Search Documents

By Thomas M. Drown

The use of bromine as an oxidizing agent, particularly for sul phur, has become very general in analysis, replacing the stronger oxidizing acids. The object of this paper is to describe briefly the experience which we have gained with this reagent in the laboratory of Lafayette College in the oxidation of metallic sulphides. Most of the simple sulphides, as blende, pyrite, etc., when exposed to the combined action of an alkaline hydrate and bromine, and finally to hydrochloric acid, are completely and promptly dissolved. The procedure is as follows: The very finely pulverized mineral is first treated, in a beaker, with a solution of sodium hydrate of a spe cific gravity of 1.25, and heated ; bromine is then cautiously added to supersaturation, and finally hydrochloric acid to acid reaction. If any of the sulphide is not taken up, the same operation may be re peated. It is necessary, however, that the mineral be very finely pulverized. Instead of using the pure bromine, a saturated solu tion of bromine in potassium bromide may be used with equally good effect. The process is advantageously simplified by making a saturated solution of bromine in the concentrated alkali. This is done by pouring bromine into a solution of sodium hydrate, of the above given specific gravity, until no more is taken up, and then adding a little of the sodium hydrate solution until the liquid does not give off free bromine. The procedure with this solution is as follows: The pulverized mineral is moistened with, say, 10 cc. of the solution, and heated, then hydrochloric acid added to just acid reaction. Two more additions of the alkaline solution, in amounts of 20 cc. each, are added at intervals of about ten minutes, each addition being followed by hydrochloric acid. The total amount of the alkaline solution (containing the bromine) used is, therefore, 50 cc., and the amount of hydrochloric acid should not exceed that necessary to make the solu tion acid after each addition of the alkali. The mixture should be kept hot. After the final addition of acid, the contents of the beaker is taken to dryness and heated in an air-bath to 110° to 115°C., to render silica insoluble. The dry mass is then taken up by hydro' chloric acid and water and, after filtration, the sulphuric acid is pre

Jan 1, 1880

By T. E. Scott, R. P. Zerwekh

The charactevistics of the deformatiotz of fcc thorium were examined between 78 and 473 K. Activation energy, actiuation volume, and the temperature dependence of the flow stress were determined and conlpared uith several theories for the rate-controlling mechnnistn of the tempemture-dependent component of the flou~ stress. It was established that the Cottrell-Stokes law does not hold, even approximately, for thorium. Through consideration of the above factors and other parameters, it was concluded that the vandom solute barrier theory proposed by Friedel demonstrates the best agreement with experimental observations of the deformation of thorium below ambient temperature. THORIUM, the first metal in the actinide series of rare-earth elements, is interesting and important from two points of view. In the more practical vein, it is a potential reactor fuel. As such, it is important to know its properties. Of specific interest here are the mechanical properties of thorium. Second, no detailed information concerning the deformation characteristics of the actinide elements has been gathered to date. In view of the interesting physical and chemical properties of these metals, their mechanical behavior might reveal characteristics which could improve our understanding of the mechanisms controlling deformation of the more common metals. For example, it has been shown1 that thorium exhibits a yield point which is greatly enhanced by interstitial solute elements such as carbon. This is not a normal occurrence in fcc metals. The goal of this investigation, therefore, was to characterize the deformation of polycrystalline thorium. MATERIAL AND PROCEDURES Thorium, made by the magnesium intermediate alloy process described by Peterson et al.,2 was rolled and swaged to 0.065-in.-diam wire. The metal analysis is given in Table I. After preparation, the oxygen and nitrogen contents had risen to 308 and 60 ppm, respectively. The 0.065-in.-diam wires were cut into 2-in. lengths and annealed in a vacuum of lo-' Torr at 750°C for 1 hr, producing a grain size of 2735 grains per sq mm. The ends of the 2-in. sections were masked off so that a 1-in. gage length could be electropolished. Specimens were polished at 35 v in a solution of 6 pct perchloric acid in methanol which was maintained at 0°C . The gage diameters after polishing were about 0.0625 in. The tests were run on a screw-driven tensile machine at a constant crosshead speed corresponding to a strain rate of 0.005 min-'. The strain rate was changed rapidly after each 0.01-in. extension between 0.005 min-' and one of three higher strain rates which were selected in order to achieve strain-rate ratios of 5, 10, and 20. Tests were run at several temperatures from 78" to 473°K; most were tested at 423", 300°, 215", and 78°K. EXPERIMENTAL RESULTS Flow Stress vs Strain and Temperature. Typical true stress-true strain curves for thorium are shown in Fig. 1 for several temperatures over the range 473" to 78°K. The curves for 78", 215", 300") and 423°K were obtained from strain-rate change tests using the lower (0.005 min-') or base strain-rate values of stress. Additional tests, using the same base strain rate at different strain-rate ratios, gave curves which virtually superposed on those shown, indicating that strain-rate changes did not materially influence the work-hardening characteristics at the base strain rate. The curves for 273") 373") and 473°K were standard tensile tests at 0.005 min-'. The behavior of the flow stress with temperature is

Jan 1, 1968

By William N. Poundstone

What attracts young engineering graduates into the coal industry? What do these young men expect of a career in coal mining? These questions are often asked and debated by mining men throughout the country. In order to present a comprehensive answer to them, an opinion survey was conducted at West Virginia University's School of Mines among the junior and senior classes and part of the sophomore class. The tabulation of the answers showed that the present-day mining engineering student is an older, more mature individual as compared with former years and as compared with other present-day college students. The average age of the country's record-breaking 150,000 college graduates is 24 years. Among this year's mining graduates at West Virginia University, 78% are of this age or older. Over half (54%) of those polled in the survey are married. This is com- pared to 30% as a national figure. Of those married, 38% have one child and over 6% have two children. The entire senior group covered by this survey has averaged almost three years in the armed forces. An article entitled "The Class of '49" in the June issue of Fortune magazine states that this year's class is the oldest, most mature class in history. Our survey indicates that the mining engineering students at West Virginia University are well above the average in this respect.

Jan 1, 1949

By D. P. Morton

SINCE 1023, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (I) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.' This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as loo, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods. Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. 2 (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should he the same. It is neces-

Jan 1, 1941

By Paul Billingsley

WHEN I was an undergraduate at the Columbia School of Mines, the mining curriculum was subdivided into two major branches's known respectively as the Metallurgical and the Geological Options, which diverged rather widely as the course progressed. When I duly elected the Geological Option, I believed, I am sure, that this divergence would continue throughout the years. The facts have proved otherwise. The mining industry is a closely knit entity in which the search for its raw materials, called mining geology, cannot be separated from the conversion of these raw materials into marketable form, called metallurgy. The mining geologist searches for materials which the metallurgist can utilize, and only such; and whenever an advance in metallurgy opens the gates for new materials, the geologist's problem is correspondingly modified. No better instance of this relationship can be given than that seen in the Salt Lake region in recent years. Our mineral industry here is of long standing. The three principal tributary districts, Bingham, Park City and Tintic, were discovered in the 1860's and have been vigorously and intelligently developed for many decades. Their production has made the Salt Lake valley one of the world's great smelting centers. The maintenance of this industry has for years depended upon the continual development of new orebodies to take the place of those being extracted. Intensive exploration in the old districts has been supplemented by prospecting in outlying districts of lesser prominence. . Many new orebodies have been discovered, such as those of the Daly West, Silver King, and Judge mines in Park City, the Utah Apex in Bingham, and the Sioux, Colorado Chief Consolidated and Tintic Standard in Tintic. New mines in other districts have been discovered also, but without affecting the dominance of the three major districts. In all cases discoveries, to be of value, had to be of ore amenable to treatment in the available metallurgical plants. This meant that, for the most part, zincy ores, both oxide and sulfide, must remain untouched, and also that ores high in iron and ores high in silica had a fictitious value, either high or low, set by the balance of these

Jan 1, 1928

By John A. Ames

Webster's dictionary nearly equates portland cement with its current primary definition of cement. While such equation may be a triumph of common usage, the confusion between the terms cement and concrete unfortunately is very widespread. Full definition of cement properly would extend to many substances, but for purposes of this chapter cement is restricted to "varieties" of portland cement including "portland-pozzolan" cement. Among the usually recited historical notes concerning cement is that it was developed by the Romans. Their use of cement in the great structures of Rome, and even in the far corners of their Empire, such as Hadrian's Wall in the north of England, testifies to the antiquity of a major cement industry. From English sources we know of John Smeaton's carefully proportioned hydraulic cement mixed in 1756 and of Joseph Aspdin's patented cement to which, in 1824, he gave the name portland cement. (He claimed that his cement mortar looked like the famous dimension limestone quarried from the Isle of Portland on England's south coast.) The year 1971 marked the centennial of portland cement manufacture in the United States. A fair historical account of the many real contributors to the cement industry between 1756 and 1972 unfortunately would be too extensive for this chapter. Development of rotary kiln practice and burning at higher temperatures clearly was the major move into today's technology. As part of the 4th edition of Industrial Minerals and Rocks, this chapter on utilization focuses on inferred interests of the anticipated readers. The main period for which statistics are cited generally is that since the 3rd edition (1960) of this same volume. Cement manufacture is the processing of selected and prepared mineral raw materials to produce the synthetic mineral mixture (clinker) that can be ground to a powder having the specified chemical composition and physical properties of cement. Cement making incorporates a number of distinct steps, but it is characterized by the key pyroprocessing (or "burning") step, which brings about the necessary changes in the raw materials. This pyro processing is a chemical process. Conversion of large volumes of mineral raw materials into specification-controlled cement at relatively low cost is the objective. Statistics on the cement industry are of uneven quality. The U.S. Bureau of Mines (USBM) is the principal collector of available data. These statistics can be only as good as the quality of information supplied by the reporting companies. The data perhaps most often questioned relate to productive capacity of the industry. The questions submitted by USBM are valid, nevertheless, and the information gained from them, as good as is available, is what is generally used. The Portland Cement Association also is a source of much quality information. The year 1972 witnessed a test of the adaptability of cement industry statistics. This was the year of conversion from barrels and sacks of cement as the units of measure to tons and hundredweights. The barrels and sacks related to volumetric measures in that a sack was judged to be 1 cu ft (weighing a "standard" 94 lb). A barrel was 4 sacks. Volumes of concrete are stated in cubic yards, and the number of cubic feet of cement in a cubic yard of concrete was a sensible approach to the mensuration involved. However, cements do not weigh the same amount from plant to plant or from type to type, and the buyer was more interested in getting an assured weight for his money than in "buying air." Thus, a sack, in accepted practice, became 94 lb instead of 1 cu ft, and a "barrel" became 376 lb, regard- less of whether it would fit into 4 cu ft of space. With the de facto dealing in weight rather than in volumes, the awkward numbers made little

Jan 1, 1975

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated

By A. W. D. Hills

This paper describes the development of a generalized integral-Wofile method for the analysis of heat transfer dwing solidification. The method is extremely flexible, and can be applied to a wide range of situations. This flexibility has been achieved by characterizing the solid metal layer in terms of two parameters, and by developing two simultaneous nonlinear differential equations for these parameters in terms of the heat fluxes crossing the boundaries of the solid layer. The use of these equations is illustrated in a series of examples which involve the solidification of pure metals at zero superheat cooling under different conditions. The simplicity with which the method can be extended to treat more complicated jwoblems is illustrated in a further example which involves natwal convection effects in the liquid metal. ThE rate at which molten metal solidifies in an industrial casting process, and the structure of the cast product, are both controlled by the rate at which heat can be removed from the casting. A knowledge of heat transfer rates is thus essential to the control of the process and to the control of the structure and soundness of the final casting. Heat transfer rates during real solidification processes cannot be predicted by formal mathematical techniques, however, because nonlinear boundary conditions are involved. Approximate methods are normally used, and these have included electrical and hydraulic analogue techniques, finite difference methods, and the integral-profile method. Considerable effort has been devoted to the development of the first two techniques, but the integral-profile method has been used very little so far. This is unfortunate because the method is capable of providing relatively accurate solutions for the heat transfer equation during solidification without involving large amounts of computer time. A further advantage of the method is its flexibility, although this is not apparent from the integral-profile solutions that have been developed to date. These solutions have been derived for the solidification of molten metal at zero super-heat under cooling conditions involving either a constant heat flux from the cooled surface;' a constant heat transfer coefficient at the surface,'-3 or a specified variation in the surface temperature.4,5 A generalized integral-profile method is presented in this paper which can be used to predict unidirectional solidification rates under a very wide range of more realistic cooling conditions. The use of the method is illustrated in a series of problems involving pure metals, or skin forming alloys, solidifying at zero super-heat. However, the principal advantage that this method has over the previous integral-profile methods is the ease with which it can be extended to treat more complicated solidification problems. This is illustrated by considering a problem in which super-heat is liberated from the liquid metal by natural convection during the solidification process. In the final section of the paper the generalized method is compared with previous methods used to predict solidification rates and its extension to more complicated solidification problems is briefly discussed.

Jan 1, 1970

By J. Handin, S. J. Bauer, M. Friedman

Deformation mechanisms in room-dry and water-saturated specimens of Charcoal Granodiorite, shortened at 10-4s-1, at effective pressures (Pe) to 100 MPa and temperatures to partial melting (?1050°C) are documented with a view toward providing criteria to recognize and characterize the deformation for geological and engineering applications. Above 800°C strength decreases dramatically at effective pressures ? 50 MPa and water-weakening reduces strength an additional 30 to 40% at Pe = 100 MPa. Strains at failure are only 0.1 to 2.2 percent with macroscopic ductility (within this range) increasing as the effective pressures are increased and in wet versus dry tests. Shattering (multiple faulting) gives way to faulting along a single zone to failure without macroscopic faulting as ductility increases. Microscopically, cataclasis (extension microfracturing and thermal cracking with rigid-body motions) predominates at all conditions. Dislocation gliding contributes little to the strain. Precursive extension microfractures coalesce to produce the throughgoing faults with gouge zones exhibiting possible Riedel shears. Incipient melting, particularly in wet tests, produces a distinctive texture along feldspar grain boundaries that suggests a grain-boundary-softening effect contributes to the weakening. In addition, it is demonstrated that the presence of water does not lead to more microfractures, but to a reduction in the stresses required to initiate and propagate them.

Jan 1, 1982

By Harold E. Thomas, Samuel S. M. Chan, Nicholas Bada

The U.S. Bureau of Mines has developed a technique for locating and evaluating bedding plane cracks in mine roof by an air-injection and hot-film flow logging technique. It is ultrasensitive to cracks and is especially useful for detecting the early stage of crack development. Potential applications include: (1) correlation with roof sag measurements, (2) locating cracks for grouting, (3) comparison of mechanical and resin roof bolt effectiveness, and (4) possible delineation of the fracture zone to confirm the arch hypothesis. The required equipment is inexpensive and simple to operate.

Jan 1, 1975

By M. C. Flemings, R. Mehrabian, G. E. Nereo

Analytic expressions were developed and applied in two preuious papers to predict effects of solidification variables on macrosegvegation. In this paper, experiments are reported to test the analyses quantitatively and qualitatively. Good quantitative agreement is obtained between predicted and measured compositions for the following types of segregation (all experiments were on laboratory-size ingots of Al-4.5 pct Cu alloy): (a) inuerse segregation, (b) composition distribution in ingots solidified with unidirectional heat and fluid flow, (c) simulated centerline segregation, and (d) segregation resulting fro, change in solidification cross section. In addition, qualitative agreement of prediction of theory with experiment is obtained for (a) segregation resulting from sudden change in heat extraction during solidification, (b) centerline segregation in a bidirectionally solidified ingot, and (c) under-riser positive segregation. IN two previous papers,''2 it was shown that a variety of apparently different types of macrosegregation result from the same basic mechanism. This mechanism is the flow of solute -rich liquid to feed solidification and thermal contractions. Analytic expressions were derived and examples given of their application to predict macrosegregation. Calculations were for Al-4.5 pct Cu alloy. In this paper, we describe a series of experiments designed to test results of the foregoing calculations. All experiments were on laboratory-size ingots (weighing 10 lb or less), of A1-4.5 pct Cu alloy, nominal composition. APPARATUS AND PROCEDURE A typical mold and chilling arrangement used for unidirectional solidification is shown in Fig. 1. Before casting, this assembly was placed in an electrically heated air furnace, and heated to 680" to 700°C. When the plaster reached the desired temperature (usually 1 to 2 hr after the furnace temperature), the mold was filled through a funnel extending from the outside of the furnace into the cavity. The assembly, with liquid, was held for several minutes to allow convection to subside. The coolant, either air or water (depending on the desired solidification rate), was turned on and the ingot solidified. With the four sides and top insulated, heat removal for solidification was through the bottom surface, resulting in a fully columnar structure. Design of the casting cavity was varied, as discussed below, to produce desired macrosegregation effects. However, for castings solidified with unidirectional heat flow, the top was always open to the furnace atmosphere and temperature. The bottom sur- face rested on a chill through which the heat was extracted, and all other surfaces were insulated with plaster. In one case to be discussed, the mold design was changed to obtain bidirectional solidification. In this case, two vertical chills were used (on two faces of the mold) and the bottom was insulated. In a last case discussed, that dealing with under-riser segregation, experiments were conducted in bottom-chilled sand molds at ambient temperature. Except for this one case, all experiments were conducted in the electrically heated air furnace as described above. In many ingots, thermocouples were used to obtain continuous records of solidification. In all cases, these were chromel-alumel couples with output continuously monitored on a twelve-channel recorder. Where thermocouples were employed, these were embedded in the refractory mold walls during mold-making so their heads extended to the vertical centerline. Six to nine couples were employed, placed at intervals from the chill. METAL-MEL TING PROCEDURE Aim analysis was A1-4.5 pct Cu; alloy was prepared from high-purity aluminum (99.9 pct Al) and A1-Cu master alloy (50 pctOFHC Copper, 50 pct high-purity Al). The A1-4.5 pct Cu alloy was cast in 5- to 7-lb ingots for subsequent remelting for the macrosegregation experiments. Melting for ingot casting was as follows. After preheating the melting crucible for an hour or more, the charge was melted and superheated to a temperature of 690" to 720°C. After stirring, the melt was degassed with chlorine for 10 min. After stirring again for 1 min, a gas sample, under reduced pressure, was taken. When the sample was gas-free, the crucible

Jan 1, 1969

By P. BOURY

THIS account of a contrivance which has been found serviceable in practice may be of interest to engineers, and' especially to those engaged in hydraulic mining. In that process, one feature which seems at first sight to possess little significance, is highly important in its effects, namely, the regular supply of water to the " giants." The chief condition of this regularity is an even flow in the pipe-line from the penstock to the nozzle. This, of course, requires that the penstock be kept full. Any considerable surplus of water, overflowing at the penstock, is a simple waste, unless it be otherwise utilized in the sluices. At all events, it does not affect the delivery of the nozzles. But a deficiency at the penstock may admit air into the pipe; and this may produce hydraulic recoil, injuring the line by incessant vibrations, giving rise to leaks, and even to blow-outs, and (when a partial vacuum exists at the time of the fracture the collapse of the pipe. An accident of this sort in our main pipe-line, occasioned partly by a settling of the ground and partly by the presence of air in the pipe, led to the employment of the device here described. The line referred to is made of 30-in. pipe, successively reduced to 18 and 15 in. in diameter, for the supply of two giants. By reason of the causes above mentioned, the 30-in. pipe burst more than 1,400 ft. from the penstock, and, despite the air-valve, the 30-in. pipe was collapsed to such a degree that one length of it, next to the penstock, was squeezed together and positively swallowed by the main pipe, through which it traveled for 750 ft., piercing through a short elbow on the way. This remarkable result was undoubtedly the effect of the vacuum suddenly produced when the pipe burst.

Sep 1, 1906

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. A. J. MAY is Engineer in Charge of Shaft Sinking, Ground Hog Unit, American Smeling and Refining Co, Vanadium, New Mexico. El Paso Meeting, October 1948. TP 2737 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Nov. 29, 1948; revision received June 22, 1949. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A Yzx4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four % in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of % yard capacity, both manufactured by Blaw-Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1951

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. A. J. MAY is Engineer in Charge of Shaft Sinking, Ground Hog Unit, American Smeling and Refining Co, Vanadium, New Mexico. El Paso Meeting, October 1948. TP 2737 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Nov. 29, 1948; revision received June 22, 1949. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A Yzx4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four % in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of % yard capacity, both manufactured by Blaw-Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1951

By Zdzislaw Specht

THIS paper discusses elementary laws pertaining to seismic reflection methods and presents a general and simple criterion for determining the direction of dipping of a reflection horizon from observational data of distance and time. The important development of practical geophysics and the successful results obtained in America, Germany, and other countries, caused introduction of geophysical methods of prospecting in Poland. Of all methods, seismic prospecting has proved most successful in the area of the Carpathian foreland, where new oil reserves are to be expected. Because of the great depth of the sedimentary column in that area, rang-ing sometimes over 2000 meters, it was obvious that only the seismic reflection method could give reliable information regarding the structural features of these strata at such a depth. During the experimental surveys it appeared that the complicated geological conditions of that area do not always allow prediction of the depth and the angle of dipping of reflecting horizons, and for that reason information about the inclination of a given horizon has great importance in the determination of subsurface structure. Therefore the problem arises of obtaining from seismic reflection data reliable information as to the direction of dipping of reflecting strata, without any previous knowledge of the average velocity and depth of geologic horizons under consideration.

Jan 1, 1940

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By Harry Seltz

INTERMETALLIC compounds are formed in many binary metal systems. Some compounds are stable to their melting points, and others decompose at lower transition temperatures. Even those of the first class are dis-sociated in the liquid state, as indicated by the continuous for in of their solubility curves at their melting points1. While the lattice structures of some of these compounds have been determined, their thermodynamic properties have not been investigated. In this paper is described the determination of the free energy and heat of formation of the compound CdSb, which is of the first class mentioned above, melting congruently at 455° C. This compound shows a rhombic structure, and the lengths of the edges of the elementary cell containing four molecules are: a =6.52, b = 8.60, c = 4.16 A.2 There are three possible methods of determining the free energy of formation of a compound of this type. The first method, applying the third law of thermodynamics, requires the measurement of its heat capacity preferably to liquid hydrogen temperatures, and a calorimetric determination of its heat of formation. The second method involves the study of the equilibrium of the compound in some gas reaction, such as: CdSb + CO2 = CdO + CO + Sb From the known free energies of formation of CdO, CO2 and CO the free energy of formation of CdSb could be calculated. The third method measures the electromotive force of a galvanic cell in which the cell

Jan 1, 1935

By Robert L. Grayson, Y. J. Wang, R. Mike Mishra

Prediction of ventilation needs in long range mining projections requires serious consideration when formulating those projections. Predicting the behavior of the ventilation system of an old, complex mine poses an especially provocative problem. Air-flow around and through mined-out areas via bleeder systems, leakage flows through stoppings or other air control devices, and the use of multiple fans all add to the basic complexity of a ventilation system and make predictions of ventilation changes very difficult. Fortunately, the task of making ventilation decisions can be greatly assisted by ventilation surveying and computer simulation. The Nemacolin Mine of Jones and Laughlin Steel Corporation, located in Southwestern Pennsylvania, is one such old mine which used the computerized approach successfully. A mine-wide pressure-quantity survey was used to obtain realistic values for airway resistance factors. These values, together with network topology, formed the basic input for computer simulation. Results from this simulation indicated that air quantities generated at critical airways by the model were generally within a couple of percent of those measured in the actual survey. It was then concluded that the model was acceptable for practical application, and it was used immediately for studying the effects on the ventilation system of changing the blade settings of fans. Additionally, the model was modified to incorporate projected mine development and used to predict future ventilation.

Jan 1, 1982

By Audley H. Snow

The general drift of the discussion as to the relative merits of pressure- and exhaust-fans has resulted, if we may judge from the prevailing practice, largely in favor of the latter. The subject has been hitherto treated, however, with special reference to highly gaseous mines, the effect of the form of ventilation upon dust-explosions having been too little considered. Even in mines containing practically no gas, dust-explosions may occur; and if, as I believe, pressure-fans are to be preferred for their effect upon dust, it may be worth while to reopen the debate, and to challenge the advisability of exhaust-ventilation under certain conditions. There are several forms of colliery-ventilation, which may be described as follows: Plain or simple pressure-ventilation, in which the fan acts as a pressure-fan, and the movement of coal is unobstructed at the surface by doors or equivalent devices in drifts or shafts, the traveling and haulage. thus being in the return-current. Plain exhaust-ventilation, in which the fan acts as an exhaust-fan, the movement of coal being likewise unobstructed at the surface, and the traveling and haulage being in the intake.

Jan 1, 1910