digital automatic instrument has been designed, constructed and tested to track the resonance frequency of the temperature sensors. It operates smoothly over a frequency range of about 30%, more than the maximum working range of most probe materials. The control uses the basic property of a resonator that the stored energy decays exponentially at the natural frequency of the resonator.The operation of the electronic system is based on a digital multichannel transmitter that is capable of operating with a predefined number of cycles in the burst. this overcomes a basic defect in the previous deslgn where the analogue time-delayed circuits failed to hold synchronization and hence automatic control could be lost. Development of a particular type of temperature probe, that is small enough to fit into a standard 2 mm reactor tube has made the ultrasonic thermometer a practicable device for measuring fuel temperature. The bulkiness of previous probes has been overcome, the new design consists of a tuning fork, integral with a 1mm line, while maintaining a frequency of no more than 100 kHz. A magnetostrictive rod, acoustically matched to the probe is used to launch and receive the acoustic oscillations. This requires a magnetic bias and the previously used bulky magnets have been replaced by a direct current coil. The probe is supported by terminating the launcher with a short heavy isolating rod which can be secured to the reactor structure. This support, the bias and launching coil and the launcher are made up into a single compact unit. On the material side an extensive study of a wide range of refractory materials identified molybdenum, iridium, rhenium and tungsten as satisfactory for a number of applications but mostly exhibiting to some degree a calibration drift with thermal cycling. When attention was directed to ceramic materials, Sapphire (single crystal alumina) was found to have numerous advantages, particularly in respect of stability of calibration which remained with ±2°C after many cycles to 1800oC. Tungsten and thoriated tungsten (W - 2% Tho2) were also found to be quite satisfactory to 1600oC, the specification for a Euratom application.

Multiphase modelling of the characteristics of close coupled gas atomization

Not withstanding the high demand of metal powder for automotive and High Tech applications, there are still many unclear aspects of the production process. Only recentlyhas supercomputer performance made possible numerical investigation of such phenomena. This thesis focuses on the modelling aspects of primary and secondary atomization. Initially two-dimensional analysis is carried out to investigate the influence of flow parameters (reservoir pressure and gas temperature principally) and nozzle geometry on final powder yielding. Among the different types, close coupled atomizers have the best performance in terms of cost and narrow size distribution. An isentropic contoured nozzle is introduced to minimize the gas flow losses through shock cells: the results demonstrate that it outperformed the standard converging-diverging slit nozzle. Furthermore the utilization of hot gas gave a promising outcome: the powder size distribution is narrowed and the gas consumption reduced. In the second part of the thesis, the interaction of liquid metal and high speed gas near the feeding tube exit was studied. Both axisymmetric andnon-axisymmetric geometries were simulated using a 3D approach. The filming mechanism was detected only for very small metal flow rates (typically obtained in laboratory scale atomizers). When the melt flow increased, the liquid core overtook the adverse gas flow and entered in the high speed wake directly: in this case the disruption isdriven by sinusoidal surface waves. The process is characterized by fluctuating values of liquid volumes entering the domain that are monitored only as a time average rate: it is far from industrial robustness and capability concept. The non-axisymmetric geometry promoted the splitting of the initial stream into four cores, smaller in diameter and easier to atomize. Finally a new atomization design based on the lesson learned from previous cases simulation is presented.

A failure criterion for fillet welds

The work constitutes a study of the strength of mild steel fillet welds subject to static loading, and the behaviour of flange welded beam-column connections under combined bending and shear. Tests are conducted on short welds in the as-welded and stress relieved conditions, and also on full-size beam-column connections. It is shown that welds under compression have a lower strength than when under tension. Failure of the fillet weld is initiated at the weld root, the important factor controlling the initiation being weld ductility. The greater the residual stress, the lower the weld ductility and ultimate strength. Thermal stress relieving increases strength by as much as 30%. Weld failure plane is rarely at the throat and varies from 0° to 45° depending upon loading condition. Failure plane average stresses are related by a circular function which is expressed in terms of externally applied forces at limit state. The tension weld of a flange-welded beam-column connection always fails before the compression weld. The shear load sharing between the welds is a complex function of elastic compression of the web, elastic/plastic deformation of the flanges, load/deformation characteristics, and the type of load application. Bearing forces between the compression flange and column face produce low level bearing stresses and frictional forces which make a negligible contribution to shear load resistance. Three modes of connection failure are possible; 'end mode', 'bending mode' and 'shear mode', with a sudden change taking place between the two latter.