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By B. R. Mohal, F. F. Aplan, S. Chander

"The wetting behavior of coal has been determined in the presence of nonyl and octyl series of nonionic surfactants containing polyethoxy groups of different sizes. The wetting behavior was determined by a modified Walker technique and contact angle measurements. The results show that the wetting rate of coal varies with coal rank, structure of the hydrocarbon chain and number of ethoxy groups in the hydrophilic group of the surfactant. A close relationship has been observed between the wetting rates and the short-time advancing contact angles.INTRODUCTIONNonionic surfactants are used in many applications to improve wettability of solids. They can be used as dispersing agents [ 1 ] or dust suppressants [ 2-5] and to control the flotation, flocculation, filtration and flowability of particulates. This study was undertaken to study the effect of a series of nonionic surfactants on the wetting behavior of coal. Two series of surfactants, namely, ethoxylated nonyl and octyl phenols were used. The nonyl phenol series contains a linear hydrocarbon chain containing nine carbon atoms ( CH3 ( CH2 ) 8-C6H4-( OC2H4 )""' where n is the number of ethoxy groups). The octyl phenol series contains a branched hydrocarbon chain containing eight carbon atoms ( ( CH3 ) 3CCH2C ( CH3 ) 2-C6H4-( OC2H4)"").Initial wetting rates - modified Walker techniqueWalker et al. [ 6] developed a sink test to determine the wettability of coal particles. In this technique, coal particles are dropped individually onto the surface of surfactant solutions of different concentrations, and the most dilute concentration in which coal would sink ""instantaneously"" is determined. This technique is a variation of a procedure initially developed by Draves and Clarkson [ 7] to determine the effect of surfactants on wettability of cotton fibers."

Jan 1, 1989

By R. Blazej

Machinery Systems Division (MSD) in the Institute of Mining Engineering at Wroclaw University of Technology specializes in belt conveying systems analyzing, calculating and design. Within the division operates the certified Laboratory of Belt Transportation (LTT) and Laboratory of Rollers. Since few years, a group of several people have begun work on developing a comprehensive system for the automatic evaluation of condition of conveyor belts working in the mines. Group uses both magnetic devices developed by specialized companies servicing belts and its own machine vision system developed for assessment of belts covers and edges during belt movement (up to 7 m / s) on the specially designed for this purpose the test conveyor. Recently they have got the research grant funded by the National Centre for Research and Development (NCBiR) for development of the system for automatic diagnosing of conveyor belts? condition and aiding of rational belt management. On the basis of previously created diagnostic tool called ABCDE (Automatic Belt Condition Diagnostic Equipment) the five modules: vision-A magnetic-B, preventive-C, forecasting?D, and determining safety factor-E will be developed. They will automatically interpret data about conveyor belts? condition to indicate the extent and timing of repairs, to prevent failures and to select the optimum moments for their replacements. The system will use results of ongoing research & development and planned research concerning modeling of belt wear using evolutionary genetic algorithms. The reached stage of research can not yet allow to start the implementation work by potential users. It is therefore necessary to pursuit research in real scale, the development of new modules (C-E) and intensive testing of the system in working condition with system calibration to optimize the economic effects.

Aug 1, 2013

By T J. Sheer

The removal of airborne pollutants from underground ventilating air is discussed. The work concentrates on the removal of CO, CO2, NOx, SO2, radon gas and respirable carbon particles. The investigation combines techniques for multiple contaminant removal using forced chemical absorption and oxidation. Both dry and wet scrubbing techniques are employed. Mixed success has been achieved in the tests carried out and this paper is seen as a progress report on the work done to date. The interference and interaction of the gases on the individual removal efficiencies is a very important factor in the finalisation of a macro air conditioner (MAC) design for treating underground ventilating air. This necessitates a specific sequence of contaminant removal. Efficiencies are discussed and recommendations made. Wet forced chemical absorption and oxidation processes, though efficient in terms of removal efficiencies, cannot be employed in the confined underground environment due to safety and health risks. Impacts on the internal water reticulation systems of the mine have been analysed to determine the effect of future large-scale macro air conditioning practices, including blow-off liquids discharged into the water circuits. To engineer the safety and health risks out of such designs can be costly and it is for these reasons the research now concentrates on dry scrubbing of the contaminants from the underground ventilating air. The paper concludes with statements on the benefits of macro air conditioning in deep hot mines, in both recirculating and series air ventilation distribution strategies. These benefits include reduced re-entry times after blasting and increased production rate opportunities.

Jan 1, 2005

By Mark Colwell

This paper summarizes the results of a research project whose goal was to provide the Australian coal industry with a chain pillar design methodology readily usable by colliery staff. The project was primarily funded by the Australian Coal Association Research Program and further supported by several Australian longwall operations. The starting point or basis of the project was the Analysis of Longwall Pillar Stability (ALPS) methodology. ALPS was chosen because of its operational focus; it uses tailgate performance as the determining chain pillar design criterion rather than simply pillar stability. Furthermore, ALPS recognizes that several geotechnical and design factors, including (but not limited to) chain pillar stability, affect that performance. There are some geotechnical and mine layout differences between United States and Australian coalfields that required investigation and, therefore, calibration before the full benefits offered by the ALPS methodology could be realized in Australia. Ultimately, case history data were collected from 19 longwall mines representing approximately 60% of all Australian longwall operations. In addition, six monitoring sites incorporated an array of hydraulic stress cells to measure the change in vertical stress throughout the various phases of the longwall extraction cycle. The sites also incorporated extensometers to monitor roof and rib performance in response to the retreating longwall face. The study found strong relationships between the tailgate stability factor, the Coal Mine Roof Rating, and the installed level of primary support. The final outcome of the project is a chain pillar design methodology called Analysis of Longwall Tailgate Serviceability (ALTS). Guidelines for using ALTS are provided.

Jan 1, 1999

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

By C. N. Logan

The Southern Company is one of the nation's largest electric utilities and is the parent firm of five operating companies: Alabama Power, Georgia Power, Gulf Power, Mississippi Power and Savannah Electric and Power. Another subsidiary is Southern Company Services (SCS) which provides engineering and technical sup-port to the five operating companies. This technical support includes the procurement and supply of over 40.9 Mt (45 million st) of coal annually for the 22 coal fired plants in the system. Approximately 80 percent of this tonnage is purchased under long term contracts and the remaining 20 percent is purchased on the spot market. The coal is principally supplied from Alabama, Illinois Basin and the eastern Appalachian coal fields. Most of the coal is delivered by unit train and barge but one plant in Alabama receives all its coal by truck and conveyor belt.

Jan 1, 1990

By William E. Schoeneck

This paper presents the problem of oil-well abandonment as a group of studies involving the compilation of physical well data, the use of special curves, maps, and interpretative Procedures, in order that operations can be analyzed and means for reducing costs can be effected. Methods for the calculation of the economic limit of production and resultant oil reserves are suggested in order that profitable production may be continued and premature abandonment prevented. INTRODUCTION Purpose Extensive studies have been made and much has been written on the procedures for prospecting, drilling, completion, production and repair of oil wells, but the writer has long felt the need for a study of the procedure that should be followed when considering the abandonment of a well. The production from numerous well bores of a fluid material (a circumstance peculiar to the oil industry) that is continually decreasing in quantity leads to an increasing ratio of operating cost to production. It is for this reason that oil fields are not abandoned as a whole and detailed consideration of each well is required before it can be determined whether more is being expended than will be returned On any well or lease in question. It is the purpose of this paper, therefore, to compile, correlate, and present all matters worthy of consideration in the problem of oil-well abandonment; to suggest interpretative procedures based on such compilations, to the end that reliable estimates of reserves and life may be obtained; to show, as a result of such interpretative procedures, the possibilities for corrective measures conducive to economical production, thereby extending both profitable reserves and length of life. Scope and Approach Compiling data and outlining a study having the complexity of the problem at hand are naturally subject to the personal experiences of one who undertakes the study; however, the chosen approach and grouping of the subject material may be helpful in the consideration of abandonment problems. Consideration has been given to wells that make gas and water incident with the production of oil; but consideration has not been given to either gas wells or condensate-producing wells, for wells of the latter type have sufficient problems to warrant separate investigation. The major subdivisions of this paper-— physical considerations and economic considerations—do not imply that either of these phases can be considered independently, but rather that the two are mutually dependent and are the component parts of an engineering study.

Jan 1, 1946

By William E. Schoeneck

This paper presents the problem of oil-well abandonment as a group of studies involving the compilation of physical well data, the use of special curves, maps, and interpretative Procedures, in order that operations can be analyzed and means for reducing costs can be effected. Methods for the calculation of the economic limit of production and resultant oil reserves are suggested in order that profitable production may be continued and premature abandonment prevented. INTRODUCTION Purpose Extensive studies have been made and much has been written on the procedures for prospecting, drilling, completion, production and repair of oil wells, but the writer has long felt the need for a study of the procedure that should be followed when considering the abandonment of a well. The production from numerous well bores of a fluid material (a circumstance peculiar to the oil industry) that is continually decreasing in quantity leads to an increasing ratio of operating cost to production. It is for this reason that oil fields are not abandoned as a whole and detailed consideration of each well is required before it can be determined whether more is being expended than will be returned On any well or lease in question. It is the purpose of this paper, therefore, to compile, correlate, and present all matters worthy of consideration in the problem of oil-well abandonment; to suggest interpretative procedures based on such compilations, to the end that reliable estimates of reserves and life may be obtained; to show, as a result of such interpretative procedures, the possibilities for corrective measures conducive to economical production, thereby extending both profitable reserves and length of life. Scope and Approach Compiling data and outlining a study having the complexity of the problem at hand are naturally subject to the personal experiences of one who undertakes the study; however, the chosen approach and grouping of the subject material may be helpful in the consideration of abandonment problems. Consideration has been given to wells that make gas and water incident with the production of oil; but consideration has not been given to either gas wells or condensate-producing wells, for wells of the latter type have sufficient problems to warrant separate investigation. The major subdivisions of this paper-— physical considerations and economic considerations—do not imply that either of these phases can be considered independently, but rather that the two are mutually dependent and are the component parts of an engineering study.

Jan 1, 1946

By Russell C. Frith, David C. Oyler, Dolinar Dennis R., Christopher Mark

Unusual circumstances may require that a longwall retreat into or through a previously driven room. The operation can be completed successfully, but there have been a number of spectacular failures. To help determine what factors contribute to such failures, a comprehensive international database of 131 case histories has been compiled. The cases include six failures where major rock falls occurred in front of the shields, and seven even more serious failures involving major overburden weighting. The case studies suggest two types of room failure mechanism. The first is a roof fall type failure caused by loading of the immediate roof at the face as the fender or remnant longwall panel narrows. The second is an overburden weighting type failure caused by the inability of the roof to bridge the recovery room and face area, and affecting rockwell above the immediate roof. The data indicate that the roof fall type of failure is less likely when intensive roof reinforcement (bolts, cables and trusses) is employed together with higher-capacity shields. The overburden weighting failures, in contrast, occurred when the roof was weak and little standing support was used. Weighting failures were not greatly affected by the density of roof reinforcement. In one of the overburden weighting cases, in a Pittsburgh coal bed mine, stress cell, convergence, bolt load and extensometer data have been used to analyze the failure in detail. Key words: coal mining, ground control, longwall, recovery room.

By N. C. Joughin

A simplified economic model is derived for the financial return from a new gold mining project. The model is used to analyze the effects of changes in the mining rate, capital costs, working costs, value of the reef and the stoping width. The most effective avenues for improving the return from a new project are indicated. It is shown that those technological innovations which would improve the return significantly, and therefore make it possible to open more mines, are the use of smaller mines, means for improving the mining rate to capital costs ratio for smaller mines, planning and control of mines by computer simulation, an improved mine valuation procedure and means for mining at a decreased stope tramming width.

Jan 1, 2014

By I. K. Chopde, M. M. Dhobe, C. L. Gogte

"The quality of machined surface is becoming more and more important to satisfy the increasing demand of component performance and its reliability. While machining any component, it is necessary to satisfy the surface integrity requirements. Heat treatment plays an important role in improving the characteristics of the material.This work investigates the effect of heat treatment on the surface characteristics of AISI D2 tool steel after Wire-Electro Discharge Machining (W-EDM). The test specimens were prepared by hardening and tempering and then machined with Wire-Electro Discharge Machining process. Optical and scanning electron microscopy, surface roughness and micro hardness tests were conducted to study the surface characteristics of the machined surface. After characterization based on microstructures and test results, it is observed that the recast layer droplets are of smaller size with reduced white layer thickness resulting in higher hardness and lower surface roughness.IntroductionWith the development of mechanical industry, the requirement of alloy materials having high hardness, toughness and impact resistance is increasing. At the same time the quality of machined surface is becoming more and more important to satisfy the increasing demands of component performance and reliability. When machining any component, it is necessary to satisfy the surface integrity requirements. Surface integrity has two important parts. The first is surface texture, which governs mainly surface roughness. The second is surface metallurgy, which concerns to the nature of surface layer produced in machining [2]."

Jan 1, 2012

By H. M. Howe

It has seemed to the writer that one important, and indeed sufficient reason, for our slow progress in learning the relation between the chemical composition and the physical properties of cast-iron, has been that the problem has not been attacked properly. It would be well to select the most probable working hypothesis which we can find, and proceed to test that hypothesis by comparison with observed facts, and by making new observations specially designed for such a test. Our first step, then, is to select the most probable working hypothesis ; and to attempt this selection, to state the hypothesis and its immediate corollaries, and to take some first steps toward testing it, is the object of the present paper. Its chief purpose is to bring the hypothesis to the attention of those who are more familiar with the evidence than the writer can pretend to be, and in a better position both to present new evidence and to discuss it. The hypothesis here selected is, that composition governs properties in the case of cast-iron, in the same general way and for the same reasons as in the case of steel, mutatis mutandis. This hypothesis, which of course makes no claim to originality, certainly seems reasonable and probable; its exposition and discussion are made easy by our existing knowledge of the constitution of normal or " carbon " steel; it therefore seems worthy of consideration.

Jan 1, 1902

By Andrew Hyett

Over the last 30 years, a transition away from end-anchored bolts to fully grouted rock bolt systems has occurred in many underground mines. It seems geomechanically intuitive that the success of such bolts, which interfere with rock movements around underground excavations through a variety of complex interactions, is precisely why they remain challenging to instrument and monitor. Whereas measuring the load profile for an end-anchored mechanical bolt is trivial, for a fully grouted system, the load may vary dramatically due to discrete rock movement at cracks and joints. Despite the challenges, measuring the strain (i.e., load) along fully grouted rock bolts remains very appealing, and a lot of valuable research has been conducted using foil resistance strain gauges, particularly in US coal mines (Signer and Jones, 1990). Despite good intentions, more widespread adoption of this instrumentation remains unlikely for the following reasons: (i) The technology is expensive, partly because Intrinsically Safe (IS) requirements limit the number of suppliers and solutions. (ii) The technology is perceived as challenging to successfully implement except by those who are skilled in the art. (iii) The reliability of the technology is questionable in harsh environments. (iv) The technology relies on discrete pairs of strain gauges that may not capture the complete strain distribution along the bolt. No existing alternative technology can offer a solution to all of these limitations. However, in this paper, we introduce results from a new Distributed Optical Sensing technology that promises significant potential. Since the technology is capable of distributed sensing, our results suggest that this new technology can, for the first time, reveal the detailed strain profile along fully grouted rock bolts.

Jan 1, 2013

By R. T. Mishler

I wish to express my keen appreciation of the article on the above subject by Coe and C1evenger.l It has been doubly interesting to me, for the reason that the experience recorded and the principles evolved practically parallel the results of similar investigations made by myself and others at The Lucky Tiger Mine, El Tigre, Sonora, Mex. An outline of the work at El Tigre may aid in confirming the principles expressed by Coe and Clevenger. El Tigre has the unenviable distinction of possessing a slime with a much lower settling rate than any recorded in the article discussed. Under most favorable conditions the settling rate is about one-third that reported for the Liberty Bell mill, and one-tenth that reported for the Nipissing, Golden Cycle, and Presidio mills. This slow settling characteristic of Tigre ore has necessitated careful investigation of settling phenomena throughout the various evolutions of the plant. Previous Settling Investigation at Tigre During construction work at the mill, the metallurgical engineer in charge, D. L. H. Forbes, ran a series of experiments on settling. His tests proved that deep settling tanks were not ordinarily necessary. The use of tanks 2 or 3 ft. in depth was suggested.2 Later experiments demonstrated that the following principles of settling applied to Tigre pulp.3 1. In settling dilute pulp, settling rates are independent of pulp depth. 2. In settling thick pulp, settling rates are approximately proportional to pulp depth.4

Jan 1, 1918

By Gabriel Aguilera, Juan Arismendy

"As a separator machine, the hydrocyclone is one of the most commonly used equipment in different types of industries and particularly in mineral processing, hydrodynamic behavior allows efficient separation, but developing tests to optimize experimental equipment is expensive, therefore Computational Fluid dynamics (CFD) becomes a useful tool for optimizing the geometrical and operational parameters, and allows to analyze and understand the dynamics within the equipment. In the research was developed to simulate of 40 mm hydrocyclone where turbulence model was used Large Eddy Simulation (LES) for the continuous phase, for the generation of the air core and for the interaction of particles at low concentrations was implemented (mixture model), after the simulation was completed validation and comparation was done between simulation values and experimental."

Jan 1, 2014

By A. E. M. Warner, P. J. Mackey

Copper metal is produced in large or small tonnages in almost all countries of the world—handling raw materials in the form of either as-mined or milled ores, custom concentrates, or other custom materials including scrap and recycled copper. The scale of operations and type of technologies used around the world varies widely. There is a certain concentration of both mining and smelter-refinery production as a total of ten countries produce some 80% of world mined copper, while ten countries—mostly different ones— produce about 80% of smelted and refined copper. As a result, international copper trade is significant. The present paper takes the reader on a virtual tour of the copper plants throughout the world with a focus on smelter facilities. Operations and technology employed at each plant visited are discussed including a brief historical sketch. Future trends identified during the world tour are also discussed. The present authors considered sufficient time was required for a thorough study tour and settled on eighty days—the same as that for the celebrated fictional story of world circumnavigation in the 1870s. INTRODUCTION The celebrated French writer Jules Verne published his book “Around the world in 80 days” in English in1873 and it is the story of Phileas Fogg and his French valet Passepartout circumnavigating the world in 80 days in the fall of 1872 on a £20,000 wager (equivalent to over 2 million pounds today) from the exclusive Reform club in London. This is an interesting period for copper as it started trading on the London metals Exchange in 1876 and the start of global copper production chains started to take off at this time with the rapidly increasing electrification of the world. The production chain includes mining, mineral processing, smelting, refining and fabrication. Since 1880 annual world copper production has increased by over 150 times from 154,000 tonnes in 1880 (nominally considered as smelted copper—essentially the only route at the time to marketable copper) to over 23 million tonnes today (including total refined copper of 19 million tonnes of smelted copper including scrap and 4 million tonnes by solvent extraction-electrowinning), in tandem with increased electricity usage, along with significant transportation usage and for manufactured products (Figure 1).

Jan 1, 2019

By J. D. Edwards

When Charles Martin Hall invented the electrolytic process for the production of aluminum, one basic requirement was a supply of pure alumina. Now, more than 50 years later, the same requirement still holds, and there are no technical straws in the wind to indicate that this situation is likely to change. Long ago, Aluminum Company of America took a number of steps to see that this country should not face shortages of alumina and aluminum in time of emergency. As one step to this end, the Company developed and used a supply of bauxite in South America in order to conserve dwindling Arkansas reserves. Another, and more a program than a step, was to investigate every type of process that might bear the possibility of utilizing the low-grade ores of aluminum that are more plentiful than bauxite. It is a long story, but the investigation included electric-furnace processes, acid extraction processes and alkaline extraction processes, with or without preliminary furnace and sinter treatments. Some of the processes developed were operated in commercial production. This work has been continuous since the first World War. The turn of the wheel came sooner than was expected when, in 1942, bauxite shipmerits through the caribbean became uncertain and hazardous through the operation of submarines. The tremendous requirements of aluminum for the war effort were consuming high-grade bauxite at an alarming rate and a national search for substitutes began. High-grade bauxites, for technical and economic reasons, have been defined as those containing about 7 per cent or less of silica. While bauxite of this grade was limited in amount in the United States, there was in sight a substantially greater volume of low-grade, high-silica bauxite not amenable to economic treatment by the Bayer process, but richer in alumina than the clays or other available low-grade ores. It was at this point, and after several years of intensive research on this particular phase of the problem, that Aluminum Research Laboratories brought to completion the invention of one of its research staff, which made practical the utilization of large reserves of low-grade bauxite in America. Bayer Process The Bayer process has been almost universally used for the production of alumina from bauxite. This process, in outline, comprises the digestion of hely ground bauxite in a solution of caustic soda (NaOH) under pressure and at an elevated temperature. Alumina in the bauxite goes into solution as sodium alumi-"ate and the impurities—oxides of iron, titanium and silicon—remain undissolved. The undissolved residue, known as "red mud,'' from its color, is separated and run to waste. AluKlinum hydrate (A12O3.3H2O) is precipitated from the solution of sodium aluminate, and the liquor containing the caustic soda and some alumina is returned to the Process for digesting more bauxite. The aluminum hydrate, after washing, is calcined at a high temperature to produce

Jan 1, 1949

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By Susanne Pignolet-Brandom

Reflected light microscopy, and scanning electron microscope energy dispersive spectroscopic analysis and backscatter electron images were used to determine if a "slick dross" with undesirable handling properties has an assemblage of phases distinct from normal dross. This study has found that in the normal dross the most abundant lead phases are lead sulfide and lead metal and the most common copper phases are copper-iron sulfide and copper sulfide. In the slick dross, the most abundant copper phase is copper-lead sulfide and the most common lead phases are copper-lead sulfide and lead sulfide. The resulting mineralogical information has provided additional insight into the causes of the handling problem and the reaction mechanism for the formation of normal and slick dross

Jan 1, 1988