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By Stephen Burke

THE oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combus-tion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the condi-tions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 21120 + 702 --> 2FeSO4 + 2H2S04 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to dis-close any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1937

By W. W. Gerberich, P. L. Hemmings, V. F. Zackay

ThE strain-induced martensitic transformation may be used to attain desirable combinations of strength, ductility, and fracture toughness. One of the parameters is the relative stability of the austenite. For example, it has been shown by Zackay et al.1 that the volume percent of strain-induced martensite is related to the combination of strength and elongation obtained. It has also been shown that the degree of transformation is an important factor in the crack propagation resistance of metastable austenitic steels.2 Considering both tensile and crack-propagation tests, it was of interest to see if there was any functional relationship between the amount of strain and the volume of strain-induced martensite. Previously,9 it had been shown that at room temperature, there was a relationship between uniaxial tensile strain and the volume percent of resulting martensite given by The data were obtained by plastically elongating tensile samples to a certain strain and then measuring the field strength to determine the strain-induced ferromagnetic volume. This was accomplished for two conditions having yield strengths of 229 and 233 ksi. The nominal composition of this material was 9Cr-8 Ni-3 Mo-2 Mn-2 Si-0.25 C-0.09 N. In evaluation of the strain-induced martensite at a crack tip: the question arose as to whether Eq. [1] would also be valid under triaxial stress conditions. Tests were conducted on 1/2-in. thick plate material having a composition of 9 Cr-8 Ni-4 Mo-2 Mn-2 Si-0.27 C. It was found that sectioning, polishing, and etching of fractured specimens could reveal the strain-induced martensite occurring at a crack tip. Care had to be taken to minimize the final polishing steps so as to avoid a smeared layer of strain-induced martensite. The method for taking metallo-graphic samples from fractured crack-line loaded type samples is shown in Fig. 1. Observations of the strain-induced martensite occurring at room tem-

Jan 1, 1970

By J. F. Crouch

INTRODUCTION Roll front uranium has unique geologic characteristics (L,) which require specialized mining procedures. Roll front uranium occurs in arkosic sandstones with the ore zone typically less than 100 feet in thickness with up to 400 feet of overburden. The areal extent of ore is often a few thousand acres. Within the ore zone, ore grade material occurs in C and S shaped rolls, which are a few feet in width and height but may run laterally for several hundred feet. Since the total mine plan may include mining all ore, a roll front uranium mine may cover a few thousand acres. For both economic and environmental reasons, a roll front deposit is mined as a series of phases or sub-pits (3, 4) as illustrated in Figure 1. A typical sub-pit is 400 to 500 feet across. Sub-pit 1 is stripped initially and the overburden is spoiled on the surface. Depending on haul distance and overburden characteristics, stripping is done with trucks and shovels (or front-end loaders) or scrapers. When ore is encountered in sub-pit 1, mining begins, and the stripping equipment is moved to sub-pit 2, with sub-pit 2 overburden also being spoiled on the surface. When ore is encountered in sub- pit 2, sub-pit 1 mining should ideally be complete so the mining equipment can move to sub-pit 2 and sub-pit 3 overburden can be spoiled in the mined out sub-pit 1 area. Ore is mined selectively in a series of 12 to 24 inch cuts by a 2-1/2 yard backhoe on the basis of radiometric probing. For effective drainage, ditches must be maintained on the boundary of sub-pits, and mining lifts are kept as level as possible, with the orebody slightly elevated as part of general good mining practice. Waste removal in the ore zone is done by self- loading scrapers near the orebodies and by push-pull or push loaded scrapers away from the orebodies. Each self-loading scraper cut is

Jan 1, 1983

By D’Arcy A. Shock

In this year's review, the concept of solution mining has been expanded to include total solution as well as the technology of leaching, or partial solution methods. Leaching methods continue to make strides in the processing of metallic minerals, particularly in copper and uranium production. No quantitative data are available on the increase of leach operations; however, it is known that there were more systems installed in 1969 and that the estimated 15% of U.S. domestic production of copper produced in 1968 was by leach methods.1 While the number of publications appearing during the year were few,2,3 there were special sessions in this field at the AIME Annual Meeting and SME Fall Meeting in 1969 and more scheduled for these meetings in 1970. Significant areas that should be mentioned are: the continuing interest in bacteria to convert sulfide sulfur to acid thus reducing reagent costs in both copper and uranium sulfide ores, the exploration of leaching agents other than common mineral acids or alkaline solutions,4,5 kinetic studies of leach mechanisms and the development of microfractures for increased leach solution penetration by use of chemical or atomic explosives.6,7

Jan 1, 1970

By H. J. Levinstein, W. H. Robinson

A method of chemically polishing silver for metal-lographic examination has been developed. The samples are prepared by polishing on 0, 2/0, and 3/0 paper. They are then polished on 600 micro-cut paper, followed by a final mechanical polish on a cloth containing 5µ diamond paste. The samples are then chemically polished in a solution of 100 cc of saturated chromic acid and 5 cc of a 5 pct HC1 solution. The chemical polishing is performed by swabbing with a cotton ball saturated with the solution. During the chemical polishing, the sample is rinsed frequently in running water. Polishing in this manner for 5 min is sufficient to remove the strained material from the previous polishing operations. The amount of material removed is approximately 4µ/min. The surface obtained is flat and free of pits. Fig. 1 is an interference micrograph of a silver surface polished by this technique. If the solution employed is of improper HC1 content, an interference color film will form on the sample. This film can be removed either by swabbing with a cotton ball saturated with ortho-

Jan 1, 1962

By G. H. Tausch, J. R. Dublin, T. A. Huber

Simplified equipment and techniques have been developed to permit cementing a completion interval in a well and recompleting higher, lower, or at the same depth in such a manner as to: 1. Eliminate the need for a conventional drilling or workover rig. 2. Eliminate mud and other cement contaminants which have long interferred with ideal cementing. 3. Eliminate need for drilling out cement. 4. Provide a more satisfactory recompletion. 5. Provide a more economical recompletion. This technique involves the use of a small-diameter, lightweight, tubing extension which is run on a wireline and set in a landing nipple previously installed in the tubing string. Low squeeze pressure and small cement volumes, with their attendant cost reduction, are successfully used when wells are completed and reworked with salt water or other penetrating fluids. Relatively low-water-loss cement is an integral component of the technique which provides that excess cement be reverse-circulated from the well to leave the casing void of cement when recompleting lower or in the same interval. Substantial cost reductions are realized by using the simplified or low-pressure cementing technique, and the ratio of successful squeeze-cement operations has been increased. Squeeze-cementing or recementing is the act of filling a channel behind casing or filling holes purposely placed in the casing. To obtain a satisfactory squeeze-cement job, it is necessary only to fill the channel or the perforation holes with a cement filter cake and to allow it to harden in that position. In the past, the presence of mud in a well has been considered the chief deterrent to obtaining a good cement bond and satisfactory cement job; however, late developments in squeeze-cementing have made it possible to eliminate cement contamination or interference. Since it is possible to form a cement filter cake with a small pressure differential, squeeze-cementing with high pressures may not be necessary in most cases. The amount of cement needed to fill the annulus about the casing and even to fill part of the casing, if necessary, is generally small in quantity. Use of low squeeze-cementing pressures and small quantities of cement provides the following advantages: 1. Longer effective life of well tubing, casing, and other equipment; and less chance of costly equipment failure due to excessive pressure. 2. Monetary savings effected by elimination of retainers and specal squeeze-cementing tools. 3. Monetary savings effected by use of small quantities of cement and fewer squeeze-cementing operations. 4. Future surface squeeze-cementing equipment may be smaller and more economical to operate and maintain.

Jan 1, 1955

By Richards R. Vandervoot

T HE creep behavior of many polycrystalline metals at moderate stresses can be described by the empirical relationship: where Em is the minimum creep rate, A is a constant, a is the applied stress, E is the average elastic modulus at the test temperature, and D is the self-diffusion coefficient.&apos; This equation is generally applicable for strain rates of less than around 10-5 per sec and temperatures greater than about one-half the melting point in absolute units. Under these conditions atomic mobility plays an important role in the deformation process, and steady-state creep occurs when a dynamic equilibrium is reached between the generation and recovery of dislocation substructure. Although several theoretical mechanisms have been proposed to explain the creep of polycrystalline solids,2"4 the dislocation climb model2 is in accord with most experimental observations. The majority of creep data used to develop Eq. [1] came from metals with either the fcc or hcp crystal structures. However, on the basis of results for a and 7 iron as well as those for a and a thallium, Sherby concluded that the high-temperature deformation behavior of close-packed metals and bcc metals is probably the same.&apos; The greater creep resistance of fcc and hcp metals and alloys on a relative temperature scale was attributed to lower diffusivities in the close-packed structures. To further compare the creep properties of fcc, hcp, and bcc metals, creep data for all six bcc refractory metals were analyzed according to Eq. [I]. The results are shown in Fig. 1. The sources of information for the quantities used to prepare this figure are listed in Table I, except for high-temperature elastic moduli. The latter data were obtained from Refs. 28 and 29. The dashed lines in the figure represent the range and breadth of data analyzed by Sherby for fcc and hcp metals. In general, the deformation behavior of all of the refractory metals, ex- cept possibly that of tungsten, can be represented by Eq. [1]. This correlation is strong evidence of the similarity that exists between creep of pure close-packed metals and creep of pure bcc metals. At (Em/D) < 108, the results of Flagella and Tarr on tungsten (W-1 in Fig. 1) agree with the five-power stress law, while those of Green (W-5 in Fig. 1) show a seven-power stress dependence. Where (Em/D) > 108, the stress exponents for other data on tungsten were in the range 10 to 15. It is possible that the creep rate dependence on stress in this region is not a power law but exponential (i.e., Em - eßo). However, it was not feasible to differentiate between these two cases because of the steep slope and scatter in the data. Note the inflection point in the curve for the data of Flagella and Tarr (W-1 in Fig. 1). The slope of the line changes from 5 to around 10 at Em/D = 108. The breakdown of the fifty-power stress law at high stresses is not uncommon in other metals, and this phenomenon may result from nonequilibrium conditions in the material such as excess lattice vacancies produced by rapid straining.30 The mechanical strength of a polycrystalline metal is related to its microstructure. Attempts to establish the influence of grain size on the creep rate of metals and alloys have led to a wide variety of results. For example, the following effects have been observed: creep rate decreases as grain size increases;31&apos;32 creep rate decreases as grain size decreases;&apos;,33 creep rate is a minimum at some critical grain size and increases with either an increase or decrease in

Jan 1, 1969

By David Keys

THE actual procedure in estimating depth of overburden from mag-netic observations made on the surface will vary with the form of the deposit and any theoretical discussion will apply only so far as the form of the deposit conforms to the mathematical premises on which the theory is based. Since the shapes of natural deposits in the field cannot be expressed rigorously in mathematical form, the best that can be done is to assume some simple form and deduce results. Fortunately many small variations in form produce only slight changes in the estimated depth of overburden, therefore the methods have a definite practical value. For the theoretical treatment, magnetic ore deposits may be divided roughly into three classes, depending upon whether the magnetic anom-alies may be considered to arise from (1) a single magnetic pole, (2) a dike or (3) a magnetic doublet. Particular cases, falling under one or other of these classes, have been discussed by different authors.1-4 In general, it may be stated that when the magnetic effects as measured on the surface are due only to one pole of the body, the other pole being so remote that its effect may be neglected, the resultant anomaly F at any point will vary as the inverse square of the distance r of the point from the pole, which may be expressed mathematically by F = k/r2, where k is a constant. When the deposit occurs in the form of a long, thin dike, the resultant anomaly will be of the form F = k&apos;/r and when the deposit is in the shape of a lens, so that both poles have an appreciable effect on the surface, the result will be similar to that caused by a magnetic doublet, and the form will be F = k&apos;/r3. The particular class under which a deposit falls may be deduced from the results of the magnetic survey. The second class is readily found, but there may be difficulty in deciding between the first and third. Isody-namic contours of both the vertical and horizontal anomalies will often be a good guide in making a correct decision.

Jan 1, 1937

By A.S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric Pressure and by heat transferred to it from rock at high temPerature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. Methods Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1943

By A. S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric Pressure and by heat transferred to it from rock at high temPerature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. Methods Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1943

By Meng-Cherng Sun, Fun-Den Wang, David M. Ropchan

A proposed technique for improving coal-mine roof stability by softening parts of coal pillars along the sides of entries developed from structural analysis is presented. This technique is based on the transference of the high stress concentration in the roof near the upper corners of a rectangular opening to the roof rock and coal over the solid away from the opening. This transferral is accomplished by softening parts of the coal pillars by drilling a series of parallel holes into the coal in the ribs and face of the entry prior to advance. The effectiveness of the pillar softening in terms of reducing the opening width (so that the stress in the roof near the corner is equivalent to that of a narrower opening) ranges from 3 to 5 ft for a 16-ft entry using a series of 4 to 5-ft-deep parallel drill holes of 3 to 6-in.-diam on a 1 to 2-ft spacing for a particular geology. Pillar softening should be highly effective in controlling roof where cutter-roof cave conditions exist, because this technique reduces the high stress concentration in the roof at the upper corners of the opening. It may also be effective for reducing tensile roof failure and coal rib sloughing for certain specific geological conditions. This technique appears to be a simple, effective, and practical method that can be used to supplement conventional roof support methods of roof bolting, timbering, roof truss, and other existing methods in underground coal mines. The authors consider the technique feasible and believe that it merits underground trials.

Jan 1, 1975

By G. A. Bole, F. W. Davis

The purpose of this paper is not to report, to the Institute, the results so far obtained in the survey, by the Bureau of Mines, of the metallurgical requirements for open-hearth refractories, but to present an outline that we hope will serve as a basis for discussion. The systematic survey that the Bureau proposes to make has not been outlined, although considerable preliminary work has been done in the way of interviewing open-hearth superintendents in several of the larger steel plants from the Chicago district eastward. At the several conferences so many of the opinions were diametrically oppoeite, when considering the same point, that it was thought that such an opportunity as the Institute offers in the way of a clearing house for moot metallurgical topics should not be overlooked. For this reason, the paper has been prepared as a basis for a discussion which, it is believed, will be of value in outlining the program of the Bureau. D. A. LYoN, Assistant Director. The importance of securing suitable refractories for metallurgical operations is daily becoming more universally recognized; particularly in the manufacture of open-hearth steel, where the life and earning power of the furnace depends largely on the judgment and care exercised in the selection of the correct quality of refractory for each of the parts. Any innovation that would make available to the steel manufacturers refractories with longer life or better suited to their needs than those now employed, and at a cost that would permit of their use, would be of enormous value to the industry at large. It is quite probable that revolutionary changes would not be necessary. Material now used in some parts of the furnace might, by more suitable preparation, be made of much greater service; in other parts, possibly entirely different material would be necessary in order to effect much improvement. Inasmuch as different parts of the furnace structure perform different functions and are subjected to different service conditions, a refractory suitable for one part will be entirely unsuited for another. For this reason, to make a comprehensive study of the refractory requirements of the processes, we should consider the furnace as built up of a number

Jan 1, 1924

By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors&apos; experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959

By J. L. Rodda

The desirability of a uniformly sized abrasive for metallographic polishing has probably been recognized in a general way for a long time. Certainly all metallographers have recognized the damage that can be done to a polished surface by a piece of grit, especially if one of the softer metals, such as zinc or aluminum, is being polished. It is to be doubted, however, whether many metallographers have had any adequate idea of the particle size of the abrasives they were using or of the range of sizes encountered in any given grade of abrasive. At any rate, the descriptions of abrasives for metallographic work found in the literature are generally very meager. It was with the idea of securing an abrasive with a limited range of particle size that a study of this problem was commenced. Commercial abrasives, even when recommended for metallographic work, are made up of particles of varying sizes. One such abrasive contains some particles so fine that they remain in suspension for days and other particles so coarse that they settle at the rate of 3 in. per minute. It is evident that the coarsest particles are over 100 times the diameter of the smallest ones, or over 1,000,000 times the volume. The hopelessness of avoiding scratches under these conditions is evident. Vanderwiltl has described a laboratory method for grading abrasives in which the elutriator is used. Le Chatelier&apos;s method, described by Goereq2 also makes use of an elutriator. However, the elutriator is too slow for this purpose and requires too delicate a control for the range of sizes desired. The method of stirring up the abrasive in water, allowing it to settle for a given time, then drawing a measured depth off the top of the suspension, has been finally adopted as the simplest procedure. The largest particle in a given portion is then determined by Stokes&apos; law:3

Jan 1, 1932

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By R. Haynes

ON the basis of compositional changes of a phase observed in a eutectoid Cu-Al alloy1 it has been suggested that mechanisms for the decomposition of the ß phase proposed by earlier workers2-5 were incorrect. These data are reinterpreted in conjunction with lattice parameter data obtained on an alloy containing 12.2 pet Al, whose isothermal transformations have been reported elsewhere.5 The a Lattice Parameters of a 12.2 Pet A1-Cu Alloy—~iffraction patterns of completely transformed specimens were obtained in a back reflection camera using copper Ka radiation. Lattice parameters of

Jan 1, 1959

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By Craig S. Hartley

Expressions are obtained for the energy changes associated with the reaction of (a& (111) slip dislocations on intersecting (110)planes in anisotropic bcc metals. An energy criterion for assessing the likelihood of dissociation of the products of such reactions is also presented. It is found that the "burrier reactions" which form a(100) dislocations at the intersection of two active {110) slip planes are more energetically favorable in metals which exhibit a high value of Zener&apos;s anisotropy factor, A, than those which have a low value. The results are presented in a form which permits the stacking fault energy to be obtained from a measurement of the separation between par-tials in a dissociated configuration. However, until accurate calculations or measurements of the stacking fault energies involved are available, it is not possible to assess the physical importance of dissociated dislocations. In a recent paper,&apos; the energy changes associated with several types of reactions between two slip dislocations, (a/2)(111){110), in bcc structures were calculated.* Isotropic elasticity and the approxima- tion v = -3- were employed. The purpose of this work is to present calculations of the energy changes for many of the same reactions using anisotropic elasticity. The problem of dissociation of a(100) and a(110) dislocations is also considered, and maximum fault energies for which dissociation will be energetically favorable are calculated for several bcc metals. Two general types of reactions are considered; those for which the reactant (a/2)(111) dislocations have long-range attractive forces and those for which the reverse is true. An example of the former is: (a/2)[lll] + (a/2)[lll]-a[l00] while the latter are typified by: (a/2)[lll] + (a/2)[111] -a[011] Only reactants lying in different slip planes are considered; therefore, the products must lie along (111) or (100) directions, which are the intersection of two {llO} planes. It will be assumed that the reactants and products are infinitely long parallel dislocations, since in this case the energy change associated with the reactions is a maximum.&apos; THEORY The self-energy per unit length of a straight mixed dislocation in an anisotropic medium can be written? where b is the Burgers vector, K is an appropriate combination of the single-crystal elastic constants, and R and ro are, respectively, outer and inner cut-off radii of the elastic solution. The energy given by Eq. [I] does not account for any variation of the core energy with orientation. This could be manifested by an orientation dependence of the core radius or, equivalently, the Peierls width, of the dislocation. However, the energy contribution due to this source is expected to be small, and current models of the dislocation core are not sufficiently accurate to justify such a refinement. It has already been shown that for the isotropic case the energy contributions due to nonzero tractions across the cores of the reactants and products exactly cancel one another in the reaction.&apos; Accordingly, it will be assumed that this contribution to the total energy change in the anisotropic case is small. In the subsequent discussion it is also assumed that the core radii of the reactant and product dislocation are the same and that, where stacking faults are formed, the faulted region is bounded by the centers of the partials. Consequently only changes in elastic energy due to the reactions will be considered. When the dislocation is parallel to either the (111) or the (100) directions, K may be written:375 K = (Ke sin2 a + Ks cos2 a) [2] where K, and Ks are the combination of elastic constants corresponding to an edge and screw dislocation lying along the same direction as the mixed dislocation, and a is the angle between the direction tangent to the dislocation line and the Burgers vector. Eq. [2] should not be confused with the isotropic approximation to the variation in energy with line Orientation.6 It should be noted that the essentially isotropic expression for K is a result of the characteristic symmetry of the (111) and (100) directions and is not, in general, valid for other dislocation directions in anisotropic cubic metals. The energy* change for a reaction in which the re- actant and product dislocations are parallel perfect dislocations can be written: where Ep and E, refer to the self-energies of the products and reactants, respectively. For dislocations parallel to (100) and (111) directions, Eq. [3] becomes:

Jan 1, 1969

By A. W. Ruff

In the last ten years large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now-prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. In the last ten years, large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. EXPANDING-GAS-BUBBLE THEORY There has been an outstanding change in the conception of how an explosive produces rock failure. The early theory which explained rock breakage was correct for some of the first force-producing agents such as quicklime. When a drillhole was filled with quicklime and water added, the material expanded and steam was generated. The expanding material and the steam exerted a slowly increasing pressure on the sides of the drillhole. The force broke the rock by splitting. Because a great quantity of gas was produced by the deflagration of gunpowder, the same process of the gas pressure splitting the rock was assumed to take place. Even after 80 years of use, the rock-breaking action of all high explosives was thought to be caused entirely by the expanding gas bubble which tore and split the rock. Fig. 1 shows a vertical section through an exploding spherical charge of high explosive. It illustrates the early theory which attributed the entire breakage to the expanding gas bubble. The basic idea of this theory is that the breakage started at the explosive charge and progressed toward the free face. REFLECTED-WAVE THEORY me expanding-gas- bubble theory has gradually been replaced by the reflected-wave theory. The reflected-wave theory explains rock failure by explosives in the following manner: The enormously high gas pressure in the drillhole produces fracturing of the rock on the sides of the drillhole. The fracturing around a 1 1/2-in. diam drillhole is usually confined to an area with about a 6-in. diam. In the fractured area, the pressure of the gas is reduced until the force on the walls is no longer capable of fracturing the rock. Although the gas pressure does not continue to fracture the rock, the pressure imposes a high impact stress on the wall rock. In addition, a pressure or seismic pulse is produced in the rock. The pulse is probably entirely a compression pulse when originally produced in the rock. But, with distance, part of the energy of the compression pulse is transformed into a tension pulse which follows the compression pulse. The explosive charges and burdens used in conventional mine blasting are such that the tension pulse of the original wave is probably too small to be considered in a practical evaluation of the theory. The compression pulse is transmitted through the rock with no associated fracturing.

Jan 1, 1961

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s&apos;S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.&apos; There are a few marked discrepancies in the intensity comparison of the two s&apos;s, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s&apos; have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955