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Past issues of Minerals and Materials have discussed such aspects of the economy as consumption and investment expenditures, interest rates, productivity, and international trade barriers and their effect on the minerals industry here and abroad. In this issue, we will (l) look at recent indications of a possible economic recovery, (2) present 1983 expectations reflecting the results of industry surveys conducted by the U.S. Department of Commerce (DOC), and (3) briefly discuss the contribution of the U.S. mining industry to total gross national product (GNP). THE RECOVERY Throughout most of 1982, DOC's Composite Index of Leading Indicators provided evidence of impending improvement in the economy. The index increased moderately during eight of the months in 1982 and then jumped an estimated 3.6 percent in January 1983 (table 1). While the leading indicators continued to predict improvement, the general economy, as measured by the Index of Industrial Production, continued its slide through November 1982 (table 2). Finally total industrial production increased in December 1982 and continued on an upward path in January and February, as predicted by the leading indicators.

Jan 1, 1983

By E. Kaya

Investigations of fine grinding of bituminous coal in a laboratory-scale pulverizer are described. The results indicate essentially "normal" breakage behavior at relatively coarse sizes (greater than about 20 µm) but show clear evidence for re-agglomeration in the fine size range (less than about 10 µm). A simplified population balance model for simultaneous growth and breakage has been formulated. Breakage rates and breakage distributions are assumed to follow the patterns typically observed in simple grinding systems. It is recognized, however, that solid particles and agglomerates may exhibit different breakage behavior. Agglomeration rates are assumed to be determined by contact probability, i.e. by the relative numbers of interacting particles. Based on comparisons of model simulations and experimental data, it appears that agglomerate re-breakage rates and fragment size distributions are quite different from those for solid particles. The result is that product size passes through a minimum and then increases with time as agglomeration begins to dominate.

Jan 1, 1996

By Paul Billingsley

NICKEL Plate mountain coincides closely with that portion of the Hedley mining district which is of economic interest. From it has come almost the entire past production, and the active mines of the present epoch, Nickel Plate-Sunnyside and Hedley Mascot, lie in a compact group near its summit. The Hedley district, which is 210 miles due east of Vancouver, is situated in the Okanagan range of southern British Columbia, where this rather gentle uplift is deeply dissected by the canyons of the Similkameen and its tributaries. The region is essentially part of the Interior Plateau of the Province (Figure 1), but is adjacent to easterly elements of the Coast Range. The Similkameen canyon, 4,000 feet in depth and frequently less than 4 miles from rim to rim, traverses the district from northwest to southeast. The deepest and narrowest portion of the canyon lies between Hedley and Keremeos, 18 miles to the southeast. At Hedley, an important tributary, Twenty Mile creek, enters from the north in a bold canyon, making a focus of unusually rugged topography. Nickel Plate mountain occupies the sector to the east of this junction (see Figure 2) and its flanks are ringed by the cliffs of Twenty Mile canyon on the west and by those of the Similkameen canyon on the south. On the east, it slopes gently to the hanging valley of Eighteen Mile creek, and on the north, with only slight loss of elevation, it merges into the moderately hilly surface of the plateau.

Jan 1, 1941

By A. Boehm

"For recycling LD slag into the steel making process, the phosphorous containing calcium silcate phases have to be removed from iron oxide phases. One possible technical solution could be magnetic separation in a wide range of susceptibilities from ferromagnetic to paramagnetic. To check the feasibility of magnetic separation the distribution of the magnetic susceptibility in size classes as well as the liberation of the phosphorous containing phase were evaluated by a new method combining two dimensional physical property analysis with QEMSCAN analysis. The particle size classes of energy controlled comminution products were subdivided into fractions of defined magnetic susceptibility using a hand magnet of well known field properties (pick up method). On the one hand the susceptibility classes were wet assayed on the other hand analyzed by QEMSCAN followed by data evaluation using iDiscover 5.3.1(FEI), which was adapted to the data structure of two physical properties (size and magnetic mass susceptibility). The results allow the comparison of mass based (3D) cumulative distribution of grades from the wet assays with the area based (2D) distribution from QEMSCAN analysis, in order to control a systematic (size dependent) stereological error for this special type of material. As the physical separation property forms a crucial parameter the results from the liberation analysis by QEMSCAN can be interpreted more profound with respect to an expectable separation result. Once the various mineral compositions of the particles are assigned to the physical properties the Henry Reinhardt chart serves to predict the best possible separation result and thus the feasibility of a separation technique.INTRODUCTIONThe two Austrian steel plants operated by voestalpine AG produce about 650,000 t (voestalpine 2014) of LD slag in the course of steel production from pig iron according to the basic oxygen process blowing oxygen in the converter by an oxygen lance. The process is also known as the Linz Donawitz (LD) steelmaking process. By the addition of lime (CaO), carbon, phosphorus, silica, manganese and sulfur, which are present in the molten pig iron, shall be oxidized and bound in the slag either as oxide or silicate phases, or leave the slag in the gaseous phase (CO). The average chemical composition of the investigated LD slag is given in table 1."

Jan 1, 2016

By Akira Yazawa

To realize highly efficient process in extractive metallurgy, continuous operation nearly in equilibrium is preferable, but most metallurgical processes consist of plural steps with different chemical potentials. Traditional two-step process of sintering followed by reduction is continuous in each step, but is heterogeneous reaction system far from equilibrium, and the chemical potentials are varied considerably along the distance the charge travels in a reactor. This route will become old-fasioned in next century due to the various inherent problems caused especially by sintering process. To establish reasonable new smelting processes, the important tasks of the metallurgists are how to introduce feed and reacting gas in the reactor, and also how to overcome the difference in chemical potential in the reactor system. Based on the ways to solve theses tasks, recent proposals of new smelting process for copper and lead are classified and discussed with the help of sulfur-oxygen potential diagram. On such potential diagram, each equilibrium step in continuous smelting is expressed at a fixed point, and two reactors with different chemical potentials must be connected by continuous molten flow through launder or partition wall. In the latter case, the reactor is apparently single, but some technical problems must be overcome. While, in a batch smelting like converter, potential variation is successively realized along a path on chemical potential diagram with the time elapsed. To establish immediate equilibrium, continuous steady flow of reactants into well mixed reactor is indispensable. In modern smelting process, the ore is mostly supplied in the form of powder which have huge surface area and fluid character, and consequently injection process must be very attractive. Several examples are discussed for both of copper and lead smelting, and promising future technologies are suggested.

Jan 1, 1988

By K. Bullock, M. Levesque, G. Lyle, D. L. Millar

ABSTRACT The options for reducing the carbon footprint of energy use in mining fall into three categories of activity: i) reducing demand, ii) improving energy utilization, and iii) adopting low carbon energy technologies. In addition to the environmental imperative, the economic case for these activities gains higher priority as the prices of electricity, gas, and liquid fuels increase. Low-carbon, energy-saving technology options that are available to mining industry companies lead to projects with return rates that must compete alongside other capital-intensive projects considered by mining company boards. Energy projects frequently involve longer payback periods and lower rates of return than those of competing bids for capital, such as new mineral property developments. For energy services companies that specialize in the financing, construction, efficient operation, and maintenance of energy projects, the same returns and payback periods can be considered acceptable or even attractive.

Jan 1, 2012

By Robert C. Johnson

Water-swelling fluormicas and fluormontmorillonoids were synthesized and described. They were found predominantly in the system Mg0 - MgF2 - Si02, with varying amounts of Li+ or Na+, Some water-swelling synthetic minerals were prepared with only strontium or lead in the twelvefold position, Water- swelling compounds containing either K+ or Ba+ were not found. The synthesized water-swelling products were shown by electron microscopy, X-ray diffraction, and chemical analysis to be typically two-silica-layer, platy compounds, Except for the complete substitution of fluoride for hydroxyl, the compounds were similar to the natural micas or montmorillonites. The stability and properties of the compounds were further established by electrodialysis, by differential thermal analysis, and by anion and cation exchange methods. Fluoride in the interlayer positions was nonexchangeable except through decomposition of the product. Exchanging the sodium or the lithium of the synthetic fluormicas or fluormontmorillonoids with potassium ion, particularly those derived from KOH provided a product from which a completely inorganic paper of extraordinary flexibility was fabricated. This paper had excellent mechanical and electrical properties except for water adsorption and a high power factor. Neither of these problems was solved during this investigation. However, papers with dielectric strength from 1,500 to 5,000 volts per mil were readily fabricated, particularly from the lithium containing fluormicas or fluormontmorill onoids.

Jan 1, 1963

By P. T. L. Koh

The effect of particle shape on the flotation process has been investigated in laboratory experiments with monosized spherical ballotini and roughly ground ballotini. The particles were treated by partial methylation with trimethylchlorosilane to achieve varying degrees of hydrophobicity. In flotation, the process of film thinning and liquid drainage is critical in the formation of a stable bubble-particle attachment and this is affected by the particle shape and surface hydrophobicity. The rate of attachment affects the overall flotation rate. Flotation tests with different particle sizes at various degrees of partial methylation have been performed in a modified Denver cell. Predictions from a computational fluid dynamic model of the cell which incorporates fundamental aspects of bubble-particle attachment are compared against flotation test results. Contact angles of the particles have also been measured using the capillary rise technique to indicate surface hydrophobicity.

Jan 1, 2014

By R. L. Levens

Researchers at the U. S. Bureau of Mines conducted investigations to evaluate the potential for ground water contamination by mine waste used as backfill. Samples of cemented waste backfill and water discharging from drillholes and seeps were collected to use in chemical analyses and laboratory tests to determine the physical and chemical factors that control release of heavy metals to ground water. Greater water retention by cemented backfill (as compared to uncemented sandfill) reduces the surface area exposed to oxidation, which in turn reduces the amount of acid produced. The acid is neutralized by the cement and minerals contained in the backfill. The grain-size distribution of tailings used for backfill affects the structural integrity of cemented backfill under attack by acidic water; breakdown of the backfill structure releases neutralizing materials faster. Backfilled stopes in rock with low hydraulic conductivities will constitute preferential flow paths after mine flooding; however, the rate of flow through backfill will be much slower than when the stope is partially saturated during mine operation. Considering all factors, acid generation and release of metal ions from cemented backfill should be less than in uncemented sandfill.

Jan 1, 2010

By E A. Agorhom, M Beyuo, C Owusu, I Quaicoe

Understanding the mineralogy and liberation of gold particles in an ore is key to the development and optimisation of gold processing operations, being cyanidation or gravity separation. This can be achieved through basic historic geological information, gold deportment studies, chemical speciation and metallurgical test works. The present study assessed the nature of the occurrence of gold particles (mineralogical composition, liberation, associations and surface chemistry) and its effect on the process route (cyanidation and gravity separation) of a typical paleo placer gold ore deposit within the Tarkwaian Rock system. The investigative approach used involved chemical assay, quantitative X-ray diffraction (QXRD) and quantitative evaluation of minerals using scanning electron microscopy (QEMSCAN). The ore samples (A, B, C, D, E, F) used were obtained from six active pits of a gold mine working on this orebody. The results of the mineralogical analysis revealed that the ore is highly oxidised and comprised quartz (>80 per cent) and Muscovite mica (>6 per cent) as the major mineral phases in all the samples. Trace amounts of hematite, kaolinite and todorokite were also identified in all the samples. The chemical analysis showed presence of gold (Au) in all the samples with samples B (3.62 g/t) and C (3.96 g/t) containing the highest concentrations. Trace amounts of copper (Cu), iron (Fe), sulfur (S), aluminium (Al), arsenic (As) were also detected in all the ores. The QEMSCAN mineralogical liberation and gold association results revealed that the gold grains were relatively coarser in all samples (P80 > 80 µm Au in size) except F (P80 < 32 µm Au in size). Gold grains were highly liberated especially in sample B with the majority of the locked gold grains forming complex associations. All the samples responded well to cyanidation and gravity separation except samples C and F, respectively.

Aug 24, 2022

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.&apos; The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.&apos; The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00&apos; were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-&apos;. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By Serhan Guner, Sundar Chiluwal

Although significant research has been conducted on helical piles, there is a lack of research and official design provisions on the helical pile-to-pile cap connections. These connections may govern the global response of pile cap systems—especially in tall and light structures where uplift forces dominate the response. To improve future industry practice, the objective of this study is to understand the influence of pile-to-pile cap connections on the global behavior of concrete pile caps and develop recommendations for their efficient design. For this purpose, 108 high- fidelity nonlinear finite element simulations are conducted to quantify the influences of bracket type, embedment depths, longitudinal reinforcement percentages, shear span-to-depth ratios, and loading conditions on the load, deformation, cracking, and failure behavior of concrete pile caps. The results indicate that the design configurations involving single bracket type may result in premature concrete cracking around the anchorage zones with a 25% reduction in the uplift load capacity. The investigations also confirm that high reinforcement percentages and low shear span-to-depth ratios result in higher load resistance in all bracket types, and that the load capacities of the double and studded bracket types are similar. For applications requiring the use of lower embedment depths, it is recommended that either double or studded bracket types be used. The research findings have applicability to both helical and micro piles given that both include similar connection types. INTRODUCTION Tall and light structures may experience significant uplift forces at their foundations due to large overturning moments from wind or other lateral loads. Helical piles (e.g., Fig. 1a) can provide a cost- effective, practical, and resilient solution for resisting significant uplift forces. In order to realize the full potential of helical piles, it is imperative that the helical pile-to-pile cap connections (see Figs. 1b, c and d for examples) are properly designed to resist the applied forces. However, there is a lack of research and associated knowledge on the influence of pile-to-pile cap connection detailing on the global response of pile caps.

Jan 1, 2019

By Ramana G. Reddy, Yuxiang Peng

The long-term corrosion behavior of Haynes 230 (H230) alloy in MgCl2–KCl eutectic salt was evaluated at 1273 K for 500 h in Ni crucible in argon gas. The results showed H230 alloy has good corrosion resistance. In addition, corrosion was noted to occur by depletion of Cr, which was deposited on the Ni crucible. Based on the calculation of Gibbs energy of Ni-Cr alloy and exchange current density of Cr in MgCl2–KCl, the Tafel model was constructed to investigate the corrosion potential and rate. The galvanic corrosion can be explained as the predicted results were in agreement with the experimental data.

Mar 1, 2017

By D. Brunner

System simulation is an increasingly popular technique for analyzing and improving existing as well as newly designed underground mining operations. An engineering firm that specializes in simulation helped a major metals producer build a long-range planning model of an existing underground mine. Subsequently the team adapted this model to assess technology alternatives in the design of a new mine. The two models differ in the level of detail used for modeling the development process. This paper discusses the differences in approach between the models along with the experiences gained and challenges faced during the construction and use of the models.

Jan 1, 1999

By L. L. Sutter

Fly ash is a by-product produced from the combustion of most hels including municipal solid waste. Currently, most combustion residuals are disposed of in landfills at a continually increasing cost and with questionable impact on the environment. Due to the presence of heavy metal compounds, municipal waste combustor (MWC) fly ash has the potential to leach these metals (e.g., lead and cadmium) above regulatory limits. The heterogeneous nature of MWC fly ash makes detailed characterization difficult. This research focuses on the identification of lead compounds in MWC fly ash. Samples obtained from the Olmsted Waste-to-Energy Facility in Rochester, Minnesota were examined in this study. The fly ash was fractionated into six size ranges and prepared as geological thin sections for analysis. The worked discussed in this paper involves using an electron microprobe analyzer to determine phase composition in MWC fly ash. In addition, backscattered electron imaging, digital image processing, and mineral liberation analysis software were used to determine phase distributions and phase associations as a function of particle size. Several lead containing compounds in several forms are identified. The results of this study show that lead can be identified in small sectioned particles which would not be apparent using normal backscattered electron imaging.

Jan 1, 1994

By Yongqi Sun, Zuotai Zhang

Hot slags, at the temperatures of 1450-1650 oC, carry a substantial amount of high quality thermal energy, which represents the largest undeveloped energy source in the steel industry. However, the waste heat recovery rate in China is less than 2%; thus there is a great potential of waste heat recovery. In this study, we investigated a chemical method to extract the waste heat from high temperature blast furnace slags, i.e., sludge gasification. Sewage sludge, another substantial waste produced in the municipal system, need to be timely disposed, the organics of which could be gasified using the waste heat in the slags for the purpose of syngas production. Both the kinetics and thermodynamics of the sludge gasification process were clarified here. Most importantly, an integrated system composed of multiple systems such as the steel industry, the cement industry, the municipal system and the chemical engineering industry, was analyzed in this study.

Jan 1, 2016

By D. W. Lui

Tangdan copper oxide deposit, the largest independent copper oxide deposit in China so far, is located in the northeast of Yunnan province, southwest of China. The ore from this deposit is characterized by: low grade, high oxidation ratio, and fine-grained disseminated, resulting in poor flotation recovery. The analysis of plant flotation data reveals that the loss of copper minerals into tailings is mainly with coarse size fraction due to insufficient liberation and fine size fractions, especially minus 10 microns fraction, which proved to be very difficult-to-float with conventional flotation. In order to improve the performances of plant flotation of this ore, laboratory flotation tests were conducted with the pure malachite, which was the principle copper oxide mineral in Tangdan copper ore deposit. The results obtained suggested that a finer grinding (up to -325 mesh or even -400 mesh) be needed to decrease the loss with coarse size fraction, and vacuum flotation is a promising way for the recovery of the fine malachite effectively.

Jan 1, 2014

By J. S. Marsh

AN incomplete statistical analysis performed wearily on the morning after Thursday, Feb. 12, indicates that the unavoidable items of conversation among steelmen were the current shortage of sleeping time and the "Normandie." No analysis is needed, however, to be certain that many thousands of valuable words were uttered, both in and out of technical sessions, concerning matters of deep interest to members of the Iron and Steel Division. The opening session consisted mostly of papers that have appeared, or will appear shortly, in Metals Technology. One, however, that was not finished in time to be printed in any form, but that aroused great interest, was by E. L. Ramsey and L. G. Graper (Wisconsin Steel Works). Its subject was the production of high-sulphur steel by treatment with sulphur dioxide derived from anhydrous sodium sulphite or bisulphite added to the ladle or to the mold. The sulphide distribution in the finished steel is such that increased machinability and longer tool life result. Both items are of obvious importance in these days of mighty production.

Jan 1, 1942

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968