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My roots span four generations. My great grandfather, Christian Frederick Fisher, along with twenty-one others was drowned in the New Australasian mine disaster at Creswick in Victoria in 1882. My grandfather, also named Christian Frederick Fisher, escaped and then followed a career of shaft sinking for large companies and operating small mines (very unprofitably according to my father) when funds allowed. My father, an excellent practical mining and mechanical engineer, was also a small miner and my early entry into the industry was, like many before me, very basic. My introductions to the business end of a No. 4 shovel, drilling with hand steel and later with jack hammers without the benefit of airlegs, feeding heavy cordwood to hungry boilers and felling trees for mine timber soon dispelled any illusions I had that mining was a bed of roses.Before it became well known I knew "Life was not meant to be easy".In a family-owned small gold mine in a remote part of Cape York Peninsula in far north Queensland I was fortunate in obtaining an excellent grounding in reef and deep alluvial mining. Operating in vertical and underlie shafts the variable ground conditions often required close timbering. Steam pumps were used underground and steam winders for hoisting.The complete absence of municipal or government infrastructure in this remote mining field threw responsibility on each mine operator to be self-sufficient, and responsible for mine development and installation of crushing and milling equipment, accommodation and water supply. Conditions, although harsh, were acceptable in the 1930s, and fostered great self-reliance.The first crushing from our Black Cat Mine in 1935 returned nearly 200 oz from 10 tons of ore. Gold was then worth $13 an ounce compared to about $400 an ounce today; but in those depression years of the 1930s our operation was profitable.This basic education not only returned dividends when confronted with difficult mining problems, but created a deep respect for the miners who develop the small mines and who continue to contribute to the industry today, often under difficult conditions.Australia and mining are synonymous. The industry has been immortalised by the famous historian, Professor Geoffrey Blainey, in his book "The Rush that Never Ended".Initial gold discoveries were concealed and exploration was frowned upon by authority as being disruptive to early rural development. But with the discovery of gold in the Bathurst area of New South Wales by Hargreaves in 1851, the rush to the gold fields began followed by an influx of migrants. The traumatic effect on industry and society that followed, created the pattern of the love-hate relationship that at times became temporarily submerged, but is so evident today.In the harsh economic climate of the 19th century with low wages and no welfare, the opportunity to wrest riches from the earth was literally "rushed" by the adventurous, the poor, the rich, people from all walks of life. Pressures developed on preFederation Governments to provide law, order and infrastructure to the rushes that have never ended.

Jan 1, 1984

By J Zhang, L Klemettinen, A Jokilaakso, J Biswas, J Partinen, H O’Brien, A Klemettinen

Waste lithium-ion batteries (LIBs) are important secondary sources of many valuable materials, including Critical Raw Materials (CRMs) defined by the European Union (EU): lithium, cobalt, manganese, and graphite. Additionally, LIBs typically contain nickel and copper, which are classified as Strategic Raw Materials for EU since 2023. In recent years, great effort has been made to develop efficient recycling processes for waste LIBs. Pyrometallurgical processes have been essential in industrial production of metals for many decades. These technologies are relatively mature, with high adaptability for different raw materials. Pyrometallurgical treatment in LIB recycling typically involves the use of smelting processes, in which waste batteries are heated above their melting points and metals are separated through a reduction reaction in the liquid phase. Through this recycling route, cobalt, copper, and nickel can be efficiently recovered in the form of a metal alloy, whereas lithium and manganese are lost in the slag phase. The goal of this work was to increase the recoveries of valuable battery metals through a combination of hydro- and pyrometallurgical unit operations. First, industrial Li-ion battery scrap underwent a selective sulfation roasting stage, where the aim was to transform LiCoO2 and Mn-oxides into Li, Co and Mn sulfates. After roasting, the battery scrap was leached in distilled water with a solid to liquid ratio of 100 g/L at 60°C and recovered 95 per cent of Li, 61 per cent of Mn and 35 per cent of Co. After leaching, the solid leach residue was mixed with industrial Ni-slag and biochar, followed by reduction at 1350°C in argon atmosphere. The high-temperature smelting experiments were conducted as a function of time (5–60 mins) to investigate the reduction behaviour of battery metals. The results show that Co and Ni from the slag and leach residue can be efficiently recovered in the slag cleaning stage.

Jun 19, 2024

By Y Cao, J C. Tien

Occupational health and safety is essential in modern mining workplaces and in China it is often not given enough emphasis due to a lack of knowledge and/or appreciation. Although many health and safety regulations have been passed over the years, serious and relevant laws and regulations on mine health and safety are of recent history (since 2002), the level of stringent enforcement is still inconsistent and accurate field data are scant and not readily available. As of year-end 2006 there were 676 562 recorded cases of occupational diseases in China, of which 616 442 or 91 per cent were miners’ pneumoconiosis. Of these, 146 195 (23 per cent) have died, and an average of 10 000 new cases were added every year between 1991 and 2006. Another report shows that 93.18 per cent of miners have never had a contract with their companies, which means their cases were not even part of China’s official statistics. This study attempts to examine the prevalence of occupational diseases in the Chinese mining industry during 2000–2013, compiled from government annual reports and academic studies. The research will review the correlational analysis among occupational diseases, ventilation practices, protection devices and legislation.CITATION:Cao, Y and Tien, J C, 2015. Occupational diseases in China, with the emphasis on its occurrence in Chinese mine workers, in Proceedings The Australian Mine Ventilation Conference, pp 155–160 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 31, 2015

By A Mooney, G Balog, P Burns, R Brooks

This paper outlines the rationale for the location of the crusher, geotechnical analysis and basis of ground support design, design and scheduling of the chamber and supporting excavations as well as the operational outcomes and lessons learned. Contributions from mining operations, planning, geotechnical and infrastructure teams enabled the Crusher Station One excavation to be completed on schedule, with opportunities taken for underground mining and infrastructure to work safely in parallel to deliver crusher station infrastructure on schedule. Installation of crusher infrastructure was ongoing at the time of writing.

Mar 15, 2021

By C I. Edwards

Phosphorous is typically present in iron ore either in the mineral apatite, Ca5(PO4)3OH, or associated with the goethitic fraction of the ore. In this paper, we present results that show that phosphorous associated with the goethitic fraction can be removed with a heating pretreatment around 300 176;C for 1 h, followed by a caustic leach with 1 - 5 M NaOH, or a leach with sulfuric acid at pH 0.5. The heating pretreatment is considered to dehydroxylate the goethite to form a haematite intermediate phase, ‘protohaematite’, that reacts during the leach making the phosphorous accessible to the leachant. In the acid leach, ten to 15 per cent of the sample was dissolved to obtain a leach product with 0.08 per cent P. In the caustic leach, as no weight loss occurs, it is proposed that iron species associated with the protohaematite have either not dissolved or have reprecipitated at the high pH values of the leach.For an ore containing apatite as the source of phosphorous, a leach with sulfuric acid dissolved the apatite, lowering the phosphorous levels in the sample. The sample treated contained carbonate minerals (including siderite) that also reacted with the acid, and in practice a balance between the dissolution of the apatite and the carbonate minerals may be needed to minimise acid consumption.

Jul 11, 2011

By Bigu J, Grenier M. G, Knight G

Particulate control is a major concern in underground mining and the subject of continuing research world wide. In Canada the federal government's Mining Research Laboratory at EIIiot Lake, Ontario, has been using two aerosol counters to aid its investigations. Specific studies with the units include: a) evaluating total and elemental size efficiencies of dust filtration units: b) characterizing the dust particulate cloud from different mining operations: and c) determining dust transportation characteristics.

Jan 1, 1988

By Shillabeer J

Paste backfill has been adopted by many underground mines in North America and a growing number elsewhere. Paste offers a number of advantages. This paper suggests wider applications of paste technology to surface tailings disposal and water management. Advantages include improved overall stability, potentially easier permitting, smaller water inventory and earlier reclamation. It may be feasible to use the same plant to prepare backfill and to dispose of surplus tailings. Example cost models are given to illustrate potential applications.

Jan 1, 1998

A 1991 survey of 48 mining companies, employing more than 24 000 employees, showed that disabling injury and disease rates continue to be the most common measurements of safety management effectivness in the Australian mining industry.Of the companies surveyed, 22 claimed to be making regular safety audits. Of these only two listed the improvement of audit scores among their goals for 1991.Influenced by loss control management thinking, some managers have expanded the scope of their safety programs to include all accidental operational losses adversely affecting mine profitability.Learning from their new experience with total quality management some managers are now recognising that successful safety management outcomes depend on the effective management of program inputs. They are thus turning away from measurements of accident consequences - the failures of the management system - to measurements of management control.The new focus of safety management attention is now on corrective actions before accidents happen.

Jan 1, 1992

By Akerkar D. D, Dey M. L, Mathur S. B, Chowdhury S. K R

The extraction of gold and silver from chalcopyrite concentrates has been investigated. In view of the recent interest in non-cyanide leachants for gold and silver, one such alternative reagent, namely thiourea, has been employed in the present work. Precious metal leaching was attempted from received copper concentrates as well as pre-oxidised concentrates. Pre-oxidation of the concentrates was carried out by three different methods, namely roasting, pressure oxidation and biological oxidation. After pre-oxidation and leaching of the base metals, the leach residues were subjected to further leaching for precious metal extraction. The results obtained on the extraction of gold and silver from received concentrates as well as pre-oxidised concentrates are presented and the effectiveness of the three pre-oxidation routes employed is compared.

Jan 1, 1992

By P Wahyono, H Vega, S Riza, P Vergara, P Gonzalez-Carbonell

PT Freeport Indonesia (PTFI), operating in the Ertsberg Mining District in the Province of Papua, is developing the Grasberg Block Cave copper-gold mine. The site aims to output 160 000 t/d and will be located underneath the current Grasberg Open Pit. Initial studies of the potential to develop a block cave mine in the Grasberg orebody have revealed that the mine will require significant volumes of air. The Grasberg Block Cave (GBC) project requires four primary fans (3750 kW each) to support production at full capacity.Fan #1 commissioning was accomplished successfully on 9 February 2012. However, Fan #2 chamber, which is separated by a 20 m pillar, had not been completed. The main challenge was Fan #2 chamber still needed to be benched. The risk of damage to the critical infrastructure in Fan #1 chamber, including ground support, cracks in pedestals, and misalignment in the impeller shaft were considered. The challenges were blasting the bench without damaging the surrounding infrastructure, completing the work safely and meeting the schedule. This was achieved with the engineering control methodology. This paper summarises the benching process of Fan #2 chamber and its impact upon Fan #1.CITATION:Vega, H, Riza, S, Gonzalez-Carbonell, P, Wahyono, P and Vergara, P, 2013. Excavating an underground primary fan chamber that is adjacent to a fully operational primary fan in PT Freeport Indonesia's Grasberg Block Cave Mine, in Proceedings The Australian Mine Ventilation Conference , pp 115-122 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 1, 2013

By A Dunne, R Kruger, H Coleman, P G. Laurens

External and internal challenges in mining are increasing the difficulty and complexity of operating mines. The external mining environment has a big impact on mining operations and is driving the focus on safety, sustainable mining, green issues, profitability and productivity. There is a very high emphasis on ‘reducing cost to improve’, lower mining and beneficiation costs by eliminating waste/inefficiencies (reduce people, use less consumables, multiskilling, etc). The internal mining environment is getting tougher to operate in, with the deposits being more difficult to mine, more difficult to manage due to external pressure along with issues associated with maintaining quality, etc.Technological and environmental developments too numerous to mention, mean that cost control models, reduction in human resource numbers, as well as other drastic measures to curtail expenditure and increase profitability have become part of everyday business. The capability to manage the mining environment in a systemic manner has been lacking and this increases the pressure for performance on those individuals operating and managing mines.Working smarter has become crucial to ensure that businesses optimise the use of their resources, become more safety conscious, more productive and remain cost-effective, while recognising the importance of sustainable mining now and in the future. The logic of determining and managing to the capability of the mining value chain will be examined and the underlying assumptions or beliefs guiding behaviour and decision-making will be highlighted.In order to identify the obstacles in the mining value chain that hinder achievement of its full potential, the following questions have to be asked:What are the factors that influence the performance of a mining value chain?What is the design capacity of the mine?How can the inherent flow and value capacity of a mine be determined?What types of solutions will allow a mine to operate at its inherent flow and value capacity?This article will discuss the way we plan, measure, assess and manage the mine value chain, by addressing the following factors:balanced capacity versus flow and value capacity designthe use of averagingoptimising individual components in a value chain versus optimising the whole value chain.Optimising flow and value through the mining value chain is one of the three pillars of Mineral Resource Throughput Management (MR™). MR™ is an entrenched and academically supported philosophy that has been successfully applied in the past decade in various mines throughout the world by EXXPLEO, a mining and beneficiation consulting company. EXXPLEO has partnered with HCL (a global IT company) to embed the MR™ philosophy, methodology and toolsets into a formal software product called Synchronised Digital Mining (SDM). The SDM system will provide mining companies with a sustainable platform to effectively apply the MR™ principles and toolsets effectively across all operations targeting increased productivity, efficiency and profitability without having to train operations and management staff into expert MR™ practitioners to successfully achieve the desired results.CITATION:Dunne, A, Laurens, P G, Kruger, R and Coleman, H, 2015. Optimising flow in the mining value chain, in Proceedings Iron Ore 2015, pp 437–442 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 13, 2015

By Jagger ND

Pressure filters were found to be necessary to produce Elura silver/lead and zinc concentrates at sufficiently low moisture contents for bulk cargo shipment by sea to smelters.The difficulty in obtaining low moistures was due to the fine primary grind, 80% passing 45 microns, and resultant fine concentrates, 97% passing 45 microns.The filtration system was designed to filter up to 90,000 tonnes/year silver/lead concentrates and up to 130,000 tonnes/year zinc concentrates.This paper details the preliminary test work to select Larox automatic pressure filters, and the commissioning and operation of these filters to achieve design criteria for both concentrates. The design criteria for both concentrates have been bettered due to the concentrates being coarser than the design sizing.

Jan 1, 1985

By C Preston, T Williams, D Roy

The easiest way to mine valuable orebodies is through the use of explosives and well-planned blasting layouts that produce fragmentation profiles designed specifically for conveyance equipment in underground mines. The design of blasting patterns is specific to not only the explosives being used but also the rock or ore type being fragmented. Many blasting designs are based solely on the experience of those developed for similar orebodies in terms of properties and orientation or individuals that have some blasting experience.The primary technical objective of this paper is to outline a unique methodology for determining underground blasting methodologies (developing specific blasting parameters) commensurate with explosive energies and rock/ore equations of state for a narrow-vein gold property located in Northern Quebec and for underground mines in general.The procedures developed are to define the desired fragmentation specification so that a specific thermodynamic break is generated, taking into account powder factor, energy factor, tonnages, explosive energies and distribution along with blasthole diameter and orebody orientation for a specific set of explosive and dynamic rock/ore properties. Determining dynamic modulus values for the ore using seismic sensors to measure P- and S-wave velocities, the aforementioned parameters will be utilised to set the design constraints to maximise recovery and minimise overbreak and dilution.New underground blasting software (AEGIS) will use thermodynamic break in conjunction with defined fragmentation profiles to create an array of blasting parameters used to design and plan ring layouts. This software will also allow mining planners, prior to drilling and loading a production blast, to appraise future intended blasting patterns to minimise the potential of diluting ore with host rock and the likelihood of damaging mine support structures.CITATION:Roy, D, Williams, T and Preston, C, 2015. Underground stope drill and blast designs optimisation program, in Proceedings 11th International Symposium on Rock Fragmentation by Blasting, pp 137–148 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 24, 2015

By B Abbasi

It is well known that most roof falls in coal mines typically occur at and around intersections. Room-and-pillar and longwall coal mining systems typically develop 3-way and 4-way intersections. This research develops an improved scientific understanding of stress distribution and associated instability behaviour around 3-way and 4-way coal mine intersections through 3-D numerical modelling and limited field observations. Numerical analyses were performed for an Illinois longwall coal mine to identify factors that influence intersection stability. The stability of immediate roof, floor strata, and coal ribs at and around intersections are considered with pre-mining regional horizontal stress. Non-linear failure analyses used the Hoek-Brown failure criterion for rock mass. Progressive failure zones in and around intersections were developed. For a typical 4-way intersection, pillar corners across the intersection fail first and lead to progressive failure of the immediate roof and floor layers. The mechanism of failure is similar for a 3-way intersection but the shape and extension of failed zones differ. For the 3-way intersection, the effect of off-set distance was analysed. It was found that minimum off-set distance of about 10 m (centre to centre distance between two 3-way intersections) was required to minimize interaction between two intersections. A simple instrumentation program monitor ground movements around intersections. These data were used to design the intersection geometry that is now being practiced by the mine. CITATION:Abbasi, B and Chugh, Y P, 2018. Instability analysis in three-way and four-way coal mine intersections, in Proceedings The Fourth Australasian Ground Control in Mining Conference (AusRock), pp 345–359 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Nov 30, 2018

By R Burgess-Limerick, J Haight

A review of mining automation experiences was undertaken on behalf of the National Institute for Occupational Safety and Health (NIOSH). The research included a review of literature and guidance materials; analysis of automation related incidents and visits to surface and underground mines in Australia, Brazil, Chile, South Africa, Sweden and the USA.

Apr 16, 2024

By C Laming, S Staude, D Hammond, S Sheppard, J Griffith, S Stanfield, S Marriott

Long Operations is located on the eastern slope of the Kambalda Dome in Western Australia. Kambalda hosts nickel deposits that are modelled to have formed from an exsolving sulfide melt from a parental komatiite melt. The nickel deposit model predicts a stratigraphical relationship where massive Fe-Ni-Cu-sulfides are deposited in troughs at the base of komatiite channels. The basal contact of the sulfides is generally tholeiitic basalt. The Kambalda geological sequence form a dome structure with a granodioritic core and have undergone tectonic and metamorphic overprinting, resulting in the formation of upper greenschist to lower amphibolite-facies units.On the basalt-ultramafic contact, within the Long Operations, there are two separate channels hosting seven different orebodies. The Moran orebody is the most undisturbed orebody at Long Operations, with many primary magmatic textures preserved, making it ideal for studies to improve the existing nickel sulfide formation model. Detailed exploration and production infill drilling and systematic sampling indicates consistent nickel tenor variations over the entire Moran orebody. This was also observed in other deposits in Western Australia and was explained as metamorphic variations. Similar variations are observed with some trace elements that cannot be explained by metamorphic overprint but with gravitational segregation in the liquid sulfide. Other more complex trace element patterns (eg Cr) require additional explanations and are partly originated from incorporation of underlain basalt and sediment and partly from gravitational segregation.From a mining perspective, the Moran orebody can be used as an example of modern high-speed mining, but at the same time preserving samples for the future and allowing knowledge from the geological context and geochemical signatures to improve future exploration.CITATION:Staude, S, Marriott, S, Griffith, J, Laming, C, Hammond, D, Stanfield, S and Sheppard, S, 2014. Improvement of existing ore-forming models due to systematic sampling during mining – an example from Kambalda, Western Australia, in Proceedings Ninth International Mining Geology Conference 2014 , pp 341–348 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Aug 18, 2014

By Vynne J. F

Drill monitors for rotary blasthole drills have been available to the mining industry since the 1970s. The early monitors were pen strip chart recorders that were developed for the oil drilling industry and adapted to mining. They recorded drilling parameters such as depth, pull-down pressure, torque, RPM, and hailing air pressure. While these recorders could generate a large volume of paper, the amount of useful data was minimal. The data was not summarised and required an engineer to interpret the chart traces. Being a mechanical recorder, the devices were also susceptible to frequent failures. Modem electronics, and the development of the personal computer and its associated software have radically changed the type of instrumentation that is now available for blasthole drills. Perhaps more important is what can be done with the data. The PC allows the logged data to be analysed, summarised, and a variety of reports to be generated. The reports can be customised to meet the specific requirements of the mine and reduce the amount of time that is required to interpret the data. There is also an increased awareness in the mining industry of the importance of production drills. Blasthole drills have typically been the piece of production equipment that received the least amount of attention in a surface mine. Management focussed on the trucks and shovels or draglines. This situation is changing, and therefore the benefits that can be derived from monitoring drill performance are being recognised. Potential economic benefits of installing drill monitors have been documented in previous papers (Peck and Vynne, 1992). Mines are finding that pay-back periods of less than twelve months and rates of return in excess of 30 per cent are not uncommon. These benefits include the following: 1. Reduced overdrilling; 2. Increased rate of penetration; 3. Helping to locate coal seams; 4. Identification of weak and strong zones; 5. Reduce geophysical logging; 6. Optimising blasts; 7. Improved fragmentation and diggability; 8. Decreased coal dilution; 9. Increased bit life; 10. Reduced maintenance costs; 1 I . Improved accuracy of data and reports.

Jan 1, 1995

By Barber S

The Golden Cross Mine is located within the Waitekauri Valley near the southern end of the Coromandel Ranges, eight kilometres north-west of Waihi, North Island, New Zealand. The mine is owned and operated in a joint venture by Coeur Gold NZ Ltd (80 per cent) and Viking Mining Ltd (20 per cent). The underground mine produces gold and silver from low sulphidation epithermal quartz veins which developed in the shallow parts of a meteoric water dominated system during the Upper Miocene (7.36 - 6.67 Ma). The Empire Vein System is hosted within a dilational structural environment which developed at the lithological contact between acid intrusives, rhyolitic-dacitic tuffs and reworked pyroclastics, and undifferentiated andesites. The formation of the Empire Vein System was controlled by the rheological properties of the host rocks and variable displacement along a series of normal, right lateral, easterly-dipping faults. These faults represent sub-parallel zones of master shearing within a Riedel shear model. Underground mining extracts ore from the steeply dipping hangingwall and the complex footwall veins of the Empire Vein System. Initially sills are driven along the hangingwall vein on ten to fifteen metre sublevel intervals. In the footwall zones where significant mineralisation adjacent to the hangingwall sill drives has been identified, a series of cross-cuts and footwall drives (sub-parallel to the hangingwall sill) are also developed. Where continuity of mineralisation and ground conditions permit a combination of post pillar flatbacking and AVOCA longhole benching methods are used. Detailed underground mapping of lithology, quartz veining and major structures provides the information for designing ground support and footwall pillars, planning mine development and ore extraction sequencing. Sectional interpretation displays the vertical extent of faults, fractures and the vein system. The mining methods used underground at the mine have evolved through a thorough understanding of the structural complexity and the systematic geological mapping of the Empire Vein System.

Jan 1, 1997

By R Barritt, P Scott, K Albano

Successful closure of tailings storage facilities (TSFs) is an environmental issue faced globally by metalliferous mines. During the initial feasibility and design phase of the mine life importance is placed on the physical stability of above ground TSFs, largely driven by legislative requirements, whilst closure planning is often a secondary consideration. However, as the landform is further developed and constructed attention must be paid to regularly revisit the original closure plan and update it to achieve the best (sustainable) possible outcome for both the environment and stakeholders. A mine in northern Queensland is in the process of developing a closure strategy at their TSF. Appropriate closure measures for the TSF are required to mitigate the impact of any seepage emanating from the TSF on the groundwater and surface water receptors. O’Kane Consultants Pty Ltd (OKC) have provided the mine assistance with the development of a TSF cover system design in order to appropriately manage tailings during operations and to prepare for the facilities’ closure. OKC has collected data since 2007 from cover system field trials located on the TSF. To enhance engineering judgement in the design of future cover systems, calibration of soil-plant-atmosphere numerical models to field data (referred as ‘field response modelling’) were completed. Calibrated model inputs can be used to provide insight into long-term cover system performance as well as a tool for design of the final landform.Following a site investigation, materials characterisation and numerical modelling program various cover system alternatives were developed. Two of the preferred cover system alternatives referred to as Test Plot #1 (TP#1) and Test Plot #2 (TP#2) (Figure 1), were constructed at the site and instrumented. Monitoring instrumentation comprised several nests of in situ volumetric water content and thermal conductivity sensors to measure changes in water content, temperature and matric suction within the cover system materials and underlying tailings waste. Run-off collection buckets and a fully-automated meteorological station were also installed. CITATION:Barritt, R, Albano, K and Scott, P, 2016. Findings and conclusions following ‘long-term’ cover system monitoring – refinement of the conceptual design for tailings storage facility closure, in Proceedings Life-of-Mine 2016 Conference , pp 85–88 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jun 28, 2016

By S Wan, F Zhang, J You, K Tang, X Tang, C Bessada, A Canizarès, Q Zhang, L Lu

Microstructure of CaO-SiO2-based glassy samples with various Al2O3 contents were examined quantitatively by Raman spectroscopy and 27Al MAS NMR (magic-angle spinning nuclear magnetic resonance). Sequence of multiple cluster models of aluminosilicate system modified with Ca2+ and Na+ cations have been designed, and Raman spectra simulation were carried out after geometric optimisation by quantum chemistry (QC) ab initio calculation. The functional relationship between Raman scattering cross-section (RSCS) and stress index of silicon-oxygen tetrahedron (SIT) for aluminosilicates was established, which was applied to the calibration of experimental Raman spectra. Some five-fold coordinated aluminium (AlV, around 5 per cent) and less than 2 per cent sixfold coordinated aluminium (AlVI) were detected by 27Al MAS NMR, while most of aluminium remained in tetrahedral sites (AlIV). The hyperfine quantitative results of Raman spectroscopy and NMR showed a gradually production of AlIV with addition of Al2O3, along with the significant adjustment of Qi species distribution, in which Q1, Q2 reduced and fully polymerised Q4 increased while Q3 showed a non-monotonic variation and obtained the maximum at Al2O3 = 18 mol per cent. Furthermore, the effects of aluminium to bridging oxygen bond types (T-Ob, T = Si, Al) and the degree of polymerisation were also discussed in detail. The evolution of microstructure and its correlation with the viscosity of CaO-SiO2 based melts, incorporating various Al2O3 additives, have been investigated by employing in situ high temperature Raman spectroscopy at 1823 K and viscosity model. These structural features related to composition are essential theoretic foundation to understand their properties. The average Qi evolution culminates in an overall enhancement of the degree of polymerisation. Viscosity was determined utilising a rigorously selected viscosity model, elucidating a consistent upward trajectory as Al2O3 content is incrementally added. Furthermore, a quantitative analysis of the relationship between viscosity and structure was conducted based on the average number of non-bridging oxygen per network-forming tetrahedron (NBO/T). It provides valuable insights for examining and predicting viscosity behaviour of aluminosilicate systems.

Aug 21, 2024