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By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By Raymond Mancha

The use of blower fans and tubina- for auxiliary face ventilation is a somewhat controversial subject. Most authorities agree upon the advantages of this system over the maintenance of line brattice for dead-end ventilation. They also recognize the system's disadvantages. However, there is considerable disagreement as to the proper relation of the advantages to the disadvantages. It is the purpose of this report to present the opinions of four authorities of diversified occupation and permit the reader to form his own opinions on the subject. ORsErvers Carel Robinson is a mining engineer consultant of wide repute, who has a background of operating experience. Thomas G. Fear is a mine operator whose present position is that of chief engineer for the Hanna Coal Co. at St. Clairsville, Ohio. E. H. Denny is chief of the Coal Mine Inspection Division of the U. S. Bureau of Mines, and is a very able engineer whose past experience well qualifies him to appraise this problem. Cloyd M. Smith, editor of the periodical Mechanization, is a ventilation consultant. For a number of years he was a member of the Mining Department of the University of Illinois and has studied mine ventilation for many years. It is Mr. Robinson,s opinion that closely spaced breakthroughs, although conducive to low gas accumulation past the last open crosscut during the driving of entries, are difficult to maintain and are constant Sources of fugitive air. Jute or canvas brattice is suitable for entry driving with

Jan 1, 1944

By Tadao Nagai, Masao Sato

Electrochemical measurements have been carried out in an auto- clave to investigate the electrochemistry of hydrogen precipitation of nickel from acetate buffered solution. After having previously obtained the rate equation for this reaction we have now made a concentrated effort to explain the rate equation electrochemically. A saturated NaC1-type Ag/AgC1 reference electrode has been improved so that it can be used in an autoclave. Polarization curves for the reaction, [H2=2H+ + 2e,] on nickel electrode were measured in solutions free from nickel ions at 185°C, and the parallel curves were obtained by changing PH2 and pH for normal and reverse reactions, respectively. Polarization curves in nickel solutions were complex, probably because the potential of hydrogen electrode is close to that of nickel and of the nickel surface altered during polarization. Then the nickel electrode potential and the reaction rate were measured simultaneously during pressure reduction at various hydrogen pressures and at various nickel concentrations. The reaction rates in terms of current density were plotted to obtain the local polarization curves for reactions Ni2+ + 2e ? Ni and H2 ?2H+ + 2e. The anodic and cathodic local polarization curves exhibit potential dependency. Therefore it is likely that the pres- sure reduction can be regarded as a coupled electrodes reaction.

Jan 1, 1973

By H. M. Roberts

H. M. ROBERTS, Minneapolis, Minn. (communication to the Secretary*). -The rifling of drill cores is a frequent source of interest to men engaged in diamond drilling. Previous to the appearance of Dr. Crane's paper, there has been little record of connected observation or rigid speculation as applied to the cause of rifling. Replying to one of Dr. Crane's letters of inquiry, I ventured my opinion that the cause of rifling was a complex problem in physics, which I had not attempted to solve up to that time, except to ascribe it to the general cause of rotation and vibration of the rods. The question is worth attention not only as a matter of curious scientific interest but also for the reason that it stimulates thought on

Jan 10, 1916

By Raymond Mancha

The use of blower fans and tubina- for auxiliary face ventilation is a somewhat controversial subject. Most authorities agree upon the advantages of this system over the maintenance of line brattice for dead-end ventilation. They also recognize the system's disadvantages. However, there is considerable disagreement as to the proper relation of the advantages to the disadvantages. It is the purpose of this report to present the opinions of four authorities of diversified occupation and permit the reader to form his own opinions on the subject. ORsErvers Carel Robinson is a mining engineer consultant of wide repute, who has a background of operating experience. Thomas G. Fear is a mine operator whose present position is that of chief engineer for the Hanna Coal Co. at St. Clairsville, Ohio. E. H. Denny is chief of the Coal Mine Inspection Division of the U. S. Bureau of Mines, and is a very able engineer whose past experience well qualifies him to appraise this problem. Cloyd M. Smith, editor of the periodical Mechanization, is a ventilation consultant. For a number of years he was a member of the Mining Department of the University of Illinois and has studied mine ventilation for many years. It is Mr. Robinson,s opinion that closely spaced breakthroughs, although conducive to low gas accumulation past the last open crosscut during the driving of entries, are difficult to maintain and are constant Sources of fugitive air. Jute or canvas brattice is suitable for entry driving with

Jan 1, 1944

By H. Souder

The object of this paper is to bring to the notice of engineers a safety detonating fuse by the use of which misfires in blasting may be eliminated and safety in blasting operations promoted.

Jan 1, 1915

By P. F. Ahner, Leonidas Petrakis, Fred E. Kiviat

High gradient magnetic separations (HGMS) is a recently developed technique in which magnetic micron-size particles contained in a flowing fluid medium can be extracted from that medium. HGMS is presently utilized on a commercial scale in the kaolin processing and steel industries, and is being investigated for solid-liquid separations in numerous other processes. The performance characteristics of HGMS in the kaolin and steel industries are briefly summarized. A discussion of HGMS performance with respect to solids removal in a coal liquefaction process is presented to illustrate its applicability to difficult solid-liquid separations. Here, the properties of the solids suspended in the liquified coal are such that the HGMS separator achieves over 90% solids removal. The optimization of the HGMS operating parameters to yield these results will be discussed. To further illustrate the potential of HGMS, its performance with respect to the removal of oil and solids (over 98% removal) from a petroleum refinery process water effluent stream will be briefly considered.

Jan 1, 1980

By Charles B. Dudley

It is evident that, as the size and weight of cars have increased, the demands on the cast-iron car-wheel have become more and more severe. Fortunately, the factor of safety in the cast-iron wheel, as originally made, was so large that it was only when freight-cars approached the capacity of from 80,000 to 100,000 lb. that the question of wheels began to give some anxiety. A moment's thought will show that, as freight- and passenger-cars have increased in weight and size, a much greater duty is required of the same eight wheels than was formerly the case. In other words, although the cars have increased in capacity from 15 tons to 50 tons each, the number of wheels under a car has not been generally increased. It is true, some cars have been equipped with 12 wheels, but this construction is not the rule. Hence the duty which the wheel must perform has become much more severe, and although it was clearly able to stand some increase, there must evidently be a limit somewhere which cannot be exceeded. Meanwhile, it is the part of wisdom to make better wheels if possible, and accordingly, no little study is now being devoted to the requirements for cast-iron car-wheels; and modifications are being made, both by increasing the weight of the wheel and by improving the quality of the metal of which it is made. The desire to improve the quality of the wheel has led to the preparation of specifications for its manufacture; and within the last 15 years a more rigid scrutiny of the wheel is char-

Jan 1, 1905

By M. W. Strong

THE technique of handling drilling muds varies somewhat, partly because of personal factors but mainly because of differences in forma-tion, the type of problems met with, and the general drilling conditions in different localities. The much greater depths to which bore holes are now carried have made necessary closer attention to and great modifications of all aspects of drilling-mud technique. Increased depth means smaller hole, smaller drill pipe, smaller clearances, higher pumping pressures, higher differen-tial pressures between shows and the mud column, less accurate control of the weight of the mud column, delayed receipt of formation data, and poorer samples. It means longer delays and greater hazards in rectifying mistakes or dealing with accidental occurrences. Equipment on a larger scale is necessary and more pains must be taken with layout. Lastly, the budget costs of raw materials have risen to high figures and economy of time and of direct monetary expenditure have come to mean much more than formerly. A mud laboratory is now part of the essential establishment of a modern oil field and to it current problems can be submitted for the most thorough investigation. The detailed chemical properties of all mate-rials purchased or quarried have to be investigated. Detailed data on the physical properties have to be ascertained and research on improve-ment of material and its most efficient use has to be carried out. In this paper we propose to discuss the main mud problems with which we have to deal in Iran, some of which are peculiar to our local conditions while others are of the general type common to all workers in this subject.

Jan 1, 1938

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.' Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By L. A. Hanson

Jan 1, 1964

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has had a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1790. Practically all of this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the "white man" Indians are known to have made salt from such salt springs as those that existed at Avery Island, La., Charleston, W.Va., Saltville, Va., and Onondaga, N.Y. In 1862 the first rock salt was mined in the U.S. from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, Va., and then at Retsof, N.Y., in 1885. Of the more than 40 million tons produced annually in the United States, about 68% or 27 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc.

Jan 1, 1975

By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons' of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it's recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By R. E. Ogilvie, N. L. Peterson

Diffi-lsion measurements were conducted at all compositims in the bcc solid solution of the U-Nb system employing incremental couples at composition intemals of 10 at. pct. Diffusion coefficients were determined by the Matano method from concentration gradients obtained with the electron-probe microanalyzer. The activation energy for inter-diffi-lsion as a function of compositim shows three distinct regions: 1) 80 to 100 pct U.6= 30 kcal per mole; 2) 20 to 80 pct U, $ - 70 kcal per mole; 3) Oto 20 pet U, Q = i40 kcal per mole. The frequency factor, fi0 and the activation energy $ were found to be roughly related by the following equation: log Do ^9.7 X IO-5Q -6,6. The Kirkendall marker movement indicates that DU is larger than DNb between 16 and 100 pct U and DNb is larger than DU from 0 to 4 pct U. FOR practical as well as fundamental reasons, the rates of diffusion in alloys are of considerable consequence. Most solid-state reactions are largely dependent upon the diffusion of atoms through the lattice structure and along grain boundaries. The high-temperature strength and reasonable nuclear properties of niobium have prompted its use as a reactor material in contact with uranium fuel. Hence, diffusion data for the U-Nb system are of considerable importance. In the previous diffusion study1 on the U-Nb system using pure element couples, reliable data were obtained only in the range of 0 to 10 at. pct Nb due to the large variance of the diffusion coefficient with composition. Also, a large Kirkendall effect and considerable porosity in the uranium-rich areas of the specimen were reported, which suggests that the true diffusion coefficients are somewhat larger. The purpose of the present study was to obtain reliable diffusion coefficients at all compositions using incremental diffusion couples with intervals of 10 at. pct. In view of the abnormal self-diffusion be- havior of y uranium2-4 and some other bcc transition elements,&apos;-&apos; it was felt that a comparison of the interdiffusion coefficients in the bcc U-Nb system with those of Reynolds et al.9 for the fcc gold-nickel system might shed some light on the diffusion mechanism involved. Both systems have similar phase diagrams, in that complete solid solubility exists above a miscibility gap. EXPERIMENTAL PROCEDURE The uranium used in this investigation was obtained through the courtesy of Argonne National Laboratory. An analysis of this material detected only Si-30, A1-7, C-6, N < 10 and 0-18 ppm. The niobium was electron-beam melted material obtained from Stauffer-Temescal. The gaseous impurities were less than 50 ppm, and the spec troc hemical analysis showed Ta-500 and W-200 ppm. U-Nb alloys were prepared at composition intervals of 10 at. pct by melting the appropriate amounts of the pure elements in an arc furnace. The buttons were inverted and remelted 6 times to assure complete mixing. The buttons were then wrapped in molybdenum foil, canned in Zircaloy-2 or stainless steel, and hot rolled 30 pct reduction in thickness at temperatures between 850" and 1100°C. Alloys with 10, 20, 30, 40, and 90 at. pct Nb rolled quite easily under these conditions, but the 50, 60, 70, and 80 pct alloys remained brittle. After melting and rolling (when possible), the alloys were annealed for 24 hr at a temperature within 100°C of their melting point in a dynamic vacuum of better than 4 x 10-8 mm Hg. These treatments produced alloys which were homogeneous on a 1 p scale within the detectability limits of the electron probe. During fabrication, the alloys picked up as much as 100 ppm Mo and 100 ppm Zr. Other elements checked for but not found were Co, Cr, Fe, Mn, Ni, and Ti. The grain size of the annealed samples ranged from 3 mm for the uranium-rich alloys to 0.3 mm for the niobium-rich alloys. This permitted measurements of the concentration gradients in the diffusion samples without crossing more than one or two grains, thereby eliminating any grain boundary effects. The specimens were bonded by theU&apos;picture frame" technique as reported by Kittel.10 Specimens of composition b)U + (100 - x)Nb were sandwiched between two specimens of composition (x + 10)U + (90 - x)Nb after they were ground flat and parallel

Jan 1, 1963

By J. Philibert, A. G. Guy

Diffusion in the presence of deformation was studied by the method of vacuum dezincification of copper-rich and silver-rich solid solutions containing 7 to 30 pct Zn. The specimens were designed to permit the study of diffusion in separate portions of a given specimen characterized by strain rates ranging from essentially zero to approximately 10 sec-. No effect of deformation on diffusion was observed. BEGINNING with the work of Buffington and Cohen: interest in the question of the effect of stress or strain on diffusion has largely been concentrated on the enhancement of diffusion in specimens subjected to Continuous plastic deformation. The present research is a contribution to this limited area. However, as a preliminary to focusing attention on this special topic, it will be desirable to make a broad survey of the larger question, especially since there has been considerable foreign work in areas outside those of current interest in the United States. Since most of the topics referred to in the following section are both complex and imperfectly understood at present, it has been expedient in most instances to offer only a guide to the general nature of the work rather than a critical evaluation. PREVIOUS WORK The effect of elastic stress on diffusion has received considerable attention, especially with regard to the thermodynamic driving force for diffusion. The thermodynamic treatments have been based on the work of Gibb, Voigt, Planck, and Leontovich.&apos; Konobeevskii and Selisski6 made a first attempt at treating the problem in 1933, and Gorskii7 a few years later gave a solution applicable to single crystals as well as to polycrystalline specimens. In 1943 Konobeevski8 published treatments that have been the basis of much Russian work up to the present. For example, Aleksandrov and Lyubov used his work in explaining the velocity of lateral growth of pearlite. Early work in the United States was that of Mooradian and Norton, which showed that lattice distortion tends to be relieved before it can significantly affect the diffusion process. Druyvesteyn and Berghoutl1 observed a slight effect of elastic strain on self-diffusion in copper, while de Kazinczy12 found that both elastic and plastic deformation increased the rate of diffusion of hydrogen in steel. On the other hand, Grimes58 observed no effect of either elastic or plastic straining on the diffusion of hydrogen in nickel. High-frequency alternating stresses have been reported by various investigator s13-l5 to increase the rate of diffusion. A special form of elastic stressing is the imposition of hydrostatic pressure, a condition that is amenable to Conventional thermodvnamic analysis. Most of the experimental results in this area are consistent in showing a slight decrease in diffusion rates at high pressures.16-l8 Although Geguzinl reported a pronounced effect of relatively small pressures, Barnes and Mazey20 failed to Corroborate this finding, while Guy and Spinelli21 advanced an explanation of the phenomenon observed by Geguzin. It has been recognized that the thermodynamic treatment of diffusion phenomena in an arbitrarily stressed body is complicated by the fact that the desired state of quasi-equilibrium of the shear stresses cannot be maintained during a general diffusion process. However, attempts have been made by Meix-ner22-24 and Fasto to treat certain restricted cases, such as relaxation. FastovZ7 has also incorporated the general stress tensor into the thermodynamics of irreversible processes. The lattice strain that accompanies the formation of a solid solution has been the subject of much study,28-s0 and indirectly it has entered into many recent theories of diffusion. However, some Russian investigators31&apos;32 have taken other views of this matter and have predicted large effects on diffusion rates because of concentration stresses.o In completing this brief resume of previous work involving elastic strains and before proceeding to a consideration of the effect of continuous plastic deformation, it should be pointed out that deformation of various additional types may also influence diffusion. The effect of cold-working on subsequent diffusion has been studied directly by AndreevaS and by Schumann and Erdmann-Jesnitzer, while indirect evidence has been obtained by Miller and Guarnieri and by Vitman.38 Thermal stresses may also influence diffusion, contributions to this subject having been made by Fastovs7 and by Aleksandrov and Lyubv. The work of Johnson and Martin,o Dienes and Damask,3Band DamaskS considered the question of radiation-enhanced diffusion. In considering previous work on the subject of plastic deformation and diffusion, attention will be directed to those studies concerned primarily with diffusion rather than with its relation to Creep, e.g., the work of Dorn, or to the acceleration of diffusion -controlled reactions. Observations of the effect of

Jan 1, 1962

By W. C. Schroeder, A. A. Berk

Practical experience has shown that at elevated temperatures solutions containing sodium hydroxide may attack stressed steel in a manner that cannot be explained in terms of ordinary corrosion. Because the ductility of the metal has been greatly reduced during the reaction, the entire phenomenon is usually called "embrittlement." Thus, after several years of operation caustic evaporators have been so badly embrittled that rivets could be cracked off with the blow of a hammer. Since fine intergranular cracks are almost always present in the zone of fracture, it has often been assumed that a process of selective corrosion in grain boundaries was responsible for the failure, although this has not been clearly proved experimentally. Concentrations of sodium hydroxide below those necessary for the uniform, rapid attack of the steel surface are reported to be most effective in producing embrittlement2, 3. In the operation of steam boilers a similar type of failure has been found, mainly in riveted seams or other capillary spaces where the solution may concentrate and where high stresses may also exist. It is believed that in such localized areas the dissolved solids may reach a value many times the few hundred parts per million prevalent in the body of the boiler. While this type of boiler failure has been the subject of investigation for a period of 20 years1, an understanding of its mechanism and a rational basis for complete protection have not yet been secured. To procure this information the present investigation was

Jan 1, 1936

By Kenneth B. Ray, George R. Gardner

The application of wet cleaning processes for the beneficiation of bituminous coal has created in some localities a problem in the recovery and disposal of fine solids in the washery water. The maximum allowable concentration of these solids in the washery circuit that is consistent with satisfactory operation of the cleaning units remains a controversial point. It has, however, been generally recognized for a number of years that some degree of control should be exerted over the concentration of such material. Early methods of control involved intermittent or continuous discharge of a portion of the plant slurry into near-by streams or settling ponds, and this persisted even after the adoption of settling tanks or cones. The practice is not always economical, for two reasons: first, because of the waste of coal, and, second, because it is sometimes difficult and expensive to obtain an adequate supply of water. The latter condition often is aggravated by chemical treatment of the make-up water that is necessary to prevent excessive corrosion of plant equipment. The modern approach to this problem has been the adoption of continuous thickening devices. However, because such equipment occupies considerable plant space and is somewhat expensive to construct, the practice of loading these thickeners beyond their rated capacity is widespread, therefore often the performance of such units is not altogether satisfactory. In recent years, European washeries have increased the rate of settling of the fine coal from the slurry by the addition of specially prepared starch solutions. These reagents cause flocculation of the solid particles and thereby increase the rate of sedimentation. The first important work on the flocculation and clarification of coal slurry was done by Henry, who developed the Henry process and used it successfully in Belgian preparation plants. Soon after the initiation in Belgium, the process was introduced into England, where subsequent, investigation developed similar processes, which were successfully used in

Jan 1, 1939