Search Results (14)

The submerged arc welding (SAW) process is operated at high temperatures, up to 2500 °C, in the arc cavity formed by molten oxy-fluoride flux (slag). These high arc cavity temperatures and the complex interaction of gas–slag–metal reactions in a small space below the arc render the study of specific chemical interactions difficult. The importance of gas phase reactions in the arc cavity of the SAW process is well established. A low-temperature (1350 °C) experimental method was applied to simulate and study the vaporisation and re-condensation behaviour of the gas species emanating from oxy-fluoride flux. Energy dispersive X-ray spectroscopy (EDX) analyses and reaction thermochemistry calculations were combined to explain the role of Al as a de-oxidiser element in gas phase chemistry and, consequently, in nano-strand formation reactions. EDX element maps showed that the nano-strands contain elemental Ti only, and the nano-strand end-caps contain Co-Mn-Fe fluoride. This indicates a sequence of condensation reactions, as Ti in the gas phase is re-condensed first to form the nano-strands and the end-caps formed from subsequent re-condensation of Co-Mn-Fe fluorides. The nano-strand diameters are approximately 120 nm to 360 nm. The end-cap diameter typically matches the nano-strand diameter. Thermochemical calculations in terms of simple reactions confirm the likely formation of the nanofeatures from the gas phase species due to the Al displacement of metals from their metal fluoride gas species according to the reaction: yAl + xMF_y ↔ xM + yAlF_x. The gas–slag–metal equilibrium model shows that TiO₂ in the flux is transformed into TiF₃ gas. Formation of Ti nano-strands is possible via displacement of Ti from TiF₃ by Al to form Al-fluoride gas. Full article

The Amarillo River in Famatina, La Rioja, Argentina, is a natural acidic river with distinctive yellow-ochreous iron precipitates along its course. While mining activities have occurred in the area, the river’s natural acidity is influenced by environmental factors beyond mineralogy, where microbial species have a crucial role. Although iron-oxidising bacteria have been identified, a comprehensive analysis of the entire microbial community in this extreme environment has not yet been conducted. In this study, we employ high-throughput sequencing to explore the bacterial and fungal diversity in the Amarillo River and Cueva de Pérez terraces, considered prehistoric analogues of the current river basin. Fe(II)-enrichment cultures mimicking different environmental conditions of the river were also analysed to better understand the roles of prokaryotes and fungi in iron oxidation processes. Additionally, we investigate the ecological relationships between bacteria and fungi using co-occurrence and network analysis. Our findings reveal a diverse bacterial community in the river and terraces, including uncultured species affiliated with Acidimicrobiia, part of an uncharacterised universal microbial acidic diversity. Acidophiles such as Acidithiobacillus ferrivorans, the main iron oxidiser of the system, and Acidiphilium, which is unable to catalyse Fe(II) oxidation but has a great metabolic flexibility,, are part of the core of the microbial community, showing significant involvement in intraspecies interactions. Alicyclobacillus, which is the main Fe(II) oxidiser in the enrichment culture at 30 °C and is detected all over the system, highlights its flexibility towards the iron cycle. The prevalence of key microorganisms in both rivers and terraces implies their enduring contribution to the iron cycle as well as in shaping the iconic yellow landscape of the Amarillo River. In conclusion, this study enhances our understanding of microbial involvement in iron mineral precipitation, emphasising the collaborative efforts of bacteria and fungi as fundamental geological agents in the Amarillo River. Full article

The scope of this work is to improve the SAW process understanding and present an improved description of the SAW process in terms of gas-slag-metal reactions with alloy powder and Al powder additions. The scope does not include the materials properties of the weld metal. The latter may easily be optimised in the future by changing the weld metal chemistry once the process reactions of different element powders in SAW are understood. Aluminium as de-oxidiser element was applied to SAW to lower the oxygen partial pressure in the process. The results show the Al-Ni-Cr-Co-Cu alloyed weld metal total oxygen content was reduced to 257 ppm O, compared to the base case weld metal at 499 ppm O, made with the same flux and no metal powder additions. Thus, the aluminium that was added as a de-oxidiser element to the SAW process effectively lowered the original flux-induced partial oxygen pressure, both in the arc cavity and at the interface of the molten flux–weld pool phases. This partial oxygen pressure lowering effect of Al also prevents oxidation of Cr, preventing loss of Cr to the slag. Carbon steel was alloyed to 3.9% Al, 4.8% Ni, 4.9% Cr, 4.8% Co, 4.7% Cu at 62% Al yield, 76% Ni yield, 77% Cr yield, 75% Co yield, 74% Cu yield. SEM (scanning electron microscope) work on the three-dimensional (3D) post-weld slag sample show dome cavities with 3D rounded structures embedded in the dome cavity walls, as well as shards and nano-strands on the dome cavity walls. The 3D structures indicate vapour formation and re-condensation of oxy-fluorides. The novel application of the EERZ (effective equilibrium reaction zone) model simulates the mass transfer effects in the SAW process. This model is novel because it is the first model used to calculate the gas-slag-metal phase chemistry changes in SAW as a function of welding time. The novel SAW process modification of adding Al de-oxidiser powder with alloying element powders of the unique combination of Co-Cr-Co-Ni-Al was successfully applied. The results confirm that the gas phase and its reactions must be included in the interpretation and modelling of SAW process metallurgy. Full article

Aluminium metal is not typically added to the submerged arc welding (SAW) process because it is easily oxidised to form unwanted slag in the weld pool. The successful application of aluminium as a de-oxidiser is illustrated in this study by preventing oxidation of Cr and Co to their oxides, thereby preventing element loss to the slag. Unconstrained pure metals of Al, Cr, Co and Cu were applied to investigate the gas formation behaviour of these elements in the SAW arc cavity. Of interest is the effect of copper in the arc cavity in terms of its possible substitution for aluminium. The results confirmed that the Al-Cr-Co-Cu alloyed weld metal total oxygen content was lowered to 176 ppm O, in comparison to 499 ppm O in the weld metal formed from welding with the original flux, which excluded metal powder additions. This lower ppm O value of 176 ppm O confirms that the added aluminium powder effectively lowered the original flux-induced partial oxygen pressure in the arc cavity, and at the molten flux–weld pool interface. Carbon steel was alloyed to 5.3% Co, 5.5% Cr, 5.3% Cu and 4.5% Al at 78% Co yield, 82% Cr yield, 78% Cu yield and 66% Al yield. Thermochemical equilibrium calculations confirm the partial oxygen pressure-lowering effect of aluminium when considering the gas–slag–alloy equilibrium. BSE (backscattered electron) images of the three-dimensional (3D) post-weld slag sample show dome structures which contain features of vapour formation and re-condensation. SEM-EDX (scanning electron microscope-energy dispersive X-ray) maps show that the dome surface matrix phase consists of Al-Mg-Ca-Si-Na-K-Ti-Fe-Mn oxy-fluoride. The spherical 3D structures of 10–40 µm in diameter consist of Fe-Mn-Si fluorides with some Cr, Cu and Co contained in some of the spheres. Cr and Co were observed in distinctive porous structures of approximately 10 µm in size, consisting partly of Cr oxy-fluoride and partly of Co oxy-fluoride. Nano-sized oxy-fluoride strands and spheres in the dome structures confirm vaporisation and re-condensation of oxy-fluorides. Cu and Na formed a distinct condensation pattern on the surface of the Si-Cu-Na-Mn-Fe-Co oxy-fluoride sphere. The results confirm the importance of including gas phase reactions in the interpretation of SAW process metallurgy. Full article

This review is focused on the thermochemical behaviour of fluxes in submerged arc welding (SAW). The English-language literature from the 1970s onwards is reviewed. It was recognised early on that the thermochemical behaviour of fluxes sets the weld metal total ppm O and the element transfer extent from the molten flux (slag) to the weld pool. Despite the establishment of this link between the flux-induced oxygen potential and element transfer, it is also well accepted that the slag–metal equilibrium does not control SAW process metallurgy. Instead, the gas phase must be taken into account to better describe SAW process metallurgy equilibrium calculations. This is illustrated in the gas–slag–metal equilibrium simulation model developed by Coetsee. This model provides improved accuracy in predicting the weld metal total ppm O values as compared to the empirical trend of Tuliani et al. Recent works on the application of Al metal powder with alloying metal powders provide new insights into the likely gas phase reactions in the SAW process and the modification of the flux oxygen behaviour via Al additions. Aluminium may lower the partial oxygen pressure in the arc cavity, and aluminium also lowers the partial oxygen pressure at the weld pool–slag interface. The weld metal total ppm O is lowered with the addition of aluminium in SAW, but not to the same extent as would be expected from steelmaking ladle metallurgy de-oxidation practice when using Al as de-oxidiser. This difference indicates that slag–metal equilibrium is not maintained in the SAW process. Full article

Unconstrained metal powders of Cu, Cr, Ni and Al were applied to submerged arc welding (SAW) to clarify the chemical behaviour of copper in this modified SAW process. Aluminium metal is avoided in SAW because it is easily oxidised. Excessive aluminium oxides in the form of slag or inclusions in the weld metal will lead to poor weld metal materials properties. Aluminium is an effective deoxidiser and can be used to prevent Cr and Ni loss to the slag by preventing oxidation of these metals. The results show that carbon steel was alloyed to 5.3% Cr, 5.3% Ni, 3.6% Al and 5.2% Cu at 80% Cr yield, 81% Ni yield, 54% Al yield and 79% Cu yield. BSE (backscattered electron) images of the three-dimensional (3D) post-weld slag sample show 3D structures within the slag dome. The 3D structures contain features of vapour formation and recondensation. In addition, nano-strands appear in the 3D structures and confirm the vaporisation and recondensation of fluorides. The chemical behaviour of copper metal powder added in SAW is to vaporise as metallic copper and incorporate in the Al-Si-Mg-Ca-Mn-Fe-Cu-Na-Cr-Ni fluoride. Copper, in combination with aluminium, has a stabiliser effect in SAW due to its formation of an initial alloy melt of low liquidus temperature, thus decreasing the temperature required to melt high-melting-point metals such as Cr into the weld pool. Although Al and Cu have similar vapour pressures at specific temperatures, it appears that Cu does not substitute for Al in the gas phase. Gas-slag-alloy thermochemical equilibrium calculations confirm the partial oxygen pressure lowering effect of aluminium and the vaporisation of copper as metallic copper with very little copper-fluoride species expected to form. The quantity of metallic copper vaporisation calculated in the gas-slag-alloy thermochemical equilibrium is much higher than the vaporisation quantity measured in welding. This may be due to recondensation of vaporised copper which is not accounted for in the equilibrium calculation at the set arc cavity temperature, as well as the effect of surface-active elements such as sulphur and oxygen in limiting the vaporisation reaction of copper. Full article

Aluminium metal is avoided as main reactant in submerged arc welding (SAW) because it is easily oxidised in this process. Aluminium is an effective de-oxidiser and can be used to prevent Cr and Co loss to the slag by preventing oxidation of these metals. In our novel application of aluminium metal powder in SAW we demonstrate the modification of flux oxygen behaviour. The Co-Cr-Al-alloyed weld metal total oxygen content is decreased to 180 ppm O, compared to 499 ppm O in the weld metal from the original flux, welded without metal powder additions. The flux oxygen behaviour is modified by the added aluminium powder through the lowering of the original flux-induced partial oxygen pressure in the arc cavity and at the molten flux-weld pool interface. Carbon steel was alloyed to 5.9% Co, 6.3 % Cr and 5.1% Al at 81% Co yield, 87% Cr yield and 70% Al yield. Gas-slag-alloy thermochemical equilibrium calculations confirm the partial oxygen-pressure-lowering effect of aluminium. BSE (backscattered electron) images of the three-dimensional (3D) post-weld slag sample show dome structures which contain features of vapour formation and re-condensation. These features consist of small spheres (sized less than 10 μm) and smaller needle-shaped particles coalescing into a porous sphere. EDX analyses show that the spheres consist of Si-Na-K-Fe-Mn-Co-Cr oxy-fluoride and the needles consist of low oxygen Si-Al-Ca-Mg-Na-K-Fe-Mn-Co-Cr oxy-fluoride. The element distribution and speciation data from the EDX analyses confirm modification of the flux oxygen behaviour via aluminium powder addition in lowering the partial oxygen pressure, which in turn prevents oxidation of Cr and Co and minimise losses to the slag. Full article

Obstructive sleep apnoea (OSA) is associated with cardiovascular and metabolic comorbidities, including hypertension, dyslipidaemia, insulin resistance and atherosclerosis. Strong evidence suggests that OSA is associated with an altered lipid profile including elevated levels of triglyceride-rich lipoproteins and decreased levels of high-density lipoprotein (HDL). Intermittent hypoxia; sleep fragmentation; and consequential surges in the sympathetic activity, enhanced oxidative stress and systemic inflammation are the postulated mechanisms leading to metabolic alterations in OSA. Although the exact mechanisms of OSA-associated dyslipidaemia have not been fully elucidated, three main points have been found to be impaired: activated lipolysis in the adipose tissue, decreased lipid clearance from the circulation and accelerated de novo lipid synthesis. This is further complicated by the oxidisation of atherogenic lipoproteins, adipose tissue dysfunction, hormonal changes, and the reduced function of HDL particles in OSA. In this comprehensive review, we summarise and critically evaluate the current evidence about the possible mechanisms involved in OSA-associated dyslipidaemia. Full article

Flux formulations are specified to target chemical and physico-chemical parameters. Chemical parameters set flux element transfer behaviours and weld metal oxygen contents. Physico-chemical parameters such as slag viscosity, surface tension and melting range are targeted to ensure an acceptable weld bead profile and surface appearance. Slag detachability is an important physico-chemical property required to ensure high welding productivity, smooth weld bead surface and no slag entrapment. Here, bead-on-plate welding tests were made with and without metal powder additions, including aluminium powder as a de-oxidiser. Difficult slag detachability was observed in weld runs made with metal powder additions. Mineralogy of the post-weld slags, and thermochemical calculations, show that the flux was modified due to the aluminothermic reduction of MnO and SiO₂ from the slag to form alumina. Increased quantities of spinel phase were identified in the post-weld slag samples, at the weld pool–slag interface. The combined effect of increased slag viscosity, from increased spinel in the slag, and lowered weld pool solidus temperature, resulted in the formation of a rough bead surface morphology, which, in turn, caused mechanical fixation of the slag to the weld bead. Flux modification to higher CaF₂ content should ensure that higher quantities of spinel phase can be tolerated in the slag. Full article

Human vitamin K epoxide reductase (hVKORC1) enzymatic activity requires an initial activation by a specific redox protein, a less studied step in the hVKORC1 vital cycle. Significant steric conditions must be met by enzymes, being that to adapt their configurations is mandatory for hVKORC1 activation. We studied, by molecular dynamics (MD) simulations, the folding and conformational plasticity of hVKORC1 in its inactive (fully oxidised) state using available structures, crystallographic and from de novo modelling. According to the obtained results, hVKORC1 is a modular protein composed of the stable transmembrane domain (TMD) and intrinsically disordered luminal (L) loop, possessing the great plasticity/adaptability required to perform various steps of the activation process. The docking (HADDOCK) of Protein Disulfide Isomerase (PDI) onto different hVKORC1 conformations clearly indicated that the most interpretable solutions were found on the target closed L-loop form, a prevalent conformation of hVKORC1’s oxidised state. We also suggest that the cleaved L-loop is an appropriate entity to study hVKORC1 recognition/activation by its redox protein. Additionally, the application of hVKORC1 (membrane protein) in aqueous solution is likely to prove to be very useful in practice in either in silico studies or in vitro experiments. Full article

Al assisted alloying of carbon steel in Submerged Arc Welding (SAW) by Al-Cr-Ti-Cu unconstrained metal powders is applied. A base case without metal powder additions is compared to two metal powder addition schedules, Al-Cu-Ti and Al-Cu-Ti-Cr. Al powder is used as a deoxidiser element to control the oxygen partial pressure at the weld pool–molten flux interface to ensure that most of the Ti and Cr metal powder is transferred into the weld pool and that the weld metal ppm O is controlled within acceptable limits of 200 to 500 ppm O. The likely sequence of alloy melt formation is deduced from the relevant alloy phase diagrams. The effect of Fe addition into the initial Al-Cu-Ti and Al-Cu-Ti-Cr alloy melt is illustrated in thermochemical calculations. Increased metal deposition productivity with metal powder addition in SAW is confirmed. The metal deposition rates increased by 19% and 40% when Al-Cu-Ti and Al-Cu-Ti-Cr powders were applied at the same weld heat input used in the absence of metal powder additions. Full article

The recycling of valuable metals from spent lithium-ion batteries (LIBs) is highly important to secure the sustainable production of new LIBs and reduce the dependence on virgin resources. The present paper aims to study the smelting behaviour of black mass (BM) from spent LIBs and investigate the effect of graphite on metal recovery in a carbon-saturated hot metal bath and in a low-carbon steel bath. The smelting trials of BM were conducted in a technical scale (150 kg) induction furnace using hot metal and steel scrap at operating temperatures in the range of 1278–1438 °C and 1470–1610 °C, respectively. Two grades of BM were applied in the current study; high-Ni BM and high-Co BM. Parts of both grades of the BM were briquettes to enhance the direct reduction of metal oxides with embedded graphite and to reduce the dust generation during loading into the furnace. The briquette BM was charged to carbon-saturated hot metal bath while the other part of the BM was subjected to de-coking in a muffle furnace in an oxidising atmosphere to remove graphite (37–39%) and to concentrate the valuable metals in the BM. The de-coked BM was loaded directly, without the need for the briquette, to the low-carbon steel bath. The results indicated that smelting of the de-coked BM in a steel bath is more efficient in metal recovery than the smelting of the corresponding briquette BM in a molten hot metal bath. The highest recovery rate of Co, Ni and Cu (98–99%) was obtained by smelting de-coked high-Co BM in a low-carbon molten steel bath, while the lowest recovery rate (38–55%) was obtained by smelting the briquette high-Ni BM in the carbon-saturated hot metal bath. Full article

Agaricomycetes fungi responsible for decay of wood and other lignocellulosic substrates constitute a valuable source of lignin-degrading enzymes. Among these enzymes, laccases (multi-copper oxidases) present remarkable biotechnological potential as environmentally friendly biocatalysts able to oxidize a wide range of aromatic compounds using oxygen as the only requirement. Laccases from saprotrophic Agaricales species have been much less studied than laccases from Polyporales, despite the fact that the former fungi are excellent sources of laccases. Here, the gene of a novel laccase of Agrocybe pediades, that is secreted by the fungus during lignocellulose degradation, was synthesised de novo and expressed in Saccharomyces cerevisiae using an improved signal peptide previously obtained and enzyme directed evolution. The characterization of the new laccase variants provided new insights on the contribution of different amino acid residues to modulate laccase production, catalytic activity or optimal pH. The selected double-mutated variant also showed interesting properties as a biocatalyst, such as the ability to oxidise a wide range of substrates, including high-redox potential mediators and recalcitrant organic dyes, improved activity at neutral pH and high tolerance to inhibitors. Finally, we demonstrate the existence of three N-glycosylation sites in the laccase and their distinct effect on the secretion or catalytic activity of the enzyme. Full article

The Copahue geothermal system is a natural extreme environment located at the northern end of the Cordillera de los Andes in Neuquén province in Argentina. The geochemistry and consequently the biodiversity of the area are dominated by the activity of the Copahue volcano. The main characteristic of Copahue is the extreme acidity of its aquatic environments; ponds and hot springs of moderate and high temperature as well as Río Agrio. In spite of being an apparently hostile location, the prokaryotic biodiversity detected by molecular ecology techniques as well as cultivation shows a rich and diverse environment dominated by acidophilic, sulphur oxidising bacteria or archaea, depending on the conditions of the particular niche studied. In microbial biofilms, found in the borders of the ponds where thermal activity is less intense, the species found are completely different, with a high presence of cyanobacteria and other photosynthetic species. Our results, collected during more than 10 years of work in Copahue, have enabled us to outline geomicrobiological models for the different environments found in the ponds and Río Agrio. Besides, Copahue seems to be the habitat of novel, not yet characterised autochthonous species, especially in the domain Archaea. Full article