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By Rudolph G. Wuerker

The progress made in testing the strength of rocks and minerals as they are encountered in mine operation is reviewed. An attempt is made to correlate these physical measurements with abrasive hardness, grindability, and behavior in comminution on one hand and fracture of rocks in pillars and roof control on the other. THIS paper reviews the progress made in testing the strength of rocks, ores, coal, salts, and other minerals as they are encountered in mine operations. It attempts to correlate the results of these physical measurements with technological properties more useful to the mining engineer: abrasive hardness, grindability, and behavior in comminution on one hand, and roof control, fracture of rocks in pillars, and mining methods with controlled caving on the other. In the following pages, the materials discussed will be referred to as rocks. Basic to rock mechanics and comminution are the problems of strength, elastic behavior, and failure, common to all brittle materials. A distinction will be drawn as to theoretical and applied research, and discussion of the progress made in each field will include test data obtained by the U.S. Bureau of Standards,1-1 the U.S. Bureau of Mines," the Iowa Engineering Experiment Station,"." the Committee on Geophysical Research at Harvard University,'" Basic Industries Research of the Allis-Chalmers Manufacturing Co.,11,12 by Philipps,13 and by Mueller," to name only a few. With refinements of testing methods and increased standardization. more useful and more comparable results have been achieved. This is especially important in testing a material like rock, as the inherent heterogeneity demands careful and exacting procedures. New measuring procedures that appear to supersede well known standard methods have contributed to faster and less costly testing yet have introduced new concepts, with implications as to comparability of results which must be watched. Reference is made to the sonic method for determining elastic properties," to be discussed in detail below. Basic Investigations Historically, all work in the field has started with the simplest determinations such as those for crushing strength, abrasive hardness, and grindability. These serve the limited objectives in the researcher's field of specialization: building construction, road ballast, roof control in mines, comminution, and seismic prospecting. Occasionally, fundamental properties like the modulus of elasticity E and Poisson's ratio v have been determined with the idea that they might have some bearing on the technological properties of the material under investigation. But it was not until the work of Philipps,13 of Harvard University,'" and of the U.S. Bureau of Mines"' that sufficient basic data were collected to allow researchers to go beyond the technological test and find the fundamental laws behind the behavior of rocks in mine and mill operations. The properties to be looked for are those that describe the elastic behavior of any material, the modulus of elasticity E and Poisson's ratio v being the ones determinable with least difficulties. Only two such properties are required to compute any other property such as the shear modulus, the modulus of rigidity, and the bulk modulus, all of which are related to each other according to well known equations of the theory of elasticity." In spite of their heterogeneous character, all rocks tested have possessed elastic properties. This does not mean that rocks of the same type always have the same modulus of elasticity, which varies exactly as the crushing strength or any other physical property of a rock can spread over a wide range. This has been explained by imperfections of the material always found in rocks, but to some extent this scattering of data is caused by inaccuracies inherent in the testing methods. Modulus of Resilience, a Criterion of Failure Increased availability of E values should allow us to test the validity of the quantity of strain energy theory which has been used in the solution of roof control problems by Philipps13 and by Holland.'" Recently Bond and Wang12 have applied this theory to explain the failure of an elastic material in comminution. Actually it is a very old theory, proposed as far back as 1885 by Beltrami.16 By its assumption the condition of yielding is determined by the term S2 M, = — x volume. Here M, is the modulus of 2E resilience, and its dimension is inch-pounds per cubic inch, that is, work per unit volume. Its numerical value is equal to the area under the stress-strain diagram. In the foregoing equation S is the yield stress (in psi) in tension or compression, whatever the case may be. E, the modulus of elasticity, is in psi. The great appeal of Beltrami's concept of stored energy lies in the fact that the two properties which seem to influence failure most, strength and elasticity, occur in the formula for the modulus of resilience. As an illustration of this, the moduli of resilience in compression of some typical materials tested by the U.S. Bureau of Mines" have been plotted in Fig. 1. The sample of concrete of conventional mix is shown only for the sake of comparison. Its determination was made in the Department of Mining and Metallurgical Engineering, University of Illinois. The values of the moduli of resilience of the various specimens in the plot are:

Jan 1, 1954

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By G. T. Davis, C. C. Mattax, M. O. Denekas

The effects of crude oil cornponents on the wellabil-ities of sandstone and limestone were investigated. Fractions containing cornponents differing in molecular weight and molecular structure were obtained from crude oils by distillation, extration and chromatography. Individual fractions were then tested for their effects on rock wettability. Tests indicate that sundstone wetta-bility may he changed by a complex variety of surfactants varying both in molecular structure and molecular weight. Limestone appears to be particularly sensitive to basic, nitrogenous surfactants. INTRODUCTION Investigations in recent years have shown that petroleum reservoir rock wettability can exert a significant influence on the efficiency with which oil can be produced by water flooding. While most reservoirs are presumably water-wet, they niay range in their degree of water-wettability from near-neutral to strongly water-wet.'" Reservoir wettabilities other than strongly water-wet are likely to be induced by adsorption of surface-active components froni the crude oil on the pore walls of reservoir rock.:' Little is known, however, about the nature of the surface-active materials which are likely to be adsorbed by the reservoir rock. Due to the complexity of crude oils. attempts made in the past90 isolate these surface-active components have met with only limited success. It is probable that many different types of surface-active materials arc indigenous to crude oils and that many of these may be adsorbed to varying degrees by reservoir rock. This was cxolored in the studies discussed in this paper. The over-all objective in these studies is to ascertain whether the wettability of a given reservoir can be determined by examining the surfactant content of the reservoir crude. To this end, crude oils were examined to determine the variability of indigeneous surfactants with regard to chemical type and molecular weight. Crude oils were separated by distillation into fractions differing principally in molecular weight, by chroma-tography into fractions containing compounds differing in polarity, and by solvent extraction into nitrogenous and non-nitrogenous fractions. Individual fractions were then tested for their effects on the wettabilities of sandstone or limestone rock samples. EXPERIMENTAL PROCEDURES Fractionation of the Crude Oils Samples of Miocene, Eocene and Jurassic crudes were distilled at temperatures not exceeding 200°C. The final stages of distillation were completed in a molecular still at pressures down to three microns of mercury. Fifteen to 30 fractions were obtained from each crude oil. These cuts were sufficiently broad that separation can be considered to have been effected principally on the basis of the molecular weights of the constituents of the crude oil. A considerable portion (20 to 40 per cent) of the crudes would not distill under these conditions. The residues were recovered and tested with the other fractions. Fractions differing in polarity were separated from a crude of Pennsylvanian age and an extracted sample of Miocene oil by chromatography, using a solid adsorbent. Since surfactants are, for the most part, polar compounds, chromatography should separate many of the surfactants from the crude oil. Such a separation should provide fractions containing compounds differing in molecular structure. Nitrogeneous compounds were extracted from Miocene crude oil with a solution of sulfuric acid in meth-anol. The residual oil was further processed by chonia-tography. Each of the fractions obtained by thesc procedures was dissolved in a non-polar solvent (xylene) and diluted to its original concentration in the crude oil. No attempt was made to maintain an anaerobic atmosphere above the samples while they were being dissolved. These solutions of the fractions were then tested for their effects on the wettability of sandstone and limcstone as discussed in the next section. Measurement of the Effects of Crude Oil Fractions on Rock Wettability No entirely satisfactory method for measuring rock wettability has yet been developed. All methods used are empirical. The imbibition test was used in these studies. This test is based on the tendency of a rock to imbibe the wetting phase spontaneously. For example, if a strongly water-wet rock is first saturated with oil and then placed in water, the water will quickly invade the rock by capillarity and much of the oil will be displaced. If the rock is slightly water-wet, water irnbibition will proceed more slowly and, in many instances, considerably less oil will be displaced. A water-saturated, oil-wet rock will imbibe oil. The initial rate with which water (or oil) imbibition takes place indicates, qualitatively, the degree of water (or oil) wettability of the rock.

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By C. C. Wright, R. J. Day

ALTHOUGH data on the exact tonnage of recoverable coal silt are not known, the quantity produced in 1943 was estimated to be over five million tons for the anthracite region of Pennsylvania alone. Since that time the recovery of the No. 5 buck- wheat size previously included in silt estimates has increased greatly thus reducing the total silt tonnage. As a compensating factor, however, the methods of recovering silt previously escaping into the rivers and streams have been markedly improved so that the net figure may not have changed materially. Comparable estimates for bituminous coal are lacking, but undoubtedly the silt represents a significant tonnage. With the trend toward increased wet cleaning of the smaller sizes of bituminous coal, it is to be expected that even greater quantities of silt will be available in the future. The raw silt from anthracite collieries usually contains a high mineral matter content, but technological developments in fine coal cleaning have been making rapid advances and it appears probable that more extensive use of these methods will be employed in the near future. Bituminous coal silt in many instances contains a similar high mineral matter content. As with anthracite silt, however, the cleaning of this material, where necessary, appears both technologically and economically feasible. With a view to upgrading the size and value of silt, considerable laboratory and pilot plant work has been conducted by a number of organizations on what is commonly known as pelletization. Actually the process is one of extrusion in which the moist silt is extruded from a die in the form of rods, which usually break into relatively short lengths-a few inches long-as they fall from the die. Fig I is a photograph of some extruded 3/8-in. diam pellets and of the anthracite silt from which they were produced. This technique of producing larger sized material from fines is by no means new, having been used extensively by the industrial carbon and clay industries for years.' The application of the process to coal silt appears, however, to be relatively new. The first major program of investigation dates back only to July 1945, when a group of engineers representing the Anthracite Institute, The Pennsylvania State College and the J. F. Pritchard and Co. conducted preliminary tests on the extrusion of anthracite silt at the Floridin Co. plant at Warren, Pa. Since that time these three organizations-individually, together, and in co- operation with other interested groups- have actively pursued work on various phases of the problem. Much of the early history and details of the laboratory and pilot plant work by the Anthracite Institute, has been reported by Mulcey and Eckerd.2 It is the purpose of this paper to report additional information on the process, especially with respect to the factors influencing the quality and use properties of the product, and the current develop

Jan 1, 1948

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"' an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)', four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By A. R. T. Denues

LIQUID-OXYGEN explosives commonly consist of a carbonaceous absorbent enclosed in a canvas wrapper and soaked with a liquid con-taining more than 90 mol per cent of oxygen. Investigation of these explosives in this country was initiated in 1917 by George S. Rice, then Chief Mining Engineer of the Bureau of Mines. The early development is summarized in two papers.1,2 Their characteristics, advantages and disadvantages were considered in a recent bulletin of the Bureau of Mines.3 Other publications of this Bureau4,5 treat the technology of these explosives and contain adequate references to pertinent literature. These investigations defined the properties of liquid-oxygen explosives and improved them greatly; however, an outstanding disadvantage is their high inflammability, a property of critical practical importance. These explosives as hitherto prepared are easily inflamed; the combustion resulting from an accidental ignition is particularly dangerous because of the ease with which it passes into detonation. For this reason the Bureau of Mines undertook a cooperative investigation, which has resulted in the development of fire-retardant treatment for the minimiza-tion or elimination of this hazard without materially impairing the explosive properties, including the ease of detonation. This presentation will offer a general description of the investigation and the outstanding results. Further phases will appear in subsequent short papers, and the entire investigation including the results of detailed experiments will be available in a forthcoming bulletin of the Bureau of Mines (Bull. 429). The effects produced by fire-retardant treatments of the carbonaceous absorbent and of the canvas wrappers were investigated separately, and the efficacy of combinations of these treatments with particular reference to the possibility of inflammation and to the development of detonation from inflammation was studied. The experimental explosive was pre-pared from a granular carbonaceous absorbent and the results described may be more or less unique for such a material. An extensive preliminary

Jan 1, 1940

By Charles Meyer, Reno H. Sales

AT Butte, successive zones of sericitized and argillized quartz monzonite occur around every ore-bearing fracture regardless of its size, attitude, or relative age. The two types of alteration always occupy the same relative positions; sericite adjacent to the ore-bearing vein, clay minerals always between the scricitized rock and fresh quartz monzonite, except where overlap of alteration effects between adjacent fissures has eliminated the lower grade mineralogical products, as is the case in much of Butte's Central zone of pervasive sericitization. As long as active circulation continued in the channel, each zone migrated away from the fissure, that is, it grew at its outer edge and simultaneously receded at its veinward edge because of encroachment by the next innermost zone. The different mineralogical and chemical responses within the wall rocks to the attack by the ore fluid are dependent not on a drastic about-face change of composition of the fluid in the channel relative to its ability to alter the quartz monzonite but on continuously varying conditions of physico-chemical environment within the wall rock outwardly from the vein.' Introduction From the economic viewpoint it is highly desirable that much effort be expended for the purpose of increasing our knowledge of ores and their origin. It has been the observation of the senior writer, many times expressed, that the mining companies have spent too little money in research on the geology of nature's deposits of copper, lead, and zinc, which we know to be of limited extent and which, when exhausted, must be replaced by new discoveries. Experience at Butte and elsewhere has forced the conclusion that observation and mapping in the field must be supplemented by laboratory work if we are to arrive at a reasonably correct understanding of the geology of ore bodies and their environments. It is only through the medium of such correct understanding of geology that we shall be able to accomplish the maximum toward aiding mine operations and at the same time provide a proper background for field examination work whether it be geological or geophysical. The Anaconda Copper Mining Company's answer to the need above expressed has been to equip a geological laboratory at Butte. The reason why Butte was selected is obvious, for situated there is one of the world's largest and geologically most interesting concentrations of copper and zinc. Furthermore, because of the great extent of underground workings both laterally and vertically, the opportunities for observation and study of ore occurrences probably are unequaled anywhere. The laboratory was established with five principal objectives in view. These were: 1. As an aid to Anaconda Company mine operations at Butte and elsewhere, this work to supplement that of the mine geologists. 2. To aid in acquiring as complete an understanding as possible of the behavior of Butte veins and ore bodies laterally and in depth.

Jan 1, 1949

By W. N. Poundstone

The mining and ventilating system used in development work in the Pittsburgh Seam in northern West Virginia is discussed. The seam conditions and the nature of the accompanying methane gas are described. The type of equipment and the mining cycle will be discussed, showing how they are well suited for very gaseous development work. Face ventilation in development work is possibly the fastest growing problem of the industry. The coal mines of the future will be faced with the prospect of mining from under increasing depths of cover. Consequently, larger and larger amounts of methane gas probably will be found. The Pittsburgh Seam, in northern West Virginia, is an example of an area already faced with this problem. At the present time, most of the development work being done in this seam lies beneath 500 to 1200 ft of cover. The Pittsburgh Seam in this area has always been very gassy—even near the outcrop—and the recent development work has been accompanied with extremely large volumes of gas. In many cases, a single development section has liberated in excess of 1,000,000 cfm in 24 hr. This problem of heavy gas liberation was the chief concern, several years ago, when continuous mining equipment was first considered at Christopher Coal Co. All of us were apprehensive about the liberation that would accompany rapid extraction in a single working place. However, the experience during the past few years has shown that this ability to mine only one place at a time, is actually the key to working this type of coal. With all of the mining or advancement concentrated in one place, the ventilation can also be concentrated. By this it is meant that continuous mining permits the active working place to be ventilated with a maximum amount of fresh air, taken directly from the intake source without first passing another working place. Continuous mining (and a good ventilating system) also permits a much greater concentration of attention or vigilance to the actual working place. There are two things that are very important to the mining of coal having high rates of liberation. First, adequate volumes of air are necessary. Second, and perhaps more important, a mining and ventilating system must be used that will provide an uninterrupted flow of air to every portion of the working section. Liberations of this magnitude take only a few seconds of interruption for a dangerous accumulation of gas to occur. With adequate volumes of air available, the ability to concentrate ventilation more than offsets the concentration of gas emission that is inherent with continuous mining. The mining system used with continuous mining equipment at Humphrey Mine is similar to the system used at many mines in the area for development work. This system is designed to favor ventilation, realizing that other efficiencies are meaningless if the equipment must stop because of ventilation difficulties. This plan is especially well suited to minimizing ventilation interruptions. Basically, the overall plan of mining is to develop headings into virgin coal and encircle or block out large areas. These blocks are generally at least 2000 ft sq. The purpose of this blocking out is to bleed gas from the area before pillaring. Experience has shown this method to be quite effective, even in the most gassy areas. The gas in this field seems to migrate or flow readily from the solid coal into the outside return headings of the development work. The numerous clay veins and slips that are found in the area are extremely good avenues for gas flow. A block of coal, surrounded with development headings, usually bleeds off readily; and since it is cut off from the virgin coal, it is not subject to gas migration, through the seam, from this source. However, the outside return of the encircling development work, adjacent to the virgin coal, may liberate gas for years. This liberation from the outside ribs in the virgin coal is the reason split ventilation is used in development work. If split ventilation were not used, there would, in many cases, be a serious build-up of gas in the intake before it could reach the working face. Fig. 1 shows a typical development section having seven headings. The two outside places on each side are returns, and the three center headings serve as intakes. This section is equipped with a ripper-type continuous mining machine. An off-track loading machine is used to load from a surge pile on the

Jan 1, 1961

By D. E. Coates, G. R. Purdy, S. V. Subramanian

The morphological stability of the planar solid-liquid interface in dilute ternary alloys, undergoing steady-state unidirectional solidification, is analyzed in terms of both the constitutional supercooling principle and the perturbation methods recently developed by Mullins and Sekerka. First, various steady-state solutions for the two solute distributions ahead of a planar interface are examined. The nature of the solutions depends on the size and concentration dependence of the off-diagonal diffusion coefficients. W~thin the framework of the constitutional supercooling principle, a cumulative contribution to instability frorn the two solutes is found to exist in the absence of diffusional interaction. It is shown that the latter can produce a further enhancement of instability or can have a stabilizing influence, depending on the form of the liquidus surface and on the sign of the solute-solute interaction. A perturbation analysis, which ignores diffusional interaction, verifies the cumulative influence of lhe solute fields and demonstrates that the Mullins-Sekerka stability criterion for binary systems (with capillarity accounted for) can be readily extended for application to ternary systems. SOME time ago, Tiller et al.' calculated the solute concentration distribution ahead of the planar solid-liquid interface of binary alloys undergoing steady-state unidirectional solidification. An earlier qualitative proposal that the transition from planar to nonplanar growth morphologies is associated solely with the onset of constitutional supercooling in the liquid layer ahead of the moving interface2 was used in conjunction with this calculation to put the now well-known constitutional supercooling (C-S) stability criterion into quantitative terms. Mullins and Sekerka,3 in a recent and very elegant analysis, established a more complete criterion (hereafter referred to as the M-S criterion). Interfacial stability was investigated by determining the time derivative of the amplitude of a sinusoidal perturbation of infinitesimal amplitude which had been introduced into the originally planar shape of the moving interface. Of particular importance is the fact that capillarity was included in the boundary conditions of their calculation. The purpose of the present paper is to extend all of this earlier work on dilute binary systems for application to dilute ternary alloy solidification. The analysis is divided into three sections. In the first the two solute distributions ahead of a moving planar interface are considered. Mathematical solutions are de- termined for situations in which: a) diffusional interaction is negligible, 6) diffusional interaction must be considered but circumstances permit use of constant diffusion coefficients, and c) the concentration dependence of off-diagonal diffusion coefficients can be described by first-order dilute solution approximations. In the next section, a stability criterion analogous to the C-S criterion is developed and the influence of diffusional interaction on interface stability is analyzed. Finally, the perturbation formalism of Mullins and Sekerka, with capillarity included in the boundary conditions, is extended for analysis of ternary systems in which diffusional interaction is negligible. The study of interface stability in binary systems usually commences with the assumption that the equilibrium distribution coefficient and the slope of the liquidus line are constant at values corresponding to infinite dilution. Similar assumptions have not been introduced into the present treatment; that is, we do not assume planar solidus and liquidus surfaces joined by tie lines which yield constant distribution coefficients. The latter involves the assumption of no ther-modynamic interaction between solute species in both the solid and liquid. We consider a ternary phase diagram for which the solidus and liquidus surfaces are, in general, nonplanar and of course pass through the corresponding binary solidus and liquidus lines. These lines are not assumed to have constant slope. In the dilute regions we are concerned with, the following assumptions are made: i) The solidus and liquidus surfaces are of a form such that both the solidus and liquidus temperatures are monotonically varying functions of each solute concentration. ii) The tie lines are such that the equilibrium distribution coefficient of a given solute is greater than unity for every point on the solidus (or liquidus) surface or it is less than unity for every point. STEADY-STATE SOLUTE DISTRIBUTIONS IN THE LIQUID As will be demonstrated in the next section, a knowledge of the steady-state solute profiles is not a necessary prerequisite for the formulation of a ternary C-S stability criterion. However, in that details, such as the complete description of the equilibrium liquidus temperature profile, require an evaluation of the solute distributions, the overall treatment is enhanced if these distributions are determined. Consider a ternary system (solvent plus solutes 1 and 2) for which a planar solid-liquid interface is in unidirectional motion at constant velocity V. At this stage it is unnecessary to limit ourselves to dilute solutions. For a stationary frame of reference the generalized forms of Fick's equations are:

Jan 1, 1969

By W. J. Millard

IT is well known that the excellent mica from Brazil played a most vital role in World War II. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the United States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. TYPE OF DEPOSIT FAVORABLE The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than I:3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. THE ECONOMICS OF STRIPPING When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run II per cent good stain and better when trimmed and contain 2 kg. of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should he used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.I4 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.I5. To this should be

Jan 1, 1946

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,' will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano' on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager' in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.' The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano's result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl's points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman' reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser' reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,' values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,' on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.' When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By R. L. Rickett, S. H. Kalin, J. T. Mackenzie

Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

By Gerald Edmunds, C. W. Siller, E. A. Anderson

In the pressurc die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger arid a complcte shutdown of the equipment. All of the zinc alloys used for pressure dir-rnsting today contain approximately 4 per cent of aLUminum, which is more than suffieient to make plunger opcration feasible. The clearancc bet,ween the plunger and its bushing is an important matter. As the space bccomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still uscd in some machines. However, the rate at which the plunger c1earance. increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new matcrinls more: capable of retaining the desired clearance during long periods of use. Today marly die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger. operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the pluriger will operatc for a long time, of course.. The authors have developed a laboratory apparat,us in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clearance area.

Jan 1, 1940