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By C. G. Dunn, E. F. Koch, K. T. Aust

Strain-induced grain boundary migration was studied in a series of silicon-iron (3% pct Si) bicrystals of controlled orientations. Each bicrystal was given a 7 pct cold-rolling strain rind annealed at 1100°C. The direction of boundary migration was found to depend on orientation; results for several orientations related by a common [110] axis are given. Analysis of the micrographic and X-ray data is made in terms of the residual strain-energy densities within the crystals (energy per unit volurne) and a driving force on the boundary due to an energy density difference across the boundary. Relative strain energies were obtained for the various orientations investigated. A CHROME-acetic acid electroetching method for revealing dislocation sites in silicon iron was previously applied to clarify the structural features and the energetics involved in strain-induced grain boundary migration.',' The present paper is a continuation of this study, but is primarily concerned with the influence of crystal orientation. Sperry, as reported by Beck,3 attempted to determine the factors that influence the preferred growth of one grain over another in aluminum due to strain-induced boundary migration. He found that the particular grain of a pair which work hardened more was invaded, although exceptions to this correlation were noted. The index of work hardening was determined from microhardness measurements of each grain before and after cold-rolling. In the present study, orientation itself was taken as a useful variable for studying the behavior of individual grains in a bicrystal and the direction of boundary migration, since the extent of work hardening is orientation dePendent." The effect of strain on boundary migration is evident from a consideration of driving forces. Thus, in the absence of inclusions, the driving force (per unit area of boundary) for growth of grain A into grain B when a bicrystal is strained and annealed may be expressed as follows:2

Jan 1, 1960

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By W. J. West, W. W. Garvin, J. W. Sheldon

One of the most important problems of reservoir mechanics is the prediction of the behavior of a gas and oil producing reservoir for a variety of production programs. In the absence of a knowledge of the behavior of even idealized systems, it has been difficult, if not impossible, to determine which production program would yield maximum economic recovery. The problem was formulated mathematically many years ago, hilt a solution of the equations had never been obtained because of their extreme complexity. The solution of the problem became possible, however, with the advent of modern computing machines. This paper describes a digital method of solving the problem and discusses some of the results which have been obtained to date. The IBM Type 701 Electronic Data Processing Machines located at IBM&apos;s New York Scientific Computing Service were used successfully to perform the computations. The flow of gas and oil through a reservoir can be described mathematically by two second-order, nonlinear partial differential equations which must be solved simultaneously. All derivatives were replaced by finite differences to bring the equations into a form suitable for digital calculations. A number of finite ditference formulations were investigated and one form was found which resulted in stable, convergent solutions. This form was used to obtain .solutions for both radial and linear systems producing by solution gas drive. The results presented in this paper are: (a) saturation profile within the hypothetical reservoir vs. time, (b) pres.strre profile within the hypothetical reservoir vs. time. (c) gas-oil ratio vs. cumulative recovery, and (d) ultimate recovery. The saturation profile clearly shows the effect of critical gas saturation. The saturation near the well-bore drops quickly to the critical gas saturation and remains essentially at that value until the remainder of the reservoir also has dropped to the critical gas saturation. The pressure profile shows a smooth variation of pressure across the reservoir. The gas-oil ratio drops slightly during the early stage of production until the critical gas saturation is reached, rises rapidly from then on and eventually passes through a sharp maximum just before the economic limit of production is reached. For the radial example presented in this paper, the average oil .saturation of the reservoir at a time corresponding to the limit of economic production was 56.5 per cent and the ultimate recovery was 6.86 per cent. The difference between change in saturation and ultimate recovery is caused by .shrinkage of the oil phase. The solution time with the 701 Computer is sufficiently short to permit an economically feasible investigation of the effects of variation of the many parameters which describe an oil reservoir. In particular, the ultimate recovery for various systems can he determined as a function of rock and fluid properties, of well spacing. and of production rate. INTRODUCTION The effective planning for maximum economic depletion of oil reservoirs is one of the major problems confronting oil producers. The most important part of the planning is prediction of the response of the oil reservoir to a particular production program. The production program can be selected by imposing certain controls available to the operator. Some of these controls are: (a) well spacing, (b) production rate, (c) time

Jan 1, 1955

By J. Lemish

Considerable research has been conducted in Iowa in recent years on carbonate aggregate reactions in concrete. Groups outside the state have become active in the past few years after recognizing that certain carbonate aggregates are reactive in concrete. The paper reviews the nature and extent of the problem and a summary is given of research by the author and his associates. In recent years considerable research has been conducted in Iowa on carbonate aggregate reactions in concrete. The research is part of a general study on the behavior of carbonate rocks as concrete aggregates sponsored by the Iowa State Highway Commission. Research on carbonate aggregates has not been extensive in the past. Laughlin1 published one of the first papers on carbonate aggregates in 1928 and was followed by others, notably H. S. sweet,&apos; B. Mather et al.,3 and K. Mather4 who emphasized the petrographic and physical aspects of carbonate aggregates. The recognition that certain carbonate aggregates are reactive in concrete has led to increased participation in research in the past few years by groups outside of Iowa. Significant contributions have been made by Swenson and Gillot,5 Hadley,6 and Chaiken and Halstead7 in work which emphasizes the expansion of carbonate rocks in alkaline environments and the reaction of carbonate minerals or dedolomitization with alkalies. It is the purpose of this paper to review briefly the nature and extent of the problem and present a summary of the research by the author and his associates. EXTENT AND NATURE OF THE PROBLEM The problem is the deleterious behavior of certain carbonate aggregates in concrete. It was first recognized in Iowa over 20 years ago when poor service records of certain highways were correlated with aggregates produced from the Glory and LeGrand quarries. Deleterious behavior of carbonate aggregates have been reported in Canada and, more recently, in New York and Virginia. As more knowledge is gained concerning the problem, distress in concrete related to carbonate aggregates may be recognized over a widespread area. The problem may potentially exist in the Midwest, the Northeast, and other parts of the country underlain by thick sections of carbonate rocks readily available for utilization as aggregates. The nature of distress in Iowa highways is a general weakening and deterioration of concrete characterized by progressive cracking and spalling away from joints and edges (Fig. 1). The distress generally occurs after 15 years of service and becomes progressively worse. Specimens of such concrete lack the toughness of sound concrete and break easily under the hammer in the manner of a soft brick. The matrix is generally highly carbonated and dark borders, or reaction shells or rims outline the argillaceous carbonate aggregate fragments (Fig. 2). Cracks observed in cores cut across the aggregates and concrete matrix. Although localized volume change (expansion) is associated with spalling, there is no definite field evidence in Iowa that excessive growth of concrete slabs has occurred. The experience with carbonate aggregates in Iowa indicates that the concrete deterioration is not the same as that induced by the alkali-aggregate reaction associated with siliceous aggregates. The principal difference is that in Iowa the distressed concrete is weakened throughout the slab. In concrete affected by the alkali aggregate reaction, the

Jan 1, 1961

By Vsevolod Krivobok

THE re-crystallization of metals has been the subject of much scientific investigation, some of which has resulted in a better understanding of this extremely important and interesting phenomenon. Unfortunately, while many have propounded theories of re-crystallization, but a few have presented experimental evidence as to how it takes place. If this can be determined the question, why re-crystallization occurs, may be answered more definitely. Re-crystallization in single phase metals consists of a complete rearrangement and re-sizing of the grains, of which the structure is composed, while the type of structure remains the same. That is to say, if the structure before re-crystallization is composed of a number of polyhedral grains of different shape and size, a particular spot after re-crystallization will be seen to consist of grains in no way different from the original except in size and shape. The re-crystallized grains may be smaller or larger, depending on the treatment received; and, while the re-crystallization may be brought about by means of heat treatment only in passing through a critical range, yet it is common knowledge that single phase metals subjected to cold working are possessed of a tendency toward re-crystallization, even if the heating does not reach critical range. The study of re-crystallization would, of course, be much easier if we had single crystals of any metal as the original material with which to study the phenomenon of re-crystallization, since it would permit the observation of structural changes at what amounts to enormous magnification, by changing the scale of the specimen. In metals of more normal grain size the crystal boundaries introduce complications, but the process, it may be assumed, is essentially the same. Such an opportunity

Jan 2, 1926

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz&apos; comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat&apos;s argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz&apos; postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge&apos;s theoretical treatment of his problem. It can be shown that Welge&apos;s method of measuring values for &apos;&apos;capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz&apos; comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat&apos;s argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz&apos; postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge&apos;s theoretical treatment of his problem. It can be shown that Welge&apos;s method of measuring values for &apos;&apos;capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By T. G. Sieber, T. D. Tiemann

The extraction of quartz from siliceous iron ores by dissolution in sodium hydroxide solution has been described in detail in AIME Transactions. l923 data reported covered the temperature range from 230-416°F, where a continuous increase in the amount of silica extracted with increase in temperature was found. It is the purpose of this paper to describe some unexpected results of more recent work exploring principally the range of 500600°F where higher rates and greater amounts of silica extraction were antici-p ted. In brief, the experimental procedure consists in digesting the ore under pressure in solutions of sodium hydroxide, filtering the suspension and weighing and analyzing the dried residue for iron content. The amount of extraction is calculated from the weight loss or from the iron analysis of the residue and that of the original ore.

Jan 1, 1969

By R. Hogg

Sintering is a process in which the pore structure of an agglomerated powder is modified. For many applications, it is desirable to be able to control the pore structure in order to optimize such properties as mechanical strength and reactivity (availability and accessibility of solid surfaces to reactant gases, for example). In general, these properties will be determined by the total porosity and the pore size distribution of the agglomerate. In the work described in this paper, a physically realistic mathematical model for the sintering process has been developed. The model is based on the usual assumption that the pore system in an agglomerate can be treated as a network of interconnecting, cylindrical pores of continuously varying size. It is further assumed that the total pore length is conserved during the course of the sintering process. Using standard expressions for the rate of shrinkage of an individual pore, the model can be used to predict the changes in total porosity and pore size distribution as sintering proceeds. Experimental pore size distributions, obtained by mercury intrusion porosimetry, for the sintering of oxides appear to be in general agreement with the predictions of the model.

Jan 1, 1977

By F. Lowell Lawrance

JOHN SMITH, citizen of the U.S.A., has become so accustomed to reading that Congress has appropriated billions of dollars to pay war costs. that he no longer is impressed by relatively small figures, such as several hundred thousand or a few million, in connection with Government departments.

Jan 1, 1944

Application of technology to the search for new deposits went on apace in 1963. Traditional methods, aided by modern communications, were successful in some out-of-the way corners of the world that had not been adequately prospected, but the co-ordination of several mutually supporting techniques is necessary to define exploration targets in most areas today. Although these obviously include geophysics and geochemistry, which are treated elsewhere in this issue, geology continues to play a major role. As the search focuses on less and less obvious targets there will be more need than ever to "pull out all the stops." Any anomaly may have significance and must be evaluated as a possible lead. Ability to detect them increases as the laboratory workers refine techniques for measuring physical, chemical, and isotopic properties; it will be increasingly the responsibility of the exploration geologist to understand and apply these to economic problems. Simple propecting, the search for outcrops of recognizable ores of traditional types, was perhaps most successful for iron. Potentially large deposits of high-grade magnetite-specularite-hematite ore have been found in the Mary River area near the north end of Baffin Island. The ore holds up four hills that stand some 1500 ft above the surrounding country; obviously they were ripe for discovery by the first person to come across them, in this case Murray Watts, president of British Ungava Explorations, Ltd, As preliminary examination indicates a lump ore averaging 68 to 70% iron, these deposits may be commercial in spite of the unfavorable climate and their isolation from world markets.

Jan 2, 1964

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.&apos; is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By Frederick Laist

THE past year has witnessed no radical changes in methods for the reduction and refining of copper. The Carson litigation was finally brought to a close ant1 the copper smelter is again free to introduce charge into his reverberatory furnaces in whatever manner suits him best. This litigation naturally led to much experimentation with various methods of charging and with various types of bath. In some cases the charge was introduced more or less centrally on a relatively dry hearth and in other cases into a bath of greater or less depth. The results of these furnaces were meticulously compared with the results obtained in side-charger furnaces, and it was apparent that it made little, if any difference how a given furnace \\.as charged so long as care was taken that there was always something in the furnace for the flames to work on. So long as this requirement was complied with, consumption of fuel per ton of charge smelted and tonnage smelted per furnace day remained substantially the same regardless of the method of charging or the depth of bath employed. In some instances the center-charged deep-bath furnaces gave slightly better results than the side-charged particularly with respect to copper losses. The slags of the deep-bath furnaces are generally a little cleaner

Jan 1, 1930

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Jan 1, 1938

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,&apos; liquid mercury upon brass,4 and liquid mercury upon nickel.&apos; Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.&apos; Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,&apos; the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

By M. R. Tek, K. H. Coats, D. L. Katz

In natural gas storage operations, seasonal pressure fluctuations in the gas reservoir cause the water from the surrounding aquifer to flow into and out of the gas sand. The theory of unsteady-state liquid flow through porous media developed by Van Everdingen and Hurst&apos; has been applied to predict the water movement into and out of the gar bubble for .several .postulated pressure cycles. Those cycles with as many pound-days above the original aquifer pressure as pound-days below, may cause the gas reservoir to slowly grow or shrink rather than hold to a constant volume. Applications to an actual field case study give the predicted gas reservoir monthly pressures and volumes as compared with the observed monthly pressures and volumes. INTRODUCTION A large number of natural gas storage reservoirs are bounded by or adjacent to large water-saturated formations called aquifers. The presence of these aquifers is usually evidenced by the production of water from wells delineating the gas-hearing sands. Some gas storage reservoirs in use today have been purposely developed on aquifers. Cyclic pressure variations in a gas storage reservoir cause water influx and efflux from the surrounding aquifer. This, in turn, results in a varying gas reservoir volume. The prediction of the effect of this aquifer fluid movement on the size and size variation of the gas reservoir can provide information valuable in the study of several reservoir engineering problems. The economics of gas storage operations are directly influenced by the influx of aquifer fluid into the reservoir since a shrinking storage reservoir requires increasing pressures for the storage of the same quantity of gas. Material balance and reserve or recovery calculations also obviously require knowledge of reservoir volume. Various other reservoir engineering calculations such as interpretation of well interference data, evaluation of physical characteristics of porous media, water coning, gas injection and pressure maintenance studies are typical problems where variations of volume due to edge or bottom-water encroachment becomes important. The solution of equations describing influx and efflux of water in the gas sand, application to gas storage reservoir behavior and interpretation of results are the main objectives of this paper. While this work was directed toward gas storage reservoirs, it applies equally well to repressuring of partially depleted oil reservoirs with an active water drive. MATHEMATICAL ANALYSIS As just mentioned, the cyclic pressure variations in an aquifer-surrounded gas storage reservoir cause water movement and varying gas reservoir volume. Prediction of this volume variation from the reservoir pressure cycles or the injection-production schedule requires adoption of a flow model, certain assumptions concerning reservoir and fluid properties, and formulation and solution of the governing differential equation. The flow model used in this study is a gas bubble located on a very large aquifer (Fig. la). Gas bubble radius and aquifer sand thickness are denoted by rr and h, respectively. Fig. lb shows the horizontal, radial two-dimensional porous reservoir attended by the unsteady, compressible motion of the aquifer liquid. Volume variation of the gas bubble is determined from aquifer water flow across the cylindrical boundary, r = r0

By George J. Young

(Cleveland Meeting, October, 1912.) I. GENERAL. THE recurrence of mine-fires in Nevada during the past decade is not only a matter of interest, but also one of considerable concern to engineers and mine-managers. The more important fires may he enumerated as follows: Forman Shaft fire., Gold Hill, April 21, 1903 ; shaft-house, machinery, and shaft, destroyed; loss estimated at $50,000.; Cause Unknown. Union Shaft fire, Virginia City, July 14, 1904; shaft-house, machinery, and shaft in part destroyed; loss estimated it $100,000; cause of fire stated as the careless throwing of a match in the rope-house. Sutro Tunnel fire, Virginia City, Jan. 27, 1909 ; 700 ft. of tunnel-timbering destroyed, and direct damage of $10,000; cause &apos; probably electric wires." Belcher Shaft fire, Gold Hill, Aug. 9, 1910; shaft-house destroyed, machinery ruined, and upper part of shaft damaged; damage, $25,000; no cause given. Belmont Mine fire, Tonopah, Feb. 23, 1911; fire started in winze ; 17 men killed. Giroux Mine fire, Kimberly, Aug. 23, 1911 ; fire originated iii shaft-station from unknown cause; 7 men killed, and $34,¬521 damage caused. (NOTE 1.-On June 11, 1912, some time after the present paper was written, a fire broke out in the pump-room on the 2475 station of the Ward shaft, Virginia City. This fire was caused by the short-circuiting and exploding of the starting-switch on No. 5 pump. The oil in the switch was scattered about and set fire to the timbers and laming of the pump-room. The pump-roan in charge notified the surface, and the * Professor of Mining and Metallurgy, Mackay School of Mines.

Oct 1, 1912

By AIME AIME

OUT of the fabulous iron ranges of Michigan?s Upper Peninsula since Pearl Harbor have come go to the steel mills to become tanks, guns, ships, and other weapons for a United Nations&apos; victory. But the contributions to the war effort, as far as Michigan&apos;s iron country is concerned, do not stop there. The same men who mine iron ore deep inside the earth also are "mining" on top of the ground, gleaning a harvest of scrap iron and steel that is writing a big chapter in the War Production Board&apos;s salvage program. At virtually every mine over an area of a hundred square miles, everyone from the top mine official and straw boss to the man in the dippings is scrap conscious. They know the importance of the ore they mine but they are equally familiar with the importance of iron and steel scrap in war production. The successful job they are doing in salvage is a tribute to the entire Upper Michigan mining industry and to the man who marshaled them into action-John M. Bush, chief of the land department for the Cleveland- Cliffs Iron Co. at Negaunee, and for ten years an A.I.M.E. member. Also, this job should be an inspiration to 611 mining. metallurgical, and petroleum communities as to the latent possibilities of organized scrap recovery.

Jan 1, 1943