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By W. C. Ellis

NONFERROUS alloys upon which desirable properties can be conferred by heat treatment are becoming of increasing industrial importance. The alloys of copper with a constituent which has a solubility varying with temperature are materials of this character. Some of the constituents which are effective in producing a change in the mechanical properties of these alloys upon heat treatment are, according to Corson,1 nickel and silicon, iron and silicon, cobalt and silicon, and chromium and silicon. In addition to these elements, Gregg2 states that the combination of beryllium and silicon is effective in producing age-hardening characteristics in copper. The effect of these elements, however, as dispersion-hardening constituents in the copper alpha solid solutions does not seem to have been studied in any considerable detail. This paper deals with the heat treatment and properties of three alpha brasses containing 3 per cent. of nickel plus silicon in the proportion necessary to form the compound nickel silicide, Ni2Si. Some information of a preliminary nature in regard to the hardening by heat treatment of phosphor bronze containing the same percentages of nickel and silicon is included. The method of hardening the alloys, which is effective in increasing the tensile strength and proportional limit, is similar to that used in, the case of duralumin type aluminum alloys. It consists of a quench from a temperature at which the hardening constituent is in solid solution, followed by an aging at a lower temperature to precipitate the dissolved constituent in a dispersed condition. This results in an increased resistance of the alloy to deformation with an attendant improvement in the tensile properties.

Jan 1, 1929

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

By W. B. Wise, H. D. Attra, W. M. Black

The purpose of this paper is to illustrate a comparatively new approach for solving a problem that has plagued oil producers for many years—how to make the most money with available field production capacity. In a very basic operation such as a top-allowable one-well field, a computer and staff of engineers are not required to determine that the best operation is to produce that well at its maximum for as long a time as it will produce. However, as the problem becomes more complex and the number of wells and number of reservoirs increase, it probably will be a wise choice to devote some engineering thought and calculation time to determine the best way to operate that field on both an ultimate and day-to-day basis. Continued developments in the field broadly referred to as "operations research" have led to a number of useful engineering analyses for optimizing field operational problems. One of these techniques, termed linear programing, is parlicularly interesting because of its potential applications to the study of complex oilfield operating problems. Linear programing is concerned with the problem of planning a complex set of interde~endenl activities in the best possible (optimal) fashion. A field application of linear programing is being used to maximize daily income from a multi-reservoir producing operation. The initial results of this study indicate that the linear programing technique (I) can be applied effectively to field problems, (2) can be used to detect unsuspected avenues for improving operations and (3) can effect a significantly improved means of controlling field operations through the use of the highspeed computer. INTRODUCTION The usual approach for studying complex field operational problems has been to look in detail at several basic plans suggested by judgement and experience and, then, to choose the best plan from those investigated. This approach is entirely satisfactory provided: (1) that judgment and experience alone will reliably pick the best or near the best program as one of the plans to be investigated; and (2), and most important, that the factors which control field production will not change. This paper deals with the large group of field operations which are at least one-step removed from a satisfactory solution using the conventional method of analysis. Problems such as pipeline- and gathering-system design, transportation studies, large field development projects and multi-reservoir producing operations fall in this latter category. To find the best program for handling these problems when the best program is not obvious, a complete optimization study is required, and high-speed computers are required to continually update the program once it is selected. Operations of this type have an extremely large number of possible solutions. However, only one will result in maximum economic return and, more important, this one program must be re-evaluated and adjusted constantly to accomodate such changing field factors as the number of producing days, the price of crude, the discovery of new reserves, declining reservoir pressure with subsequent decline in production and a host of other factors which characterize specific operations. One of the most widely used, direct methods of optimization is a numerical procedure termed "linear programing", which is designed to investigate systematically each of the possible solutions involved in a given problem, determining rapidly and uniquely the optimum answer. As implied by the name, linear programing requires that all field variables be either defined or expressed in a series of interdependent linear equalities or inequalities. These relationships are solved simultaneously, using a form of matrix solutions to determine the optimum values for each producing variable that will maximize net profits. The solution techniques used in a recent field case study is termed the "simplex method" and is discussed in full detail in Ref. 1.

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By Arne F. Westgren

X-ray analysis and single-crystal study have been utilized in recent years as a new means of following constitutional changes in alloys. If such transformations can be suppressed by rapid cooling, they can be followed at room temperature in a particularly convenient manner. In the following we shall consider changes in solubility and polymorphic transformations with particular reference to phenomena of the age-hardening type. Finally a thermodynamic viewpoint is developed for examining such transformations. Changes in Solubility 1. Determinations of solubility limits in the solid state which show decreasing solubility with falling temperature are made as follows: A series of alloys extending into the heterogeneous region is prepared and quenched fromas high a temperature as possible, whereupon their lattice parameters are determined. Then one or more alloys are quenched from temperatures at which they are heterogeneous and their lattice parameters likwwise determined. For the purpose of determining the parameter the apparatus shown in Fig. 1 has been very useful for it produces sharp films in a short time which can be accurately read. High-order reflections (interferences) from the object are recorded on a film which is placed exactly perpendicular to the X-ray beam. The specimen usually has the shape of a small round bar.l Fig. 2 shows a selection of such exposures of silver-rich Cu-Ag alloys, and Fig. 3 gives the measurements made from these films. Fig. 4 gives the solubility curve which results.2 This curve is shifted to lower concentrations than the curve that is obtained from metallographic or physical methods. The X-ray method unquestionably gives more reliable data

Jan 1, 1931

By Clarence P. Linville

A previous article1 by the authors contained a general description of the new roasting furnace herein described but it did not go into detail as to the metallurgical behavior or the results obtained. Believing that such information would be of great value, they have elaborated on the subject and have given many unpublished details. The furnace described applies the principle of roasting finely divided zinc-sulfide ores, now produced in large quantity by the flotation process, in gaseous suspension; that is, the ore particles are carried, in suspension, in a current of air and gaseous products of the roast. The relatively great fineness of flotation concentrate presents difficulties and problems of roasting in furnaces of the ordinary type; the fine ore is forwarded through the furnace in the form of a shallow bed and its very fineness leads to dense impervious bedding which prevents oxygen from reaching the interior of the bed, thus unduly lengthening the time of roasting and preventing the elimination of the last of the sulfur. The fineness of the concentrate, normally, should lead to a rapid and complete roast, for the speed of roasting is a function of the surface exposed to oxygen, which surface is greatest, per unit of weight, in very fine material. The difficulty in bed roasting is to get the oxygen to the particle. If the fine ore, during the roasting, could be freely suspended in oxidizing gases, full advantage could be taken of the great surface conferred by its fineness. This fundamental idea, of course, is not new, for the Stedtefelt furnace, familiar to the older metallurgists, is an example of it; but the manner in which this is accomplished may be new. The numerous efforts to roast in gaseous suspension show that the idea is attractive; in fact, an analysis would indicate that it is the most reason-

Jan 1, 1925

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By Robert J. Anderson

DURing the past 5 years no subject has aroused more interest or received more attention among mill operators than flotation. One reason for this is, undoubtedly, the remarkable success of the process in Australia where that country has risen to the position of furnishing one-fifth of the world's supply of zinc. The plant of the Butte & Superior Copper Co., designed by James M. Hyde in 1912, was the first important large flotation plant in this country; other installations have been made since then with considerable frequency, particularly so in the last 2 years. Without going into complete detail, it may be safely said that although flotation is a highly successful commercial process, it is more or less on an empirical basis. Upon scanning the literature, it is found that the flotation investigations have, in the main, dealt with a solution of the problems which accrue to practise; until recently no attempt was made to remove the difficulties in the way of the formulation of a consistent and harmonious theory. Of late this phase of the work has been receiving considerable attention, particularly by the United States Bureau of Mines at its Salt Lake City station, by the Mellon Institute at Pittsburgh, by the General Engineering Co. at Salt Lake City, by many of the mining schools, and private individuals almost ad infinitum. There is, at present, an enormous amount of laboratory work being carried on in flotation research, and probably the time is not far away when a generally acceptable explanation of flotation phenomena can be set forth. However, at this time, it seems as though the current technology is befogged with a superabundance of contradictory evidence; this confusion can only be dispelled as time proceeds and the knowledge of the subject becomes more complete. Many phenomena are supposed to contribute to the flotation of minerals, whether in whole or in part is a mooted question. I shall only sketch roughly the present tendency of ideas and make no reference to the first early and crude notions which have little value other than histori-

Jan 1, 1917

By J. R. Campbell

A dozen years or so ago, the general superintendent of our company, now the president, Mr. W. H. Clingerman, asked me to study the coal-washing problem. This work brought me into contact with the best washery men of the country. I investigated many kinds of coal-cleaning schemes, made numerous tests, and collected voluminous data, yet I confess frankly that I have had little practical washery experience and that little has been at the Middlefork washery of the United States Fuel Co. at Benton, Franklin Co., Ill., which was put in operation last fall. While this washery installation may not be the "last word," I am quite sure it embodies some long steps in advance of the older designs and constructions. From the washery man's standpoint, the removal of pyrites or marcasite, a disulfide of iron, is the one vital problem, and the one productive of the most beneficial results, so far as elimination of sulfur is concerned. Sulfates and so-called organic sulfur occupy quite a sec-. ondary position and are generally lost sight of in coal washing. The elimination of sulfur in coal in the past has usually been accomplished by jigging in water, but lately concentrating tables have been successfully employed. The flotation process has been applied to fine coal, but is hardly considered practicable. Coal washing is rapidly coming into its own, due to the depletion of low-sulfur coals for coking purposes, and we predict that soon the same careful attention will be given to the design and construction of coal washeries that is now being given to byproduct plants and other allied industries. Heretofore, coal washing has been considered only an incidental and necessary evil instead of the big problem it is—one worthy of the most careful study by men well trained along technical lines and capable of delving into the fundamental principles. Preparation oF Coal It is usually necessary to crush the mine-run coal before sending it to the jigs, the degree of crushing depending on the occurrence of the sulfur and other impurities in the coal and the type of jig over which it is to be sent. The feldspar jig requires finer and more uniform crushing

Jan 1, 1920

By J. D. Rice, P. L. Wearden, W. L. Hensou

Solutions to the unsteady-state partial water-drive reservoir performance problem can be obtained through the use of analogue computers or high-speed electronic digital computers. The solutions that have previously been resolved for use on digital computers, however, demand a knowledge of the aquifer parameters. Generally, the analogue computers now in use do not require this knowledge. A solution is presented herein where the aquifer performance, expressed in terms of difference equations, is related to the reservoir performance as expressed by the modified Scbiltbuis material-balance equation. A numerical procedure for a medium-sized digital computer also is presented in which a solution to the set of equations defining the aquifer and reservoir performance is obtained and the aquifer parameters (permeability and sand thickness) are automatically optimized while simultaneously matching the known pressure behavior. Predicted pressure behavior can be calculated using rates from any assumed future production practice. The procedure provides an output format which presents the cumulative, incremental and average rate of natural water influx, the per cent gas-cap expansion, the calculated reservoir pressure, the measured reservoir pressure, and the difference between the measured and calculated pressures. Results of a test problem are presented in comparison with results obtained by the Bruce Analyzer, Ohio Oil Co. 's Pace General Purpose Analogue Computer, and Sun Oil Co.'s Single-Pool Electronic Reservoir Analyzer. These results indicate that unsteady-state reservoir perlormance for a single-pool system can be adequately simulated by a numerical method employing a digital computer and that the special-purpose analogue computer can be supplanted by this method. INTRODUCTION The numerical approach to the unsteady-state partial water-drive reservoir performance problem heretofore has been limited in that solutions have been resolved only for certain fixed parameters. Also, prior to the advent of high-speed electronic digital computers in the last few years, calculations were so tedious and time-consuming that they ordinarily were neglected, or some other means of obtaining the solutions were used. The analogue approach had been used for obtaining solutions to the transmission-of-heat problem and, consequently, means were developed for applying the electrical analogue to the unsteady-state reservoir performance problem. Bruce submitted a paper for AIME publication in Sept. 1942, in which he described an electronic device (now called the Bruce Analyzer) for analyzing the water-drive performance of any reservoir, based on either steady or unsteady-state flow characteristics. 1 Sun Oil Co. adopted the analogue approach in 1949 and now has two special-purpose high-speed electronic reservoir analyzers in use.2,3 Two main features of Sun's analyzers are (1) the high repetitive rate of reproducing the entire history of reservoir performance cyclically a number of times per second, and (2) the elimination of the necessity of knowing the properties of the associated aquifer. Since the advent of larger and faster digital computers, the possibility of incorporating this second feature into a numerical approach appeared feasible. Previous work has been done and material published covering the application of numerical methods to the behavior of the pressure with respect to time at any point in an associated aquifer? However, the aquifer parameters must be known from some source. The material presented in Ref. 4 has been used to a great degree in developing the numerical method described herein. DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS The problem of simulating the performance of a reservoir and the associated aquifer is to determine the characteristics of the aquifer such that the

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By J. F. Peters

The term solution loss is discussed and defined. Examples are given showing that solution loss may either have a favorable or unfavorable effect on blast furnace performance. A theory is advanced explaining the contradictions encountered during earlier studies of the problem. MANY papers have been written and numerous theories advanced concerning the chemical reactions in the iron blast furnace. Richards, discussing the utilization of fuel in the blast furnace, said: "All the carbon burnt in the furnace should be first oxidized at the tuyeres to CO and all the reduction of oxides above the tuyeres should be caused by CO, which thus becomes CO,. This dictum is not Gruner's own words, but expresses their sense, and from the point of view of the present discussion, it is the correct principle upon which to obtain the maximum generation of heat in the furnace from a given weight of fuel." Richards also said the cubic feet of wind per pound of coke does not express how efficiently a furnace is running, but it will be shown later where Howland paid much attention to this figure. Richards pointed out a shortcoming of Grun-er's discussion in that Richards claimed there is not enough CO generated in a good working blast furnace to possibly combine with the oxygen of the ore, so some of it must be reduced by solid carbon. Mathesius2 made two important contributions. First, he wrote the direct and indirect reduction equations showing the heats of formation in each case and stressed that the indirect reduction reaction produces heat while direct reduction absorbs heat. Secondly, he substantiated Richards' conclusion that there may be a deficiency of CO gas and that some direct reduction is required, but he pointed out that "direct reduction in the hearth has often been confused with direct reduction in the stack, which more correctly should be termed 'premature combustion'." Then he said that "as this carbon is consumed partly by economical (direct reduction in the hearth) and partly by wasteful reactions in ever varying proportions, it is evident that the relation of this total carbon gasified above the tuyeres to the fuel consumption of a furnace cannot possibly have a direct bearing on the economy of furnace operation. The premature combustion of carbon (CO2+C?2CO) must therefore in all cases be considered a detrimental reaction." Johnson3 discussed this whole problem. Through experience Johnson found that when departure from Gruner's ideal working is considerable, the fuel economy is poor, and when the quantity of blast goes up, the fuel economy goes up in the same proportion. Johnson said that the wind per pound of coke is a measure of fuel economy, which will be shown to be wrong. Howland4 established the fact from operating data that there was no relationship between the coke consumption of a furnace and the percentage of coke burned at the tuyeres. But some of his calculations have led to questionable conclusions, such as "it is practically impossible to obtain low coke consumption unless we keep our wind low." Howland made an important contribution when, in his concluding paragraphs, he reached certain negative decisions as to why one coke works better than another. He said the reason one coke works better than another in a blast furnace is not because: 1—there is any difference in the percentage gasified at the tuyeres, or 2—there is any difference of wind required per pound of coke. Korevaar5 propounded a new theory on combustion which disagrees with Gruner because "as far as we can see, this is sufficient proof for the invalidity of Gruner's ideal, for if it was valid, the Low coke consumption should always be accompanied by a higher percentage of carbon burned at the tuyeres. This not being the case, we must deliberately give up our belief in Gruner's ideal." The part in italics will be proved to be wrong. Martin" contended that there was not enough reducing capacity in the blast furnace unless solution loss occurs. He came to a series of conclusions, such as: 1—The greatest efficiency of the blast furnace may not be attained when the reduction is performed entirely by carbon monoxide as demanded by Gruner's definition of the ideally perfect working of the blast furnace. 2—The so-called solution loss reactions, which should more properly be termed direct reduction reactions, promote furnace efficiency. 3—In modern blast furnace practice, the carbon consumption of the process is determined primarily by the carbon needed for reduction purposes, any thermal deficiency created by the reduction process being balanced in practice by the use of blast heat. From a practical standpoint further discussion of the theory of chemical reactions is of little moment. There is however one phase of the general theory of chemical reactions which is very important and that is the combustion of coke in the blast furnace. The purpose of this paper is to show that the reaction

Jan 1, 1955

By T. W. Guy

The increased moisture due to water-spraying for coal dust control is of interest even for mines from which the coal is to be wet-washed before screening, because in many cases wet coal dust materially de- 20-mesh X 0 sizes as pct ROM average ............................... 6.3 pct Range 2.3 to 9.5 pct 20-mesh X 0 sizes as pct 3/8 X 0 sizes average........'...................... 18.9 pct Range 12.7. to 23.9 pct creases the loading efficiency of men and equipment at the faces. It also causes a serious increase in the normal wear and deterioration of all equipment with which it comes in contact. It is important to the consumer if it increases his as-received moisture. No attempt will be made in this paper to cover the entire subject of water-spraying of coal for dust control. It will be confined to discussion and data on (I) percentages of dust in bituminous coals, (2) moisture increases due to spraying for dust control in mines or plants by methods which have proved satisfactory for periods of one to five or more years, and (3) a few suggestions for research. Size and Percentage or Coal Dust The U. S. Bureau of Mines1 classifies as coal dust all bituminous coal passing a 20-mesh sieve (0.0328 in. square opening). The percentage of such dust to be found in ROM coal, of course, varies widely with the characteristics of the seam, and with the methods used in the mining and in the preparation of the coal. ROM screen analyses of 12 U. S. coals selected at random from personal files given in Table I show: A few other screen analyses examined indicating 40 pct or more of 20-mesh X 0 dust in 3/8 in. X 0 sizes were not included because of uncertainty that they were representative. The number of results in Table I is not sufficient to give a reliable estimate of the average, or of the range to be expected, but it indicates that in every case the coal dust is a relatively large percentage of the total ROM coal, and, of course, a progressively larger percentage of resultants as the larger sizes are separated for marketing.

Jan 1, 1949

By Harlan A. Walker

Rock-drill steel has an important bearing on costs in many mining operations, both directly and indirectly. Direct factors include such items as shop expense, steel consumed per ton of ore produced, cost of distribution and the dust hazard. The latter, although no specific amount may be assigned to it, is an ever-present problem, and is receiving increased attention as the science of mining progresses. Indirectly drill-steel performance affects consumption of compressed air, maintenance of drills and drilling speed. The latter, in turn, increases or retards the tempo of mining and development. These factors, while not all inclusive, are preponderant in their importance. Thus it is evident that in an extensive operation drill-steel expense may run to many thousands of dollars and that thoughtful research leading toward more efficient practice is warranted. Experimental Work During the late spring of 1939, experiments were undertaken at Homestake in reducing changes in drill-steel gauge from ? in. to 1/16 in. In drifts and crosscut headings mounted machines were set up and holes were drilled with ?-in. bit-gauge changes and other holes a few inches

Jan 1, 1940

By Harlan A. Walker

Rock-drill steel has an important bearing on costs in many mining operations, both directly and indirectly. Direct factors include such items as shop expense, steel consumed per ton of ore produced, cost of distribution and the dust hazard. The latter, although no specific amount may be assigned to it, is an ever-present problem, and is receiving increased attention as the science of mining progresses. Indirectly drill-steel performance affects consumption of compressed air, maintenance of drills and drilling speed. The latter, in turn, increases or retards the tempo of mining and development. These factors, while not all inclusive, are preponderant in their importance. Thus it is evident that in an extensive operation drill-steel expense may run to many thousands of dollars and that thoughtful research leading toward more efficient practice is warranted. Experimental Work During the late spring of 1939, experiments were undertaken at Homestake in reducing changes in drill-steel gauge from ? in. to 1/16 in. In drifts and crosscut headings mounted machines were set up and holes were drilled with ?-in. bit-gauge changes and other holes a few inches

Jan 1, 1940

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By T. M. Chance

The first bituminous coal cleaning-plant to use the sand-flotation process1 was placed in operation on Oct. 1, 1925, at the tipple of the East Broad Top Railroad & Coal Co., at Mt. Union, Pa. The general principles governing the design of plants of this type and typical operating results of anthracite sand-flotation units have been previously outlined.2 I will, therefore, confine myself to a description of this particular plant and to some of the elements of design it incorporates. The Original Mt. Union Tipple The plant was installed to transfer coal.from steel narrow-gage cars of 60,000 and 70,000 lb. capacity to standard-gage equipment. The coal was hauled about 30 miles from the East Broad Top field. This coa1, mined by the Rockhill Coal & Iron Co. and other operators, is a low-volatile slow-coking coal with ash of high-fusion point. It is normally a high-grade coal that does not contain an excessive amount of free impurities, but it requires careful handling to secure a fair domestic yield, and, naturally, the need for narrow-gage transshipment increases the difficulty of the problem. The narrow-gage cars were discharged into an 8-car track hopper equipped with two feeders passing the coal to two 42-in. apron intake conveyors. Twin units were installed throughout the original plant, two lump-and-egg shaking screens, two lump picking-tables, two egg picking-tables and two stoker conveyors. The stoker coal was loaded without cleaning. The loading tracks and booms were in duplicate and, with the layout as originally installed, either unit could be run independently, each unit shipping a different class of coal or both units making the same product.

Jan 1, 1927