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By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

By D. R. Parrish, F. F. Craig

In some respects, forward combustion (alias: fie-flooding, underground combustion, in-situ combustion, dry combustion) is an efficient oil recovery method. For example, its displacement efficiency (as much as 95 percent in reservoirs with high porosity and high oil saturation) is good. In its use of heat, however, forward combustion is grossly inefficient. Most of the heat generated during forward combustion is wasted. About one-fifth of the heat is picked up by the incoming air and re-used (regenerated); the remainder is left behind the combustion zone and ultimately is lost. Compressed air is expensive, and heat generated from compressed air via underground combustion is too valuable to be thrown away. Improvement is needed. Since the early 1950's, improvements in forward combustion by addition of water injection have been discussed, particularly in the patent literature, with increasing frequency.'-'' These concepts are based on the fact that relatively inexpensive water can be used to pick up much of the heat that is ordinarily wasted during forward combustion, and transport it forward to a more useful place, thereby reducing the amount of air required to move a heat front through the reservoir. Several approaches have been proposed. Merriam and Squires1 taught that a combustible (fuel) gas should be injected along with the air and water. This, however, would give at least a tendency toward reverse combustion instead of forward combustion, and would reduce the velocity of the heat bank, defeating the primary purpose of the water injection. Pelzer2 described primarily a batchwise method of forward combustion and water flooding. He advocated burning part way through a reservoir with forward combustion, then switching from air to water injection alone to push the heat toward the producing wells. Though possible, this method has serious disadvantages, the major one being that, by the time water injection is started, much of the heat has been irretrievably lost to the overlying and underlying formations. We have described what is considered a practical Combination Of Forward Combustion And Water-flooding (COFCAW).3,4 Air and water are injected simultaneously (or alternately) after a small heat bank has been formed by forward combustion. Some of the injected fluid fills up the region behind the heat bank; the rest enters the heat bank. Upon encountering heated rock, the water is converted into steam, which then flows ahead of the combustion zone and displaces much of the oil in place. Only enough air is injected to provide heat for vaporization of the water and to compensate for reservoir heat losses. Since the size of the heat bank is minimized, heat losses also are minimized. Because of more efficient oil displacement ahead of the combustion zone, fuel consumption is reduced. Too, unlike a forward combustion zone that cannot move until all fuel at a point has been consumed, COFCAW leaves some

Jan 1, 1970

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By Robert Stefanko

With passage of the Clean Streams Act of the Commonwealth of Pennsylvania and its impact on the coal industry, considerable research has been conducted to explore various approaches to the problem, including deep-well disposal. Available drillhole data from gas and oil wells were used to develop cross -sectional maps for various portions of the state and potential disposal zones were evaluated. Bethlehem Mines Corp., faced with a severe water problem at its Marianna operation in Washington County, cooperated with the Dept. of Mining at The Pennsylvania State University in establishing a 1500-ft well into the Salt Sands for the purpose of determining the feasibility of mine water disposal. The thickness, porosity, and permeability of the formation at the well site proved to be below what had been anticipated from drillhole data. Further, subsequent hydraulic fracturing did not improve the flow characteristics of the well; pumping pressures remained in the range of 1800-2000 psig for disposing of water at the rate of 150 gpm. The legal problems of disposal at the site were very formidable. When the Salt Sands proved to be less than satisfactory, permission could not be obtained to dispose in other promising formations. The paper details many of the problems associated with the experimental well and makes an assessment of the potential for deep-well disposal of mine water. The concept of disposing of liquid industrial wastes by deep-well injection is not a new one. Brines associated with crude oil long have been disposed of in this manner, with the additional benefit of aiding secondary oil recovery. More recently, with the expansion of nuclear energy, the lethal, highly radioactive wastes which are by-products of the fission process have created severe disposal problems. During the past ten years, a variety of industries have resorted to subsurface disposal, some of the details of which are given e1sewhere.l,2 The list reveals wide variations in injection rate, pumping pressure, cost, and waste disposition. Included are successful installations in Western Pennsylvania. Enactment of more restrictive clean-water legislation in Pennsylvania recently had a great impact on the coal industry. Among its provisions was the reclassifica-tion of most mine water as industrial waste whose dis-posal is prohibited in any stream of the Commonwealth. This had the effect of accelerating research in a variety of areas, although treatment methods still retained primary interest. When a feasibility study of deep-well disposal was proposed to the Pennsylvania Dept. of Mines and Mineral Industries, the Coal Research Board (CRB) approved it. This paper summarizes the efforts on this project. Acid mine water is a chemically complex liquid. having no definite quantitative relationship among its constituents. However, it is the iron disulfide (FeS2) associated with practically all coal seams that produces the objectionable products present in acid mine water when combined with air and water. The principal contaminants are sulfuric acid (H2SO,) and ferric hydroxide (Fe(OH)2. Ferric hydroxide is a rust-colored gelatinous precipitate that coats stream bottoms and destroys aquatic life. However, other ions and bacteria are present in acid mine water in varying amounts.

Jan 1, 1971

By P. T. Allsman

INTRODUCTION The honor of being the recipient of the Mining Society's Daniel C. Jackling Award for 1966 imposes on me the responsibility to search for the subject that I would be best qualified to discuss. It seems that my experience in the mineral industry — nearly 15 years in private and 30 years in public employment — should uniquely qualify me to comment upon the relationships between the mining industry, mineral engineering as a profession, and government, and the changing economic, technologic, political and social changes that dictate their relationships. Such conditions, the increasing knowledge of the world mineral resource base, the greater demands of an expanding population with a rising standard of living, shall be evaluated with respect to our profession — mineral engineering. In all of these forty or so years, I have been in close touch with many phases of the mineral and energy resource industries, especially those of the United States. Particularly during the past 10 years, I have had a ringside seat at the "goings on" in Washington. During all of this period I have observed and analyzed many of the problems of the industry and its relations with the government. During the past few years, I have had increased opportunity for doing research and have found a need to learn something about the mathematical techniques that are undergoing such a revival since electronic computers were developed. One of these techniques is multivariate analysis, which is a system for correlating a large number of complex variables. By applying this technique to the seemingly chaotic present-day situation, there emerges a course of steady improvement in the minerals resource industries that wars, depressions, and political strife have failed to obstruct for long. In short, I advocate a need for new concepts in mineral engineering to cope with the changes, pos- sibly adding many more specialized areas on one end of the spectrum, and broad engineer-generalist approaches at the other. The meeting place shall be where the intricate mineral resource problems at the frontier of knowledge merge into the socio-techno-logical problems of the world. HISTORICAL INVOLVEMENT OF GOVERNMENT IN MINERAL RESOURCE PROBLEMS Involvement of government in mineral resource problems undoubtedly is as old as government itself. But passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of our Federal Government into the problems of mining. Passage of the law was necessary to resolve many conflicting claims and disputes in mining. The General Mining Law of 1872 and the Mineral Leasing Laws of 1920 apply to millions of acres of public lands and to certain privately owned land on which the mineral rights have been reserved to the Federal Government. The extensive involvement of government in the mineral industry business today often comes as a shock to the mineral engineer who has begun to climb the ladder to the top in his company. He is often poorly prepared to cope with the situation and becomes frustrated and even hostile. Better knowledge of the role of government perhaps would ease his situation. In our political system, private industry is responsible for producing minerals. To make certain that the production is adequate for a peace-time economy, and to guarantee the Nation's security in an emergency, the Federal Government finds it expedient to develop policy and engage in regulatory, educational, and research activities. A few examples will illustrate the varied role of government in relation to mineral problems. In varying degrees many agencies of the Executive Branch of Government have responsibilities that influence the functioning of the mineral and energy industries. In addition, of course, Congress, the Judiciary, and State and local governments exercise great influence. The Department of the Interior is primarily responsible for activities to promote the development and conservation of mineral and fuel resources, and the

Jan 1, 1967

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By E. P. Whittemore

Experience with the ASC multipoint gas lift system was obtained in Colonia zone of the West Montalvo field near Oxnard, Calif. The wells in this pool produce from depths varying from 10,500 to 12,000 ft. Oil gravity is generally 14 to 15&apos; API with a few extremes of 12 and 20" API. Some salt water is produced which causes some very viscous emulsions. Viscosities at 150F (which is the approximate wellhead temperature) vary from 5,000 to 100,000 SSU. Most of the production is by gas lift, although a few wells are produced by rod and hydraulic pump. About half of the gas-lift wells are on continuous flow and the remainder are on intermittent lift using large, ported, pilot-operated valves for single-point transfer of gas from casing to tubing. Gas-liquid ratios vary from about 6 to 10 Mcf/bbl of gross fluid lifted. Wells are produced to a 450-psi trap system. The following remarks will be confined to intermittent lift only, since this is the type of lift which has been achieved with the ASC valve system. The maximum gross fluid which has been produced by single-point intermittent lift is about 350 B/D in 3-in. tubing and 200 B/D in 21/2-in. tubing with gas-liquid ratios of approximately 7 to 9 Mcf/bbl. Some design changes could reduce this ratio. The ASC multipoint system has provided production as high as 480 BOPD in 21/2-in. tubing with gas-liquid ratios just under 4 Mcf/bbl. To be able to apply the multipoint system, it is recommended that a detailed explanation be obtained concerning transition-point pressure and stabilizer setting—what its significance is to the string design, how it may work for or against the operation of the well, how it is related to tubing sensitivity and how it affects the unloading operation. The unloading operation may only be of academic interest in a technical paper, but to the production foreman, unloading and setting the valves in operation is a very real problem and should be understood in detail. One item touched lightly in the paper was the unloading valve. This valve controls the maximum pressure at which the well can be operated. When lifting heavy viscous fluids, it is most important to set this valve for the maximum possible realistic operating pressure at the surface. If the well lifts easily, it is simple to set the ASC valves at a lower operating pressure and the unloading valve will remain closed; but if the well happens to be heavier to lift than anticipated, it may be desirable to operate on the unloading valve itself and use all the energy obtainable at the bottom of the hole. In the Colonia pool very heavy wet-gas gradients are experienced due to the viscosity of the liquid and the dense mist which is left behind a slug of fluid. There are many combination strings of 3- and 21/2-in. tubing. This aggravates the wet-gas gradient problem and provides wet-gas gradients of about 50 to 70 psi/1,000. An advantage which multipoint lift has provided is increased slug efficiency through better maintenance of pressure under the slug and decreased fall back as the slug passes up the tubing. By using multipoint injection, wet-gas gradients have been reduced to about 30 psi/1,000. This has reduced bottom-hole operating pressure and given a production increase. The ASC valve is not a simple device. It&apos;s operation is difficult to understand, and it must be understood to be used efficiently in gas-lift design. Operating problems are difficult to diagnose—whether they be caused by the fluid lifted, valve malfunction, lift gas rate, or operating pressure. Calculations and reasoning are required to find out what is causing the problem. Inherent in the ASC valve is the inability to create large pressure differentials across a slug. Large differentials may be required to overcome the inertia of very viscous fluid as it is being accelerated in the bottom of the hole. This is tied back to the design of the unloading valve and is one reason for the importance of setting the unloading valve for the highest possible operating pressure. ~u; to the narrow spread the ASC valves provide, it is impossible to cycle slower than about 24 cycles/day on choke control. If small production of 150 BOPD and less is expected, a surface time-cycle controller will be required if the most economical operation is to be achieved. To achieve a satisfactory operation, the operator must keep a record of any changes made in the operating pressure of the ASC valves. Anything which may cause changes in casing pressure in excess of the stabilizer setting will change the valve operating pressure, and if this is not noted from daily inspection of the well casing-tubing pressure recorder charts, the operator will lose control of the well. Significant results can be achieved using ASC valves; however, considerable knowledge is required to design with them, and attention to detail is required for satisfactory field operation.

Jan 1, 1965

By V. N. Krivobok

THE study and use of low-carbon manganese steels have been curiously neglected in the general history of developments in alloy steels. Hadfield1 made an extensive study of manganese-iron-carbon alloys about 1886, which culminated in the wide application and use of Hadfield austenitic manganese steel. His alloys were nearly all high in carbon, as compared with the steels discussed in this paper, and he found a marked tendency towards brittleness in the alloys of medium and low manganese content, that is, below 7 per cent. manganese. As a result, there has been a widespread prejudice against the use of manganese steels containing between 1.0 to 3.5 per cent. manganese with comparatively low carbon. Steels of this composition have never been studied adequately in comparison with other alloy steels, and have had little use in practice. In a very recent paper by Sir Robert Hadfield2 the following statement appears: ?. . . manganese-iron alloys with little or no carbon do not seem to offer any practical employment; they only become valuable in the presence of quite high percentages of carbon, 0.90 to 1.50 per cent." The results of the present investigation are so contrary to the findings of Hadfield that the writers feel fully justified in presenting the preliminary report incorporated in this paper.

Jan 1, 1927

Lake Superior Meeting . PAGE Gathmann, Emil.-Casting and Molding Steel Ingots. Discussed by J. W. Richards.. 2 McCaffery, R. S.-The Acid Bessemer Process. Discussed by Bradley Stoughton, J. W. Richards 3 Elliott, S. R.-Athens System of Mining. Discussed by F. W. Sperr, Lucien Eaton 4 Mercer, H. T. and Paulson, A. C.-Handling and Treatment of Rock-drill Steel at Copper Range Mines. Discussed by Harrison Souder, H. T. Mercer, W. H. Schacht, C. M. Haight 5 Hayden, J. E. and Eaton, Lucien.-Building Reinforced-concrete Shaft Houses. Discussed by William Kelly, T. L. Condron, Lucien Eaton 7 Eaton, Lucien.-Mechanical Ventilation at Lake Mine. Discussed by C. A. Mitke 8 Schacht, W. H.-Steam Regenerators Reduce Coal Consumption. Discussed by 0. P. Hood, W. H. Schacht ? 9 Linton, Robert.-Standardizing at North Butte Mining Co. Discussed by Grant H. Tod, C. A. Mitke 10 Smith, H. DeWitt and Sirdevan, W. H.-Mining Methods and Costs at United Verde Mine. Discussed by C. A. Mitke 12 Davy, Myron A.-Reflecting Microscope for the Mining Engineer. Discussed by C. P. Berkey, W. A. Rukeyser 14 , Norden, J. A. and Willson, A. R.-Hoisting Equipment at Utah-Apex Mining Co. Discussed by E. M. Norris 17 Aldrich, H. R.-The Dip Needle in Stratigraphy. Discussed by H. R. Aldrich, W. 0. Hotchkiss, Carl Zapffe, E. A. Kronquist 18

Jan 1, 1921

By Arthur Forsyth

A SEARCH through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1.

Jan 1, 1940

By Cyril Stanley Smith

Although alloys of copper and silicon were examined several years ago,&apos; and their excellent mechanical properties were shown, it was not until C. B. Jacobs 2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. Review of Previous WORK on the BinaRy Systems There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described," which indicate that there is a change in solubility with temperature. Copper-silicon System The copper-silicon system has been studied in detail by the author and is described in two papers published in 1928.V he portion of the diagram up to 8 per cent. silicon, as determined by this research, is reproduced in Fig. 1. The author&apos;s previous papers include a complete review of the work of other investigators and it is not necessary to deal further with this system here. Copper-manganese System The copper-manganese system has been investigated by several workers, notably Lewis,5 Wologdine,6 Sahmen7 and Schemtschuschny,

Jan 1, 1930

By J. J. Beeson

Fox the past fifty years or more, the structural features of the Cordilleran mountain system of western United States have presented some most interesting problems. Any geologist or engineer living in this region, or even making occasional examinations. of the mines, will lose much of interest and importance if he is not familiar with the literature. Some of the greatest works on geology have been the, result of studies carried on in sections of this region. Among the more important of the earlier works are those of Dutton,1. King,2 Gilbert,3 and Powell;4 of the more recent Lindgren,5 Ransome,6 Spurr,7 Butler,8 and others have contributed much. Many of the papers are largely of scientific interest but even these lay the foundation for the commercial application of the broader features of the geology. I have read many of these works with the keenest interest and pleasure; in fact, some have been read until some of the more important findings seem to be my own. In this paper, however, it is my aim to accept credit for little more than the labor of assembling some of the ideas of others. This is done with the hope that an interesting and valuable discussion will be the result. If some of the ideas presented should

Jan 9, 1925

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By Lyall Zickrick, R. S. Dean, F. C. Nix

The first attempt to establish an equilibrium diagram of the lead-antimony series was made by Roland-Gosselinl in 1896. This investigation classified the system as a purely eutectiferous one, with the eutectic at 12.5 per cent. antimony and 228" C. In the next year, Stead2 placed the eutectic temperature at 247&apos; C. The error in temperature made by Roland-Gosselin, however, has been perpetuated in the literature with a remarkable degree of persistency; this value was accepted by Campbell (1902), and Ewen (1910),3 and will be found in the last edition of Desch&apos;s3 Metallography (1922). Gonterman&apos;s investigation, made in 1907, was the most complete one available at the time .the present investigation was started. He concluded4 that the system was a simple eutectiferous one and placed the eutectic at 13 per cent. antimony and 247° C. Other investigations by Tammann (1907),5 Garbow (1909),6 Rudolfi (1910),7 Loebe (1911),8 and Leroux (1913)9 added little, if anything, to Gonterman&apos;s diagram. A number of investigations have been made of physical properties of the alloys. The electrical conductivity of the series was studied by Matthiessen (1860)10 and by A. W. Smith (1921);11 the thermoforce by Rudolfi (1910),12 and Pelabon (1923) ;13 the specific heat by Durrer

Jan 1, 1926

By George Stern

THE purpose of this investigation has been to study one method for making ordinary carbon steel by the powder metallurgy technique. This method con- [ ] sists of pressing and subsequently sintering an intimate mixture of iron powder and graphite in a suitable atmosphere to produce a steel. Two types of iron powder have been studied, electrolytic and reduced. The sintering of mixtures of loose carbonyl iron and carbon black for several hours at 1000° to 1100°C. (1830° to 2010°F.), followed by forging of the resultant ingots to bars, has been studied by Offermann.1 Trail&apos; has reported on the properties of hydrogen-reduced and electrolytic iron powders, both containing 0.5 per cent carbon. Methods for making steel bodies by powder metallurgy have also been sug- [ ] gested by Goetzel,3 who recommends the addition of steel powder of well-defined carbon content to pure iron powder, and Volterra,4 who suggests compaction and subsequent sintering of a mixture of steel powder, iron oxide and iron powder. Additional methods for making steel bodies by powder metallurgy have been reported in the literature by Koehring,5 Allen,6 Balke,7 Wulff,8 Boegehold,9 and others. 10,11,12 It is felt that the method of pressing iron powder and graphite, as described herein, lends itself best to production because of the lubricating action of the

Jan 1, 1946

By Bradley Stoughton, M. Miyake

The importance of magnesium alloys as engineering materials has increased rapidly in the past few years. The most important properties of magnesium alloys are their lightness and strength, which result in their extensive use in aircraft and automobile construction. Recent progress in the metallurgy of magneaium seems to offer hope of the production of the pure metal at a reasonable cost. The use of magnesium would doubtless increase greatly if it could be produced at a cost comparable with that of aluminum. A preliminary survey of the magnesium-base alloys shows that the most promising from a practical standpoint are magnesium-aluminum and magnesium-zinc as binary alloys, and magnesium-zinc-aluminum as ternary alloys. The research reported in this paper is a preliminary study of binary magnesium-aluminum and magnesium-zinc alloys, as an introduction to a series of further investigations. Magnesium-aluminum System The magnesium-aluminum system was first studied by Boudouard,1 who merely determined the liquidus. An accepted constitutional diagram was given by Grube,2 who found a compound A13Mg4 (melting point = 462.7" C.) and two eutectics at 35 per cent. magnesium (451.6° C.) and at 68 per cent. magnesium (440" C.) Between the first eutectic and the compound a solid solution exists. This diagram was checked or supplemented by Pécheux,3 Broniewski,4 Eger,5 Schirmeister,6 Voge17

Jan 1, 1926

By George Stern

The purpose of this investigation has been to study one method for making ordinary carbon steel by the powder metallurgy technique. This method con- sists of pressing and subsequently sintering an intimate mixture of iron powder and gaphite in a suitable atmosphere to Produce a steel. Two types of iron Powder have been studied, electrolytic and reduced. The sinkring of mixtures of loose Car-bonyf iron and carbon black for several hours at I000 to 1100 C. (1830&apos; to 2010°F.), followed by forging of the resultant ingots to bars, has been studied by Offermann.&apos; TrailZ has reported on the properties of hydrogen-reduced and electrolytic iron powders, both containing 0.5 per cent carbon. Methods for making steel bodies by powder metallurgy have also been sug- gested by Goetzel13 who recommends the addition of steel powder of well-defined carbon content to pure iron powder, and Volterra,~ who suggests compaction and subsequent sintering of a mixture of steel powder, iron oxide and iron powder. Additional methods for making steel bodies by powder metallurgy have been reported in the literature by Kohering Allen,6 Balke,7 Wulff,8 Boegehold,9 and others.,0,11,12 It is felt that the method of pressing iron powder and graphite, as described herein, lends itself best to production be-Cause of the lubricating action of the

Jan 1, 1946

By George Stern

The purpose of this investigation has been to study one method for making ordinary carbon steel by the powder metallurgy technique. This method con- sists of pressing and subsequently sintering an intimate mixture of iron powder and gaphite in a suitable atmosphere to Produce a steel. Two types of iron Powder have been studied, electrolytic and reduced. The sinkring of mixtures of loose Car-bonyf iron and carbon black for several hours at I000 to 1100 C. (1830&apos; to 2010°F.), followed by forging of the resultant ingots to bars, has been studied by Offermann.&apos; TrailZ has reported on the properties of hydrogen-reduced and electrolytic iron powders, both containing 0.5 per cent carbon. Methods for making steel bodies by powder metallurgy have also been sug- gested by Goetzel13 who recommends the addition of steel powder of well-defined carbon content to pure iron powder, and Volterra,~ who suggests compaction and subsequent sintering of a mixture of steel powder, iron oxide and iron powder. Additional methods for making steel bodies by powder metallurgy have been reported in the literature by Kohering Allen,6 Balke,7 Wulff,8 Boegehold,9 and others.,0,11,12 It is felt that the method of pressing iron powder and graphite, as described herein, lends itself best to production be-Cause of the lubricating action of the

Jan 1, 1946