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By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By Jack L. Lytton, Oleg D. Sherby

RESULTS of recent investigations1 on the creep of metals at high temperatures have revealed that the activation energies for creep of pure metals, AH,., about equals the respective activation energies for self-diffusion, hHD. This fact strongly suggests that the rate-controlling process in creep at high temperatures might be that of dislocation climb, as first postulated by Mott.' It would be desirable, however, to relate the creep rate of a metal at a given temperature and stress with actual diffusivity data, rather than with a comparison of the tempera-

Jan 1, 1957

By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By D. J. McAdam, G. W. Geil, D. H. Woodard, W. D. Jenkins

.In a series of papers, the authors and their associates have shown that the resistance of a metal to fracture is a function of all three principal stresses. Consequently since a technical cohesion limit is defined as the technically deter-minable resistance to fracture under a specific stress system, the technical cohesive strength comprises an infinite number of technical cohesion limits corresponding to the infinite number of possible combinations of the principal stresses. As shown in the previous papers, the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. The effect of each of these factors on the fracture stress is qualitatively the same as its effect on the flow stress. The effect of any of the factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. Since the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. In the general investigation described in the previously-mentioned papers, 10-18,20,21,23 the influence of the stress system on the fracture stress was studied by means of tension tests of notched specimens. When a circumferentially notched cylindrical specimen is subjected to longitudinal tension, the minimum cross section is under transverse radial tension. The mean radial stress increases with the depth and sharpness of the notch, but is always less than the longitudinal stress. The greatest principal stress (S1), therefore, is longitudinal, and since the radial stress is effectively equal to the circumferential stress, the transverse principal stresses are equiaxial in that plane (Sz = S3). By the use of notched specimens in tension tests it was shown that the fracture stress increases with increase in the radial stress ratio (s3/s1) The evidence is based not only on the results of tests to fracture at various constant temperatures, but also On results of two-stage tests, in which each specimen was plastically deformed a predetermined

Jan 1, 1949

By George B. Clark

7.1-1. Introduction. The fundamentals of blasting involve both the properties of explosives and of the rock being blasted. While the knowledge of property correlation between rocks and explosives for most effective blasting is far more complete, many quantitative evaluations have been made. Four of the most important explosive properties appear to be energy density, bulk density, rate of energy release, and the pressure-time history of the gases produced. Important rock properties are density and porosity strength, and energy absorption properties, including the effective moduli of elasticity. Rock structure also has a marked effect on its breaking properties, i.e., joints, bedding, fractures, alteration, etc. Several mechanisms enter into rock fragmentation by blasting. These include slabbing, radial fracturing, crushing, and bursting by the gas bubble. All of these factors are closely related to properties of both explosives and rock. Slabbing depends upon the character of the first generated stress wave, whose shape and magnitude are a result of the pressure generated by the explosive, its time history, and the resultant response of the rock, including its ability to sustain the stress wave. Actual slabbing, in turn, is a function of the magnitude and shape of the pressure pulse and the tensile strength of rock. Further fragmentation depends to a great extent upon the amount of gas in the bubble and its energy and pressure. Blasting rounds are best designed by taking the above factors into consideration. This is effectively accomplished by use of cratering curves which relate breakage- parameters to the explosive energy. Optimum depths from single charge cratering curves must be adjusted to changes in shot geometry and related to multiple hole blasting. Blasting damage may occur from either air blast or ground waves, and in the latter ease may be due to direct vibration or to settlement caused by vibration. Technical information indicates that blasting damage is often

Jan 1, 1968

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring's predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,' who applied Eyring'sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann's constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers' data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By K. E. Merklin, F. D. DeVaney

In the past most of the research in pelletizing has as its aim the production of a physically strong pellet. Now that this problem is solved, more attention is being paid to uniformity in grade and chemical composition. Consideration has been given in recent years to a study of additives which will make pellets partially or fully fluxed. Blast furnace tests show fluxed pellets to have advantages over both fluxed sinter and acid pellets. Lower slag volumes are used more frequently in the blast furnace and the uniformity of the charge, both physically and chemically, is becoming increasingly important. A considerable improvement can be secured by having all of the flux uniformly distributed through the pellets in a calcined state. A fluxed pellet, therefore, should be a superior product. The use of an ore burden that contains an appropriate quantity of fluxing materials is not new to the blast furnace industry. For years the Minette ores of France and Germany, the Clinton ores of the Birmingham, Ala., areas, as well as others, which are low in iron but contain calcium carbonate in sufficient quantities to give them self-fluxing properties, have proven economical. The adaption of the sintering process to the preparation of ore burdens provided a means for artifically associating the fluxstone with the iron ore prior to charging to the blast furnace. In 1944 Torpl discussed the effects of using lime in sinter made in Sweden on the sinter's metallurgical performance in a blast furnace. Hessle2 reported in 1945 on the advantages of using lime in sinter to increase the sintering plants' capacity and reduce fuel requirements. Robinson3 discussed the use of lime in Swedish sintering practice at the 1950 Blast Furnace, Coke Oven, and Raw Materials meeting. One of the suggested advantages was the combining of lime with silica to prevent the formation of a fayalite slag, which is difficult to reduce in the blast furnace. Nilson4 at the same meeting commented briefly on experimental work that had just started in the U. S. on the use of lime in sinter. The literature tends to indicate that most of this early work was directed towards improvement in sinter physical quality, and the fact that the feed to the blast furnace was partially fluxed was incidental. It was not long, however, before blast furnace advantages were being claimed. The matter was forcibly called to the attention of North American operators by reports of remarkable production records established by the Russians using fluxed sinter. The leading step was taken on this continent by the Steel Company of Canada in 1957; McMahon5 reported on the marked improvement in performance of an 18-ft blast furnace using fluxed sinter at its Hamilton works. Other North American operators quickly followed theStelco lead.

Jan 1, 1963

General discussion on the above subject, presented at the Pittsburgh meeting, October, 1914. GEORGE S. Rice, Pittsburgh,. Pa.-Undoubtedly there is a serious problem through the juxtaposition of gas and oil wells and coal mines, not only at the present time, but possibly of far more serious import for the future. If one examines a map of the coal fields on which is superposed the oil and gas fields of the country, one finds that they overlap to a very great extent. I may say at the beginning that we have not, so far as I know, had any very large number, of accidents growing out of this situation causing loss of life. Such accidents, or rather incidents, that have occurred have all been rather potential possibilities for disasters due to the leakage of gas from wells into the adjacent coal mines. The condition has been most acute in the Fairmont district of West Virginia, and in the general coal fields southwest of Pittsburgh in Pennsylvania. The accidents which have actually occurred were summarized in Bulletin No. 65 (Oil and Gas Wells through Workable Coal Beds) issued by the U. S. Bureau of Mines, reporting the transactions of several meetings in Pittsburgh, February, 1913, of oil and gas well representives, State geologists, State mine inspectors, coal-mine operators, and representatives of the U. S. Bureau of Mines. This conference was partly brought about through a case in which the Pennsylvania State inspection department had brought suit to restrain a gas company from completing a well through a certain mine. The office of the Attorney General of Pennsylvania asked the opinion of the Bureau of Mines upon the matter; about the same time the Association of State Geologists, at its New Haven meeting, asked the Bureau to take up the problem. Accordingly, it was thought advisable to bring together the several, interests. For the most part the danger is, I think, greater in the future, than at the present time Many parts of the coal fields of Pennsylvania, in Greene County particularly, have been penetrated by numerous wells very close together, and with the present practice of having a large coal pillar around each well, has made or will make the mining of many areas difficult or pro-

Jan 4, 1915

By O. C. Holbrook, George G. Bernard

A new theoretical treatment has been obtained for the behavior of pattern waterflood injection wells when closed in. Two cases are treated: Case I where oil and water are assumed to have the same properties, and Case 2 where they arc different. In applying the method, one plots log (p — p,) vs closed-in time, where p is well-bore pressure at any tims and p, is static pressure. The value of p. is determined by trial and error as that value which makes the plot linear at large time. A value for the permeability-thickness product can be determined from the intercept of this linear part, and a value of the skin factor from the injection pressure at time of closing in. Application of the method to data from water floods at three fields seems to give reasonable results. For the case of unit mobility ratio, it is proved that this new method should give the same value for permeability-thickness product as the conventional pressure build-up method. In addition, the new method gives correct values for static pressure, whereas the conventional method does not, often indicating negative static pressures. The new method may be used in cases where the surface pressure persists after closing in as well as in cases where it does not. INTRODUCTION It is of considerable interest and importance to be able to determine the characteristics of the reservoir in an area surrounding a water injection well. Thus, if we can determine early in the life of an injection well that there is a considerable "skin effect", remedial measures can be started before a full-scale pattern flood begins. Similarly, if it can be shown that a gradual buildup of skin effect is occurring with time, measures to free the water of plugging material can be taken. Determination of static pressure in the water-injection well may show that the water is entering a thief zone and not the desired reservoir. Finally, determination of the permeability of the sand around the injection well will allow estimation of the future relation between injection pressure and rate. It should be possible to determine average reservoir permeability, skin effect and static pressure from pressure fall-off data. However, at the time we began work on this subject, it was thought that no adequate theory on which to base such determinations' was available. According to the conventional method which considers the reservoir to be filled with one fluid of small compressibility (see Van Everdingen, Joers2, and Nowak2), shut-in pressure is plotted vs log where is injection time, and At is closed-in time. The physical significance of injection time, may well be questioned in this case, since in a reservoir completely filled with a single fluid (as required by this theory) and with input and output rates equal, the pressure behavior after an initial transient is independent of t,. Attempts by our Tulsa area to use this theory led to negative values of static pressure in most cases. Because of these limitations of the method discussed above, it was decided to attempt to develop a new theory of pressure behavior in water injection wells, one which would apply when there is a gas saturation, as is so often the case in water floods. In the following treatment the assumptions and basic equations are given first, then the method of application of the equations. A complete example is given to clarify details of application. All difficult mathematics has been placed in the appendices so that the reader can follow the text without difficulty. However, if he wishes only to apply the results without knowing the basis for them, he can learn how to do this from reading only the sections entitled "Plotting of Experimental Results" and "Example." ASSUMPTIONS AND BASIC EQUATIONS Statement of Problem It will be assumed that a horizontal layer of constant thickness contains in its pore system a mixture of oil, gas and water. While water is being injected into this pore- system through a well at constant rate, an oil bank is built up, gas being expelled from the space taken by the oil as shown in Fig. 1. The saturations within each

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By A. W. Cochardt

THERE are a number of effects that can cause material damping or internal friction. Some of these are frequency dependent, such as the thermo-elastic effect' and the stress-induced ordering.' Others depend on the amplitude of vibration, i.e., the damping related to the motion of dislocations3 and that due to magneto-mechanical hysteresis.' While many of these effects have been studied, only the magneto-mechanical effect has found extensive practical application. It is the principal source of damping in the current blade material in steam turbines.A magneto-mechanical hysteresis loop is seen in Fig. 1. If an unmagnetized, polycrystalline wire of a material exhibiting magneto-mechanical hysteresis, such as an Fe-14 pct A1 alloy, is twisted in torsion, a relation between shear stress and shear strain y is observed as indicated. The stress-strain curve does not follow Hooke's law -dashed line. Instead, the strain y increases nonlinearly and partly irreversibly, due to the motion of ferromagnetic domain walls,* until a critical stress is reached, which in this case is about 3,500 psi. If the applied stress is raised further, the strain appears to increase linearly and reversibly in accordance with Hooke's law, since all domains are now aligned in easy directions of magnetization nearest to the direction of the applied stress, and plastic flow has not yet started noticeably. On removing the applied stress, a remanent shear strain y, is observed, which is related to the irreversible magnetostriction of the material.' The energy dissipated in the material during a stress-strain cycle is proportional to the critical stress t, and the remanent magnetostrictive shear strain 7,. The purpose of this investigation was to make a survey of the magneto-mechanical damping of ferro-

Jan 1, 1957

By Carl E. Swartz

For many years kettles used in the melting and refining of lead and other nonferrous metals and alloys have been made of cast iron. The logic of this probably lies in the fact that cast iron has been known as a material of construction for vessels of this type much longer than steel, and satisfactory fabrication from it has been more easily accomplished and better understood. As the capacity of lead refineries has increased, it has been only natural to increase the size of kettles. Today kettles of 150 to 250 tons are not uncommon. As the size of the kettles increased and better shapes were designed, the uniformity of material of construction became more important. Records kept over comparatively long periods of time have shown that the length of service of kettles has not been uniform. Many causes contribute to this and the importance of each has not yet been evaluated. Kettle design, kettle setting, method of firing and material of construction have been changed from time to time to obtain better service, but the variation in length of service is still great. A kettle may fail during the first few heats or may last through more than one thousand heats. The purpose of this article is not to present the conclusions of a finished piece of research on kettle manufacture and use, but to present a series of observations made over considerable time in the hope that others will publish data and that all may be correlated into a logical scheme which will result in better service and longer kettle life.

Jan 1, 1931

By William J. Priestley

In the manufacture of gun forgings and other steel parts that, in service, are subject to sudden high stresses and shocks, it is most desirable to use steel possessing the greatest toughness and ductility possible without sacrifice of strength. In order to obtain this condition, it is necessary to procure steel that shows the highest possible elongation and reduction of area without lowering the tensile strength and clastic limit. Proper heat treatment of the steel can control this condition within certain limits. When heat treatment has failed to produce the desired results, metallurgists have used steels containing molybdenum, zirconium, vanadium, chromium, tungston, etc. The purpose of this paper is to describe a method by which these desired physical properties may be procured—by the elimination of certain impurities that inherently exist in steel made by the open-hearth process, and without the use of expensive alloys. Design of Gun Forgings In the manufacture of gun forgings, a certain elastic limit is fixed by the designer, and the walls of the gun arc made of the proper thickness, allowing a suitable factor of safety for the high stresses and sudden shocks that occur during gun firing. The clastic strength of the gun is about 1.4 times the stress set up at any point along the bore of the gun during firing with the maximum powder charge. As the stresses set up in the walls of the gun during firing are mostly "tangential," all physical tests are taken in this direction. Due to the length of the forgings, these tangential test bars are always taken at right angles and transverse to the direction of flow of the metal in forging. Furthermore, test bars taken across the grain of the metal will more frequently expose defects and foreign inclusions in the steel than will bars

Jan 1, 1922

By William J. Priestley

In the manufacture of gun forgings and other steel parts that, in service, are subject to sudden high stresses and shocks, it is most desirable to use steel possessing the greatest toughness and ductility possible without sacrifice of strength. In order to obtain this condition, it is necessary to procure steel that shows the highest possible elongation and reduction of area without lowering the tensile strength and clastic limit. Proper heat treatment of the steel can control this condition within certain limits. When heat treatment has failed to produce the desired results, metallurgists have used steels containing molybdenum, zirconium, vanadium, chromium, tungston, etc. The purpose of this paper is to describe a method by which these desired physical properties may be procured—by the elimination of certain impurities that inherently exist in steel made by the open-hearth process, and without the use of expensive alloys. Design of Gun Forgings In the manufacture of gun forgings, a certain elastic limit is fixed by the designer, and the walls of the gun arc made of the proper thickness, allowing a suitable factor of safety for the high stresses and sudden shocks that occur during gun firing. The clastic strength of the gun is about 1.4 times the stress set up at any point along the bore of the gun during firing with the maximum powder charge. As the stresses set up in the walls of the gun during firing are mostly "tangential," all physical tests are taken in this direction. Due to the length of the forgings, these tangential test bars are always taken at right angles and transverse to the direction of flow of the metal in forging. Furthermore, test bars taken across the grain of the metal will more frequently expose defects and foreign inclusions in the steel than will bars

Jan 1, 1922

By N. E. Norman, R. Stier

The mining industry is continually seeking out new and better underground mining techniques. One of the most recent-also, perhaps, the most significant-of the new concepts in underground mining is the use of mechanical rock-boring machines. And one of the problems that concerns us all in this matter is the cost of mechanical rock tunneling. To help answer the oft-quoted question "What will it cost me?" the following pages deal with the operating costs of so-called "medium to medium hard rock" boring machines-i.e., those designed to meet the drilling requirements in 8000 psi to 25,000 psi rock. A few machines are capable of drilling hard rock above 25,000 psi, but the economics of mechanical tunneling in rock that hard is limited at the present time. [ ] For mechanical rock tunneling, there are five main cost factors influencing the expense: Capital Investment, Cutters, Labor, Power Requirements, and Maintenance. These factors give us a good basic picture of the cost of excavation, although muck handling, erecting supports, and other costs directly related to conventional tunneling and mechanical boring enter into the final picture.

Jan 6, 1967

By Mark C. Malamphy

During colonial times, Brazil was famous for the richness of her alluvial gold deposits. Paul Ferrand has estimated that the gold produced during the period from 1700 to 1820 was the equivalent of some 64 million pounds sterling. Since that time, most of the more prolific alluvial deposits have been exhausted. A few gold mines are still functioning, notably the Morro Velho mine, which is one of the deepest mines in the world. Today, the gold production of Brazil is insignificant when compared with world figures, but there are still many gold-bearing regions and it is probable that in at least some of them profitable returns would result from an exploitation program taking advantage of all the most modern innovations in gold mining and ore treatment on a large scale. In order to demonstrate the value of some of these abandoned prospects and stir up interest in increasing the national gold production, the government has stimulated research. Experimental plants have been and are being established in various places, and tests on large quantities of ores are being carried out on a semicommercial basis. The Geological Survey of the State of Minas Geraes is very active in this line and the Federal Institution is also showing an increased interest in the matter. One of the lesser known gold-bearing regions of Brazil is in the vicinity of Lavras, in the State of Rio Grande do Sul. Gold was first reported from this region in the early part of the nineteenth century. In 1811, D. João VI sent an experienced prospector from Minas Geraes to investigate the validity of the reports. According to the reports of Baron Eschwege, he succeeded in extracting some 30,000 Oitavos (about 105 kg.) during the first few years, but the production costs exceeded the value of the gold obtained.

Jan 1, 1934

By John A. Church

IT is a well-known fact that under similar conditions a ton of pig iron can be made from any ore with less fuel when charcoal is used than when coke or anthracite is employed for heating. The cause of this superiority is entirely undiscovered, and no explanation has yet been offered which has won even temporary acceptance. Such as they are the hypotheses heretofore presented are of two general kinds, and they come from those two divisions of the working force which are so often antagonistic in all professions, the scientific and the practical men. The theory of the scientific men is drawn from the chemical reactions which are known to go on in the furnace, and it is well expressed in a recent paper by Prof. Akerman, of the Stockholm (Sweden) School of Mines. It makes the superiority of charcoal as a fuel in the blast furnace to depend upon its quick and thorough reduction of carbonic acid. This property belongs to charcoal in virtue of its porous structure. Its cells have a diameter of only one twenty-four hundredth of an inch, and one grain of charcoal has been computed to have a surface of two and four-tenths square feet. According to the theory in question, carbonic acid is formed by the first impact of the air upon the fuel; but in charcoal furnaces the acid is immediately reduced to oxide by taking the necessary amount of carbon into combination, and the gas reaches its highest reducing power even in the near vicinity of the tuyeres. Coke, being harder, does not produce so strong a reducing gas in that part of. the furnace. Carbonic acid is formed as in the case of charcoal, and remains longer before its reduction to oxide is completed. Anthracite is the

Jan 1, 1879

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962