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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 Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By L. J. Klinkenberg

It is pointed out that the current concept of pore size distribution is not unequivocally defined and that different methods aiming at a determination of such a distribution therefore do not lead to the same results. A pore size distribution should not be based on the idea that a core should, under all circumstances, behave as a bundle of straight non-interconnected capillaries of the same pore size distribution. This is illustrated by calculations and experiments on the displacement of miscible liquids. INTRODUCTION The introduction of the concept of pore size distribution has been an attempt to characterize the intricate geometry of the flow channels in porous media. As pores in a porous medium are interconnected it is impossible to describe exactly what is meant by a "pore" and, therefore, the term pore size distribution requires further amplification. In the visual method for the determination of pore size distribution "the pore" is considered to be the hole between the grains as observed on thin sections or on a polished surface of the rock under a microscope. In all other presently known methods,1,2 a displacement process is studied and it is ascertained what as- semblaae of straight cylindrical capillaries would show the same behavior. The distribution of the capillary diameters of this assemblage is said to represent the size distribution of the pores of the actual porous medium. From the foregoing it is already apparent that it is useless to try to decide which process or which method of investigation leads to a "correct" pore size distribution. To illustrate this further a displacement process in which a fluid is displaced by another miscible with it will be discussed and the results will be interpreted in terms of a pore size distribution. DISPLACEMENT EXPERIMENTS WITH MISCIBLE LIQUIDS OF NEARLY IDENTICAL VISCOSITY AND DENSITY Interpretation in the Form of a Pore Size Distribution If distilled water is displaced from a homogeneous unconsolidated sand pack by, for instance, a dilute solution of NaCI, the breakthrough recovery i.e., the amount of distilled water produced at the moment the first trace of NaCl can be detected in the effluent water, is between 95 and 100 per cent of the pore volume of the pack. This result can be understood by following in imagination the course of one particle of the liquid. Imagine a length, ?l, at the end of which a liquid particle has an independent chance of a renewed choice of pores of different diameters. In other words, the particle has a choice of traveling time, at, for any length ?l; instead

Jan 1, 1958

Dr. F. W. C. Schniewind, New York, N. Y.:—Mr. Vogel speaks of briquetting the flue-dust by means of lime. I learned recently in Europe of a process employed with considerable success at one of the blast-furnaces, where blast-furnace cinder is used with lime. The lime and cinder are mixed with the flue-dust, and exposed to superheated steam, which converts the blast-furnace cinder into cement. Briquettes are then formed in the usual way. Mr. Vogel :—The process referred to is the " Scoria process," which has not been in use for some time past. For that reason, I did not mention it. Prof. Arthur L. Walker, New York, N. Y.:—I would ask the commercial name for magnesium chloride, and where it can be obtained ? Mr. VoGel :—I mentioned magnesium chloride, because it has been used abroad to a large extent. In Germany it is obtained as a by-product in the manufacture of potash-salts; in the United States we have been using chloride of lime, which is cheaper. Otto Sussman, New York, N. Y.:—What is the cost of this process ? Mr. Vogel :—The cost is exceedingly low. I can give you the figures from abroad, but not for the United States, because the system has not -yet been used here commercially to

Jan 1, 1913

By Chester A. Rowland

INTRODUCTION Comminution is generally a feed preparation step for subsequent processing stages; exceptions being when a final product such as aggregates, specification sand, Portland Cement, and similar products is produced. Grinding, the fine product phase of comminution, requires a large capital investment and frequently is the area of maximum usage of power and wear resistant materials. Grinding is most frequently done in rotating drums utilizing loose grinding media, lifted by the rotation of the drum, to break the ores in various combinations of impact, attrition and abrasion to produce the specified product. Grinding media can be the ore itself (autogenous grinding -- primary and secondary), natural or manufactured non-metallic media (pebble milling) or manufactured metallic media -- steel rods, steel or iron balls. This chapter will discuss general mill design and the specific design and application of the following types of tumbling grinding mills. [Overflow Rod Mills Figure 1 Peripheral Discharge Rod Mills Figures 2 and 3 Compartment Mills Rod and Ball Figure 6 Ball Figure 6a Pebble Mill Figure 6b Overflow Ball Mills Figure 8 Diaphragm (Grate Discharge) Ball Mills Figure 9] I. GENERAL MILL DESIGN A. Liners The interior surface of grinding mills exposed to grinding media and/or the material being ground are protected from wear and corrosion by rubber, metallic, a combination of rubber and metallic, or non-metallic wear resistant materials. B. Drives Economics at the time of plant design and mill purchase determine the drive to be used. The simplest drive is the low speed synchronous motor with speeds in the range of 150 to 250 RPM connected to the mill pinion-shaft by either an air clutch or flexible coupling.

Jan 1, 1982

By W. Rostoker, D. W. Levinson, A. Yamamoto

The influence of carbon on tensile strength, tensile ductility, transformation kinetics, and grain growth characteristics of selected Ti-Mo base alloys was studied. No systematic influence of carbon in tensile strength or significant deleterious effect on tensile ductility was observed. There was a marked increase in transformation rate due to carbon. Dispersed carbides exert a marked inhibiting effect on grain boundary migration, and thus effectively prevent grain coarsening during solution treatment in the ß phase field. AS part of a research program directed toward the illumination of factors governing modes of transformation, transformation kinetics, and mechanical properties obtainable through these transformations by heat treatment, Ti-Mo base alloys were selected for study. The binary system is a characteristic phase diagram type which has been studied in some detail', ' in relation to transformation kinetics and mechanical properties. Although carbon bearing alloys have acquired a bad reputation, the possibilities of melting titanium under conditions which occasion some carbon pickup are very attractive. It is therefore of considerable importance to know whether carbon, present as a dispersed carbide phase, is actually deleterious when all other detrimental factors are minimized. Basic alloy compositions containing nominally 3, 5, 7, and 11 pet Mo were prepared with systematic carbon addition up to 1 pet by weight. Various of these alloys were subjected to a series of critical and definitive experiments to delineate the effect of carbon on the transformation behavior and associated mechanical properties. Experimental Procedure Alloys were prepared from 115 Bhn magnesium-reduced sponge titanium. This sponge analyzed ap- proximately 0.05 pet C. Ti-Mo and Ti-C master alloys were made by arc-melting the sponge with high purity (99.9 + pet) molybdenum and spectro-scopic grade graphite, respectively. Alloys were then prepared from the master alloys and sponge by double are-melting. One kg ingots were prepared by melting in a nonconsumable electrode furnace. These ingots were forged at 1000°C to '/z in. rods, and cleaned and processed into electrodes for the second melting operation. The final ingots were ground to remove surface defects, then forged again to 1/2 in. or 3/8 in. diam rods for processing to test samples. It is significant that all of the alloys at all carbon levels forged satisfactorily. For convenience, the alloys will be referred to throughout the text by their nominal analyses. Samples for the study of transformation rates were prepared from 1/2 in. diam round stock. They were then solution treated in a helium filled tube furnace at 1000°C for 30 min prior to the isothermal transformation treatments in lead bath furnaces. Temperature control in both cases was within ±3oC. Following the isothermal transformation treatments the samples were water quenched. These experiments were carried out before the general adoption of the resistometric procedure for kinetic studies. The data were therefore obtained entirely by metal-lographic analysis. M, temperature was also determined by the metallographic method. Shoulder-type tensile test pieces were machined from heat treated, 1/2 in. diam slugs to provide a 0.252 in. test diam and a 1 in. gage length. The isothermal-type heat treatments were chosen from previous data' to provide three levels of strength and ductility.

Jan 1, 1957

By D. C. McLean

This report summarizes the work that has been done during the past several years in adapting resins for use as auxiliaries in mine roof support. The resins were applied in two ways: 1) by injection into the strata, and 2) as a bonding agent for roof bolts and reinforcing bar. The Explosives and Mining Chemicals Department of the American Cyanamid Co. has worked during this period in cooperation with the Roof Control Research Group of the U.S. Bureau of Mines, the Pattin Manufacturing Co., the J. H. Fletcher Co., the Homestake Mining Co., the U.S. Steel Corp., the National Mines Corp. and the Pocahontas Land Corp. in an effort to create resin formulations and methods for applying them as a practical and sate type of roof support for mining areas particularly where conventional support is inadequate, yet expensive. This, work has involved much pioneering in a field where theory, speculation, and pure mythology predominates, and little basic engineering data is available. It is strange butt true that, despite the importance of roof control both from an operational and safely standpoint, there is scarcely a mining' company in this country that has an engineer, or anyone, assigned to the study of roof support problem, except temporarily--after a bad roof fall. The responsibility for improving roof control methods seems to have been placed entirely upon the shoulder, of the USBM, various State departments of mines, and individual roof bolt manufacturing; companies. It was in cooperation with the USBM that Cyanamid first developed resins for mining use.

Jan 1, 1964

By Alan Probert

IN his inaugural address in 1949, President Truman made a policy declaration which launched the foreign technical assistance program known to the world as Point Four. Congress passed Public Law 535 defining the scope of the program and holding activities to certain limitations. It also provided $34.5 million for the first fiscal year. The Technical Cooperation Administration was established within the Department of State to coordinate and direct a program to include "economic, engineering, medical, educational, agricultural, fishery, mineral and fiscal surveys, demonstration, training and similar projects." The mineral programs of Point Four have been staffed and managed by two agencies of the Department of Interior, the Geological Survey and the Bureau of Mines. The Geological Survey is concerned primarily with water-supply problems, the discovery of mineral deposits, and the determination of habit, shape, and grade of mineral deposits. The Bureau of Mines is concerned with determining the commercial potentialities of mineral deposits, mineral technology, and the production and distribution of mineral commodities. Mineral projects comprised only 1 pet of the first year's budget. In spite of the relatively insignificant expenditure compared to those for food, agriculture, and health, a commendable record has been achieved.

Jan 1, 1952

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 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 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 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 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 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 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 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 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