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By H. P. Leighly, J. W. Marx, H. L. Walker

A relationship between recrystallized grain size and prior deformation is predicted from elementary statistical considerations, and reasonable agreement with experiment is obtained. RECRYSTALLIZATION phenomena have received much theoretical and experimental attention, and very adequate discussions of the various mechanisms suggested have been given by Anderson and Mehl,' Cook and Richards,' and Burgers," and others. It suffices to note here that the initial concepts fitted one of two general hypotheses: I—The new crystals are nucleated within microscopic regions at which there is a concentration of internal stress, i.e., volume elements of maximum strain energy. 2—The new crystals have their inception in volume elements of minimum strain energy. In a comprehensive early review of the subject, van Arkel' considered both possibilities and came to the conclusion that hypothesis 2 was inconsistent with the experimental fact that the number of nu-cleations increased with increasing deformation. He suggested that, if allowance was made for a preliminary atomic rearrangement at the points of large internal strain, hypothesfs 1 provided the more reasonable concept. Following the initial observations of Collins and Mathewsonb nd Crussard,Y he systematic X-ray investigations of Cahn' and Guinier and Tennevin" established the existence of a polygonized structure in metals that had been cold-worked, and subsequently annealed, under conditions such that re-crystallization did not occur. This new experimental evidence by no means disproved the first nucleation hypothesis, a fact recognized by both Beck" and Cahn,10 who independently suggested nucleation mechanisms based on the idea that regions of large strain might polygonize before the bulk of the less deformed material. These mechanisms, together with others recently proposed," are dependent upon the prior existence of some degree of polygonization in the deformed material. On the other hand, a critical examination of the published data leads to the supposition that polygonization may not be the necessary precursor of recrystallization, but merely its favored energetic competitor. In regions where the lattice distortion is not too severe, the limited adjustment afforded by polygonization may permit the lattice to drop to a relatively stable low energy state in which the nucleation of a new crystal becomes improbable, even at elevated temperatures. Such structures, of course, might provide a fertile field for the growth of nuclei, if these could be introduced. In regions of concentrated lattice distortion, polygonization alone may not be able to accomplish an adequate strain reduction, and in these volume elements sufficient thermal activity permits the more drastic atomic rearrangement involved in nucleation. Completely polygonized structures are known to withstand extended heating close to their melting points," with no other effect than a slow enlargement of some of the subgrains at the expense of others. Once started, macroscopic recrystallization might be expected to go to completion in a matter of minutes under similar heat treatment. Crussard12 and his coworkers have found that recrystallization may occur in single crystals of impure (about 99.7 pct) aluminum without any detectable prior polygonization. The indication here is that large Cottrell impurity atmospheres inhibit dislocation movement, thus suppressing polygonization to such an extent that the alternative process, recrystallization, dominates the lattice restoration. Experimental studies relating recrystallization directly to stored energy have not, at the present time,

Jan 1, 1954

By P. J. Jacquard, C. Jain

Interpreting pressure measurements is one of the fundamental problems in the operation of oil reservoirs. The principal methods and means of study zuhich are currently used are reviewed. Emphasis is placed on the necessity of improving the quality of the information to turn it to the best possible account. One of the important aspects of the problem is the development of a system of automatic interpretation of the pressure measurements. The proposed method aims at this objective: starting from the relation which exists between a local perturbation of permeability and its effect on the velocity potentials in the wells, we determine by successive approximation the modifications to be made to the permeability map by fitting the least squares between the measured pressures and the pressures indicated by the mathematical model. The method has already been successfully employed in the case of heterogeneous reservoirs of radial- circular symmetry. Its application is extended here to the two-dimensional case, and is illustrated by two examples, for which the results are presented. The conditions required for the method to become fully operational are likewise analyzed. I — INTRODUCTION One of the basic problems of production and recovery from oil fields is interpreting pressure measurements made in wells in the single-fluid-phase regime. Simplifying assumptions, for example supposing the reservoir to be homogeneous, make it possible to use more or less simple methods which permit the estimation, from these pressure measurements, of a mean value of the permeability around the wells. Considering the actual heterogeneity of the majority of reservoirs, and the phenomena of interference between wells, these methods are only indicative. Much has been published on the studies of different cases of comparatively simple heterogeneity: some have discussed the radial heterogeneity around a single wel1,l or vertical heterogeneity.2 The results of these works have shown the influence of variations of permeability on the pressure, but unfortunately they are not very useful in practice because they all are concerned with the phenomena around a single well, without interference between wells, and they correspond to relatively simple and theoretical schemes. These studies of reservoirs or parts of reservoirs on a larger scale are made by the electric analyzer or digital model. We define a permeability map and a porosity map, then reproduce the production history of the wells on the wells of the model, and note the corresponding pressures. These pressures are then compared with actuality, and the discrepancies observed are analyzed. From this analysis we deduce the modifications to be made to the maps of permeability and porosity, and repeat until the coincidence between the pressures indicated by the model and the actually observed pressures is considered adequate. We have adjusted the model. Obviously, in this method of investigation, everything depends on the formula which permits the modification of the permeability to approach the adjustment. Considering the complicated nature of the problem, some oversimplified formulas are poorly adapted to reaching a good adjustment. For example, we have shown that the elementary operation of increasing the permeability not far from a producing well to compensate for too low pressures in the well can, in certain cases, express itself by an effect exactly opposite. 3 The project described here is for a system where we begin with the pressure measurements and the several known parameters of the reservoir, and develop the most probable permeability map, taking account of the measurements available and a subdivision of the reservoir fixed a priori. Ideally, this system is conceived as one in which no manual intervention would be necessary. The model simulating the reservoir is only one part of the whole system, and it is neither the longest nor the most complex part. The need to integrate the model into an aggregate of much more extensive processes has led to the adoption of the digital solution, even though a solution combining the digital and the analog is perfectly conceivable. The simulating model is in that case no more

Jan 1, 1966

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By Raymond Mancha

The purpose of an accurate underground pressure survey is to obtain a pressure gradient along the circuit or circuits under investigation. The pressure gradient shows the rate of pressure drop between various observation points along a circuit. This determines excessive resistance regions and the economic feasibility of correcting such conditions by cleaning airways, driving additional airways, or modifying existing airways. A pressure gradient is useful for predicting the effect on other parts of the circuit when adjusting the air regulation on any one split or when planning a field airshaft or slope or a new drift to the outcrop. A single-compartment airshaft often produces disappointing results because it relievcs only a part of the circuit instead of the over-all mine pressure. It is valuable to know how the circuit pressure drop is distributed. The underground pressure survey is used also to determine the friction coefficient for various types of airway. High precision work is required to establish these vital data for predicting the characteristics of mine pressure volume when projecting new mine developments. Methods Regardless of the type of instrument used to conduct a circuit pressure survey, the work should preferably be performed at a time when the mine is idle, in order to avoid air-flow disturbances from moving trips and cages or from the opening or closing of trap doors. Preferably the survey should be made when the barometer is comparatively steady, to restrict variation in the air specific weight at observation stations while the circuit is traversed. The two most commonly used instruments for underground pressure surveys are: (I) the altimeter; (2) the inclined manometer with hose extensions. The altimeter is sufficiently accurate for determining the underground pressure gradient and is preferable to the nianometer for such work because of greater flexibility and shorter time required for the traverse. With the altimeter it is possible to select more widely separated observation stations than is practical with the manometer, with its restricted hose extension lengths. The altimeter also permits easier travel along haulage roads between airway observation stations, avoiding badly obstructed airways. The inclined manometer is more reliable than the altimeter for establishing friction coefficients in mine airways. Manometer readings are unaffected by differences in elevations between stations, which require corrections to altimeter data. The manometer provides direct reading without temperature correction, which may or may not be true with the altimeter, depending upon the make of instrument used. The elimination of correction factors combined with the instantaneous, simultaneous and

Jan 1, 1947

By Raymond Mancha

The purpose of an accurate underground pressure survey is to obtain a pressure gradient along the circuit or circuits under investigation. The pressure gradient shows the rate of pressure drop between various observation points along a circuit. This determines excessive resistance regions and the economic feasibility of correcting such conditions by cleaning airways, driving additional airways, or modifying existing airways. A pressure gradient is useful for predicting the effect on other parts of the circuit when adjusting the air regulation on any one split or when planning a field airshaft or slope or a new drift to the outcrop. A single-compartment airshaft often produces disappointing results because it relievcs only a part of the circuit instead of the over-all mine pressure. It is valuable to know how the circuit pressure drop is distributed. The underground pressure survey is used also to determine the friction coefficient for various types of airway. High precision work is required to establish these vital data for predicting the characteristics of mine pressure volume when projecting new mine developments. Methods Regardless of the type of instrument used to conduct a circuit pressure survey, the work should preferably be performed at a time when the mine is idle, in order to avoid air-flow disturbances from moving trips and cages or from the opening or closing of trap doors. Preferably the survey should be made when the barometer is comparatively steady, to restrict variation in the air specific weight at observation stations while the circuit is traversed. The two most commonly used instruments for underground pressure surveys are: (I) the altimeter; (2) the inclined manometer with hose extensions. The altimeter is sufficiently accurate for determining the underground pressure gradient and is preferable to the nianometer for such work because of greater flexibility and shorter time required for the traverse. With the altimeter it is possible to select more widely separated observation stations than is practical with the manometer, with its restricted hose extension lengths. The altimeter also permits easier travel along haulage roads between airway observation stations, avoiding badly obstructed airways. The inclined manometer is more reliable than the altimeter for establishing friction coefficients in mine airways. Manometer readings are unaffected by differences in elevations between stations, which require corrections to altimeter data. The manometer provides direct reading without temperature correction, which may or may not be true with the altimeter, depending upon the make of instrument used. The elimination of correction factors combined with the instantaneous, simultaneous and

Jan 1, 1947

By F. C. Langenberg

It is the purpose of this paper to present a limited amount of experimental data obtained on the Charpy impact machine. Several concrete examples will be given showing the relation existing between the results obtained upon the Charpy impact machine and the behavior of the parts tested when in service. Although it is pointed out by G. Charpy and A. Cornu-Thenard1 that it is first necessary to determine a satisfactory working process before studying the correlation between the results of these tests and the behavior of the parts tested in service, this ideal course cannot be strictly adhered to. If a certain part repeatedly fails in service and the available tests give no indication of its cause, advantage must be taken of any possible means that will solve the problem; therefore, even though the reliability of the results obtained by the Charpy impact machine have been questioned by many, it was necessary to use this instrument without giving careful consideration to its possible sources of error. It would seem that the conclusions arrived at by Charpy -and Cornu-Thenard justify the assumption that the precision obtained by this machine is comparable to that obtained by the other more common forms of testing. The second general conclusion arrived at by them, namely, that the impact test upon notching does not offer any direct correlation to the ordinary tests, is also borne out by many hundred determinations made in the laboratories at Watertown Arsenal. This statement, however, should be qualified as follows: Other ordinary tests include the static tensile test from bars taken in a longitudinal direction and the Brinell hardness. The author agrees that no law is yet known for the computation of the energy absorbed in the rupture of bars of the same material but of different dimensions. Although Charpy and Cofnu-Thenard do not refer in their valuable article to the use of the Charpy machine in industrial practice, it should be stated that this instrument has been in constant use in the laboratory at Watertown Arsenal for several years, and is now employed for both routine and experimental testing.

Jan 1, 1920

By W. J. Slatosky

As a means of effecting better control of endpoint temperatirres at the Jones & Laughlin basic oxygen furnace plant, a set of mathematical equations has been developed. The eqlutions are the product of a themlochemical anaysis of the process and aye designed to calculate the required scrap, lime, and hot metal additions in terms of a number of independent variables. Results of test heats have warranted adoption of this technique by the Prodrrction Department. BECAUSE of the autogeneous nature of the basic oxygen steel-making process, bath temperature can be controlled without an external fuel supply by charging the furnace with additions that are thermally balanced. The thermal requirements of the charge materials are such that, during the refining process, they throttle the heat generated by the metallurgical reactions in a manner designed to result in a speci-fied temperature at the completion of the heat. In the past, operating personnel at the basic oxygen furnace plant of Jones & Laughlin's Aliquippa Works relied on their experience and technical knowledge of the process to determine the quantities of charge additions needed to result in a finishing temperature in the range 2880"to 2920" F. (The charge consists primarily of 93 tons of scrap and hot metal plus an amount of lime sufficient to maintain a basicity ratio of 2.8 to 3.2). Estimates of these materials are based on a consideration of the effects on finishing temperature of 1) iron silicon content, having a variation of 0.8 to 1.8 pct; 2) iron temperature, ranging from 2250°to 2600°F; and 3)any excessive cooling of the furnace due to a production delay. The end temperature of the preceding heat also serves as a guide in that, if a heat was within the specified temperature range, the succeeding heat could be charged with materials of nearly the same proportions, provided the hot metal used in each of the two charges was of approximately the same temperature and composition. On the other hand, if a heat was outside the specified tapping range, or if the hot metal used in that heat was of different analysis and temperature from that of the iron to be charged, an adjustment in the proportion of additions is in order for the following heat. Due to the complex thermochemical behavior of the process and to the inexact and subjective nature of the described method of determining charge additions, consistently accurate temperature control was not to be expected. Therefore, those heats out- side the specified tapping range necessitated subsequent adjustments by either reblowing the cold heats for a suitable length of time so as to elevate the bath temperature to the desired level, or cooling hot heats with a proper amount of scrap. Because extra time is required to make these adjustments, production is delayed. In an attempt to devise a method for improving temperature control, an analysis of the thermochemistry of the process was undertaken. This, in turn, led to the development of a set of mathematical equations which enable the calculation of the quantities of scrap, lime, and hot metal needed to result in any specified tapping temperature range. The analysis was not intended to be a repetition of work done by others such as McMulkinl or ~hilbrook.' It was meant to be an extension of their work so that charge additions could be calculated not in terms of silicon alone but, rather, as a function of all independent variables. This paper presents the derivation of these relationships, their effectiveness in controlling bath temperatures, and a method of utilizing them on an operational basis. The Heat Balance—The first step undertaken in the analysis of the problem was the enumeration of the pertinent variables. A list is presented in Table I where it is noticed that these quantities have been separated into the following three categories: important variables, variables considered as constants, and variables to be neglected. The breakdown was an arbitrary one designed to facilitate the analysis; otherwise, the mathematical treatment would have been exceedingly cumbersome and complex. Fortunately, experience has shown that these simplifying assumptions do not seriously impair the accuracy of the calculations. These variables along with the limiting assumptions listed in Table n were then used to write a heat balance of the process by applying the equation of continuity, Rate of Rate of Rate of Increase = Income - Outgo PI ] of Heat of Heat of Heat.

Jan 1, 1962

By C. M. Loeb, A. M. Gaudin, J. H. Brown

THE object of most size reduction operations in the mineral industry is to liberate the grains of valuable minerals in the ore from those of the gangue. This is usually accomplished by crushing and grinding the entire mass of ore until there is only a small probability that any single particle contains more than one mineral. During this size reduction only limited control exists over size or composition of the particles exposed to the breaking action, and there is no control over the paths followed by cracks generated during the operation. This lack of control usually results in overgrinding and in production of large quantities of very fine material. The first detriment, overgrinding, is costly in itself, but when combined with the second factor it is doubly so. Not only is the fracture of a free particle unnecessary—the fracture of these particles may also make subsequent separation operations difficult, inefficient, and wasteful. It has been pointed out' that if the object of size reduction is to liberate the valuable mineral component of the ore then, ideally, fracture should follow intergranular paths to the exclusion of trans-granular ones. This would result in liberation of the valuable minerals with as little size reduction as possible. This ideal comminution operation is referred to as intergranular comminution, and it was the object of the investigation to determine the extent to which it could be developed by heat treatments. There are many indications in the literature that heating rocks prior to crushing may be favorable. Reports by Holman,2 Yates3 and Myers' are pertinent. These investigators showed that heating certain rocks prior to crushing them did, in fact, improve their crushing characteristics in that fewer fines were produced, although the fact that intergranular comminution was being effected apparently was overlooked. In addition, Sosman noted that if there is appreciable anisotropism in the thermal coefficients of expansion of even a pure mineral, then considerable permanent separation of the grains of the rock can be expected as a result of heating the rock to a high temperature.' By the same token, if there are ap- preciable differences in the thermal expansion coefficients of the various minerals of a multi-component rock, similar results should be obtained by heating this rock. This has been tested, partially, by Brenner," who obtained patents covering the heat treatment of some pegmatitic rocks in order to facilitate comminution of these materials. It has also been demonstrated that this may occur in taconite." Also, the possibility of causing decomposition of one mineral in a rock as a means of promoting intergranular fracture has been considered. Seigle2 and Schiffman et al. have obtained patents on such processes as applied to calcareous iron ores. These reports all indicate that heat treatments prior to crushing may contribute materially to intergranular comminution, but they also indicate that no organized attempt has been made to determine the controlling factors of the method or to determine its applicability in general. The present article is a report on the initial phase of such an investigation. The authors have reviewed the claims of prior investigators and have attempted, also, to establish the factors that might determine the applicability of heat treatments in the mineral industry. In this work 2000-g samples of various rocks were heated in a small laboratory furnace and crushing and sizing operations were carried out in standard laboratory equipment. All samples of each rock were as nearly identical as possible in particle size, grain size, and composition and contained only lumps coarse enough to contain many grains each. Tests on Granite A number of tests were made on a coarse grained Finnish granite obtained in the form of coarse chips from a local monument yard. This rock exhibited little variation from piece to piece in either composition or grain size. The minerals contained were quartz, orthoclase, small amounts of hornblende, and minute quantities of mica. Grain size ranged from about 1 mm to about 3 mm. Temperature of the Heat Treatment: In some cases the granite was heated to a particular temperature and crushed, hot, immediately upon withdrawal from the furnace—in others the rock was allowed to cool before crushing, but without quenching to room temperature after heating. In most tests on granite the heating period was about 2 hr with the furnace at the highest temperature for about 1 hr. Cases in which these periods were varied greatly will be presented separately.

Jan 1, 1959

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By Thomas Fraser

"AIR-SAND" is the term which has been given to a process of separating refuse material from coal by means of a body of dry sand artificially fluidized and maintained in that condition by a continuous stream of air bubbles flowing through the sand body. By proper regulation of the rate of air flow, this fluid air-sand body may be maintained at such a density that coal will float near the surface and the refuse, which is heavier, will sink through the sand to the bottom of the container. This separation is a float-and-sink operation similar to the separation of wood chips and stones in water; the one floats and the other sinks, irrespective of size of pieces. This was the objective sought in the development of this method of cleaning coal-a dry process which requires no preliminary sizing of the coal. METHOD OF PRODUCING THE AIR-SAND MEDIUM Figure 1 shows the cast-iron cell used for testing at the Central District Experiment Station of the Bureau of Mines, Urbana, Ill. This consisted of two castings: a. rectangular box 12 in. square in cross section and 18 in. tall, open at both ends and flanged on the bottom; and a cubical box also 12 in. square inside, with a closed bottom and flanged top. A porous diaphragm is bolted between the flanged ends of the two castings. The upper part of the cell above the diaphragm is filled with river sand screened through 20 mesh without removing the dust. Air under suitable pressure is admitted to the lower part of the cell below the diaphragm. The air passes through the diaphragm and bubbles up through the sand, distending the mass and throwing the sand particles into motion.

Jan 2, 1926

ZAY JEFFRIES (author's reply to discussion *).-Messrs. Merica's and Humfrey's criticisms of some of my conclusions are rendered in the true scientific spirit by means of which differences of opinion are gradually smoothed out and all participants are benefited. It is true that the statement of generalizations on such a complex subject is hazardous, but I shall endeavor to point out the explanations for the discrepancies noted. Owing to the fact that I am now submitting a long paper on the same general subject to the Institute, my present remarks will be brief. Dr. Meric&s Assumptions' I agree with No. 1 and No. 2, with the modification that the A (amorphous) metal between grains of annealed metal has substantially the same properties as that at slip planes in deformed metal, but the two have different arrangements with reference to C (crystalline) metal and they may be in different conditions as regards internal stress, thickness, and nature of contact with C metal. Assumption 3.-I believe Fig. 1 is wrong. I know of no evidence to substantiate the curves. I believe cc (elongation of C phase) = 0 (approximately) at all temperatures and ?A (elongation of A phase) has finite values at elevated temperatures only; but these play no important direct role in the ordinary deformation of metals at low temperatures. I believe Ec (elastic limit of C phase) = Tc (tensile strength of C phase) because as soon as C metal begins to deform permanently it would rupture were it not for the A metal generated by its breakdown. We know that Ec = Tc in brittle crystals and a crystal cannot be permanently deformed without generation of A metal. Therefore Dr. Merica's

Jan 12, 1918

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By G. T. Brookman, P. B. Katz, D. K. Martin, J. A. Ripp

With the increasing emphasis on using American fossil fuel resources, more facilities are evaluating coal conversion. In addition, those facilities now using coal are considering better coal storage procedures to minimize negative environmental impacts. For example, rainfall and snowmelt on a coal pile produce a drainage stream high in acidity, suspended and dissolved solids, iron, sulfate, and trace metals. Usually, the characteristics of the runoff stream do not allow for direct discharge to streams and lakes. Detention in a holding pond and pH adjustment are traditional methods of treating coal pile runoff before discharge. Historically, this treatment methodology has been performed inefficiently without a good data base to assess how much runoff treatment is needed to meet effluent guidelines. A model was developed to simulate runoff volume and pollutant loadings under different rainfall conditions. This model will be used to size and design treatment works for coal pile drainage. The Ohio State University (OSU) version of the Stanford watershed model was selected as the base model. The OSU model simulates overland runoff in a rural area. It includes factors such as soil moisture, depression storage, infiltration, and flow to a ground water reservoir. TRC also used the OSU co-model for acid production in coal refuse piles as the basis for qualitative modeling work. A number of modifications were made to the OSU models to make them applicable to coal storage piles. The physical/chemical reactions included in the models are described in more detail in the project report. In addition, the models were altered so that a standard NOAA magnetic tape of historical meteorological data can be used as data input instead of requiring the user to create a data file. The resulting TRC coal pile drainage model is actually two models - a quantitative model, termed H2OTRC, and a qualitative model, TRCCOAL.

Jan 1, 1984

By Chester Washburne

AT present it is impossible to estimate closely the amount of oil obtainable from a given area of land. However, after the completion of a few properly distributed prospect wells, one can calculate the approximate yield of the sands penetrated, with a probable error of say 50 per cent. Even rough predictions of this kind are of value in, large operations. Without wells upon it, one can never be absolutely certain that an area will produce any oil whatever, and one can only indulge in wild guesses of the probable productive area, before the geological structure has been carefully contoured and the top of the basal water plotted on a map. This requires wells. At times it is desirable to form an idea of the possible yield of oil in advance of drilling, as in cases where the price asked for undeveloped land seems too high, but where the probability of finding oil is furnished by neighboring development, supported by the geology. In such cases the most one can do is to make an estimate of possible maximum yield, which may of course far exceed results, and which is of use mainly in the prevention of excessive initial investment. The method is very significant in a general way, as in regions like the Bighorn Basin, Wyoming, where the productive sands in the Cretaceous shale are so few and so thin and fine that they cannot develop very great production, although the high quality of the oil probably will counterbalance this defect sufficiently to give local profit in favorable areas. Reservoir Capacity of Sands.-The porosity of a stratum is the measure of its maximum reservoir capacity for liquids and gases. The porosity may be determined experimentally and must be used in connection with the total volume of the sand.

Jan 2, 1915

AN earthquake caused an upheaval in Japan, started fires which destroyed large parts of Tokio, Yokohama and Hakone, and with tidal waves and other consequences extinguished some 68,000 lives and much property right at the beginning of September." Also on Sept. 1, the Italians, offended by the murder of members of the Albanian frontier commission by Greeks, occupied the Island of Corfu, which was viewed as an act of war by Italy against Greece. An appeal by the Greeks to the League of Nations was flouted by the Italians. One of the consequences of these affairs was to throw discredit upon the League of Nations and to excite doubts whether it would be able to survive. On Sept. 19, Greece made the formal apology to the Allies collectively and following that the Italians with-drew from Corfu. During this month also the embroilment between Italy and Jugoslavia over the matter of Fiume came again into prominence. In Bulgaria there was a communist uprising which was promptly put down by the government. The whole country was put under martial law. On Sept. 13 there began a military revolution at Barcelona, in Spain. On Sept. 14 the king of Spain accepted the revolution and charged the leader with the formation of a new government. Cosgrave was reelected president of the Irish Free State, without there being any disorder. Great Britain paid the remainder of her silver debt to the United States, thus writing finis to the Pitman Act. The position of Germany went from bad to worse during September. The mark has become valueless and the business that is being conducted is largely on a gold basis once more, in terms of dollars and pounds sterling. Chancellor Stresseman announced Sept. 24 that the German government had decided to abandon pas-sive resistance to the French and Belgians immediately and unconditionally.

Jan 10, 1923

By HOWARD I. YOUNG

F. W. SPERR, Houghton, Mich.-Why does 10 to 20 per cent. of the ore formation have to he lost? It is not clear to me why it should not all be taken out, from the conditions as I saw them underground this afternoon. H. I. YOUNG.-The grade of our ore is so low that we cannot stand the expense of timbering to support the roof, which, in a sheet-ground mine, would be from 25 to 50 per cent. of our total mining cost at present. After the orebody is mined out, we can often recover 10 to 20 per cent. of the material that is left. F. W. SPERR.-I think it should be a very simple mining engineering problem to mine all of that mineral without the use of a stick of timber. Similar work has been done in the mines of Grand Rapids Plaster Co. The usual operation in deposits of this kind is to open up and excavate as far as the roof will stand; when it caves, start in and dig somewhere else. But in the case I referred to they learned that by working the ground more systematically and leaving in a sufficient amount of pillar, they could later draw those pillars and get them all, and avoid uncon¬trolled breakages which would be likely to occur if they tried to hold up the overburden permanently. From the point of view of safety and also from the financial point of view, I contend that it is better to keep the caving under control and make it do what you want it to do, rather than to take out what you can conveniently for the time being and after a while be compelled to let the overburden do what it pleases.

Jan 1, 1918

By Colin C. Rae

The absence of paraffin and other oil hydrocarbons in the soil although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. Present-day Evidence There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. Sample No. 1, SamplE No. 2. PXr Cent. PER CENt. Water......................... 20.0 29.6 Ash.......................... 3.0 3.05 Fiber.......................... 47.0 54.95 Humus acids................ 30.0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea. Many of the rivers carry much humus acid in solution, and some tropical rivers carry in the aggregate millions of tons of humus each year. The amount of humus is a variable factor, depending on climatic conditions, and on the salts and alkalies present in the water, also on the density and temperature.

Jan 1, 1923

By Colin C. Rae

The absence of paraffin and other oil hydrocarbons in the soil although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. Present-day Evidence There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. Sample No. 1, SamplE No. 2. PXr Cent. PER CENt. Water......................... 20.0 29.6 Ash.......................... 3.0 3.05 Fiber.......................... 47.0 54.95 Humus acids................ 30.0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea. Many of the rivers carry much humus acid in solution, and some tropical rivers carry in the aggregate millions of tons of humus each year. The amount of humus is a variable factor, depending on climatic conditions, and on the salts and alkalies present in the water, also on the density and temperature.

Jan 1, 1923