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By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By W. E. D. Stokes

The application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government rccords, 30 Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the railway at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a community of 1000 whites have been transported by airplane. A 31/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 1936, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photographed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods. However, sounding a word of caution, a Commonwealth of Australia government report on aerial survey operations had this to say: It is necessary to repeat ad nauseam that aerial photographic survey is in no sense a substitute for geological investigation, though it is a very valuable adjunct thereto, and greatly facilitates and aceeleratcs geological mapping. There are many details

Jan 1, 1937

By S. G. Epstein

Using the capillary-reservoir technique, electromi-gvation rates of cadmium and indium in liquid bismuth were measured at several temperatures. The electric mobility of cadmium Jrom 305° to 535°C and indium from 310° to 595°C can be expressed as a function of temperature by the equations UIn = 1.52 x 10-3 exp sq caz per v-sec Migraion of both solutes was cathode-divected at a rate rnore than four tiMes tHAt previously found for siluer in liquid bisnmth. The electric mobilities of cadmium and indiulrz in liquid bismuth at 500° C are nearly identical with their respective mobilities in mercury at room temperature. AS part of a systematic study of the variables which are considered to control electromigration in liquid metals, the electromigration rates of cadmium and indium in liquid bismuth have been measured. Mass transport properties of silver in liquid bismuth have been reported previously,&apos; and measurements of tin and antimony in liquid bismuth are forthcoming. Comparisons will be made with literature values for these same solutes in mercury.2&apos;3 This series of solutes was selected to determine the effect of the solute valence on its electromigration. Silver, cadmium, indium, tin, and antimony have nearly equal atomic masses but have chemical valences ranging from +1 to +5. They are all fairly soluble in bismuth above 300°C and all have radioactive isotopes, which are an aid in making analyses. EXPERIMENTAL TECHNIQUE Electromigration of cadmium and indium in liquid bismuth was measured by the modified capillary-reservoir technique previously described.&apos; In this method irradiated cadmium or indium is added to bismuth to form alloys containing about 1 wt pct solute (<2 at. pct solute). Several quartz or Pyrex capillaries: 1 mm ID and 5 cm long, vertically oriented, are simultaneously filled in the reservoir of the liquid alloy. A direct current is passed through two of the capillaries, which contain tungsten electrodes sealed in the upper end. The other capillaries sample the reservoir during the experiment. After a measured time interval the capillaries are removed from the reservoir and rapidly cooled. The glass is then broken away from the solidi- fied alloy, which is then weighed, dissolved in acid, and analyzed for solute content by chemical and radiochem-ical techniques. An electric mobility (velocity per unit field) can be calculated from the amount of solute entering or leaving each capillary by the simplified expression1 in which Ui is the electric mobility of the solute, ?mi the solute weight change, Ci the solute concentration of the reservoir, I the current, p the alloy resistivity, and l the duration of the experiment. This expression is valid as long as the experiment is terminated before a concentration gradient develops across the capillary orifice. Earlier experiments showed that the concentration gradient formed initially at the electrode changes with time and eventually reaches the orifice, due to back-diffusion. This condition produces a solute exchange between capillary and reservoir by diffusion or convection, opposing the electromigration, which results in a lower measured value for the electric mobility. To determine if the concentration gradient had reached the orifice, the capillaries used in some of the experiments were sectioned at 1-cm intervals and the solute content of the alloy from each section was radiochemically determined. A typical concentration profile for an experiment with indium in bismuth is shown in Fig. 1; cadmium in bismuth showed similar behavior. As illustrated in the graph, very little back-diffusion has occurred in the capillary containing the cathode, since the concentration gradient is confined to the upper 1 cm of the capillary. In the capillary containing the anode, however, the concentration gradient is much broader, extending nearly to the orifice, even though the net change in solute concentration is nearlv the same in both capillaries. Since cadmium and indium probably lower the density of bismuth when alloyed, depletion of the solute from the alloy adjacent to the anode would increase the density of the liquid in the uppermost region of the capillary. This would give rise to convective mixing within the capillary, causing the broadened concentration gradient. Conversely, the alloy adjacent to the cathode should have a reduced density as the solute concentration is increased by migration, explaining the "normal" concentration profiles found in these capillaries. This disparity was not found for electromigration of silver in bismuth. Both metals have similar densities at the operating temperatures, and nearly symmetrical concentration profiles were found in the two capillaries of each exueriment. This density effect was also apparently encountered when an attempt was made to measure diffusion coefficients for indium in liquid bismuth by the same technique which was successfully used to measure diffusion of silver in bismuth.&apos; Capillaries 1 mm ID and 2 cm

Jan 1, 1968

By van Wert, L. Russell

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By D. W. Philips

The problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized rescarch began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board&apos;s publications.&apos; - Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the chief Mining Engineer of the Research Board, and was coordinated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: 1. To provide. by supports, means to prevent falls of fractured ground. 2. TO develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the properties of supports and their correct application. The second aspect is perhaps more fundamental, and involves also the properties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient frequency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1947

By David J. Mack

The structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on. the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the 0 solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lind1ief³ ho investigated the decomposition of the 0 phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman&apos;s review&apos; of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, Obinata,18.&apos;9 Greninger,20.21 and Others. The work to be described in this paper was an outgrowth of preliminary studies on the isothermal transformation of a entectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. Preliminary Experiments The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper—88.07 pet, Aluminum—11.89 pct, Iron-—0.02 pet, Manganese—-.OI pct, Others—Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1949

By Charles B. Dudley

THEO. N. ELY, Esq., Superintendent of Motive Power. DEAR SIR: It is now nearly three years since my first report to you on the subject of steel rails was written. That report, as you will remember, dealt principally with the question of the relation between the chemical composition and physical properties of steel rails and their power to resist crushing and fracture in actual service. Other matters were referred to or touched upon in that report, but the main question was, Why do some rails crush or break in service while others do not? You will doubtless remember that the principal conclusion arrived at was, that the softer rails are less liable to crush or break in service than the hard ones. Or, in other words, so far as conclusions could be drawn from the chemical analysis and physical test of 25 samples of steel rails which had actually been in service, these conclusions were that those rails which have the smaller amounts of carbon, phosphorus, silicon, and manganese are less liable to crush or break in service than those which have larger amounts of these elements. Or, again, looked at in the light * At the Lake George meeting of the Institute in October, 1878, I had the honor of presenting to the Institute, through the kind permission of the officers of. the Pennsylvania Railroad Company, the results of a study of twenty-five samples of steel rails, which had all been in actual service. Considerable discussion followed the publication of that paper, and there seemed to be a strong disinclination, especially on the part of the steel-rail manufacturers, to accept the conclusions presented. One of the principal objections urged against the conclusions drawn was, that they were based on too few samples; in other words, that no conclusions safe to act upon could be drawn from the examination of twenty-five rails. In view of this criticism it was decided to repeat the investigation with a larger number of samples, and with the aid of the experience gained in the first investigation. The results of this second study of steel rails are, by the permission of the officers of &apos;the Pennsylvania. Railroad Company, herewith presented to the Institute, with the sincere desire that they may aid in adding to our knowledge of this most important product. Like the previous paper, this is in the form of a report to one of the officers of the company, which will account for the style, and the manner of presenting the data

Jan 1, 1881

By Shun-ichi Satoh

STUDIES by many authorities have proved that nitrogen exerts an injurious influence upon iron and steel, but in the casehardening of steel by carbon, nitrogen has the advantage of accelerating the process of cementation. Its influence upon special steels is quite remarkable; it can produce the hardest layer ever known in metallurgical products-a fact hit upon by A. Fry and studied and ascertained by L. Guillet. As there have been very few investigations on the influence of nitrogen on special steels, the writer has listed important articles dealing with this problem and has conducted experiments on nitrification. He also has tested the influence of nickel upon the penetration of nitrogen in electric-arc welding.

Jan 1, 1929

By Y. C. Liu, G. A. Alers

The effect of rolling reduction on the textures of Cu-A1 alloys has been investigated both by pole figure and by modulus methods. In alloys which exhibit complete copper or brass types of rolling texture, the rolling reduction has little effect on the texture except to increase the degree of preferred orientation. In alloys which exhibit a transition texture, however, increased rolling reduction increases the amount of brass-type texture at the expense of the copper-type texture. The present experimental results show that there is no one-to-one correspondence between the SFE and the rolling texture of fcc metals. Additional data taken from the literature for fcc metals also support this conclusion. On the other hand, the present and previous experimental results are shown to be in good agreement with the suggestion that the texture transition occurs at a critical value for the separation distance between two partial dislocations—a consequence of the "dislocation interaction" hypothesis for texture. formation. This critical separation occurs when the parameter .r/ub is 3.75 x 10&apos;3. From this, a value for the SFE of 39 ergs per sq cm may be deduced for a Cu-2.85 at. pct A1 alloy. ThE correlation between the rolling texture of fcc metals and the stacking fault energy, SFE, was one of the first attempts to relate atomistic properties with the type of rolling texture.&apos; This correlation gives a qualitative explanation for the experimental observation that the addition of alloying elements, which generally lower the SFE, changes the copper-type texture to a brass-type texture. The simplicity of this correlation had led to its general acceptance and even its quantitative use.&apos; However, it is only a correlation and is largely based on descriptive features of pole figures, and on the poorly known SFE values in dilute alloys. Quantitative verification of this phenomenologi-cal correlation is, in fact, completely lacking. One purpose of the present study is to test this correlation. Another atomistic description for the formation of rolling texture is the "dislocation interaction" hypothesis of texture formation.3 In this hypothesis, the factor controlling the type of rolling texture depends on whether or not the separation distance between two partial dislocations exceeds a critical value. Materials having a separation of less than the critical value are supposed to exhibit a copper-type texture while those with a separation above the critical value are supposed to have a brass-type texture. At the critical value, it is expected that the material should show equal amounts of copper- arid brass-type orientations in their textures, i.e., a 50 pct transition texture. The SFE appears in this hypothesis as only one of several factors which determine the separation distance between partial dislocations. It is possible to test the validity of these two concepts by studying the rolling texture as a function of rolling reduction. Since the SFE per se is an intrinsic property of the metal, it should not, by definition, be influenced by local irregularities, such as variable stress conditions. Thus, no change in texture-type is expected to occur with changes in rolling reduction. On the other hand, according to the "dislocation interaction" hypothesis, any factor that effectively influences the separation distance of partial dislocations would be expected to change the rolling texture. Since the separation distance between partial dislocations is known to depend upon local stresses,4-6 it is anticipated that there would be an effect of the degree of reduction on the texture-type. Also, since applied stresses are more likely to increase, rather than to decrease, the separation between partials,4&apos;5 the overall effect would be to increase the amount of material in the brass-type orientations as rolling reduction is increased. Furthermore, this reduction dependence would be most prominent in alloys exhibiting the transition texture since the distance between partials in those alloys is thought to be close to the critical value. Experimental data in the literature is insufficient to distinguish between these two alternatives. Haessner studied the effect of rolling reduction on textures in a series of Ni-Co alloys by means of the X-ray intensity-ratio technique,&apos; and found that while one texture parameter indicated no reduction dependence the other indicated a slight dependence of the rolling texture on reduction in the range of 96 to 99 pct. As has been noticed previously, the intensity-ratio technique is a convenient but controversial method7 because there is no a priori reason to suggest which intensity-ratio would describe the texture most meaningfully. A more quantitative method of describing textures is found in terms of the orientation dependence of Young&apos;s modulus. Here, the type of modulus aniso-tropy associated with the copper-type texture is sufficiently different from that observed for the brass-type texture to allow the two types to be easily distinguishable and a quantitative measure of the amount of each can be deduced from the numerical results. This ability to provide quantitative data is particularly valuable when the two textures occur simultaneously in one alloy as is the case for the transition textures. In this paper the modulus method, supplemented by pole figure data, is used to look for an effect of roll: ing reduction the texture. Also by combining the texture measurements with recent determinations of the SFE in Cu-A1 alloys&apos;0&apos;" it should be possible to test for a relationship between the SFE and textures.

Jan 1, 1970

By Herbert Haas

1. INTRODUCTION COPPER matte is now converted into blister copper at a cost of only $5 per ton of copper, or, based on a 40 per cent. matte, $2 per ton of matte, which is the record of at least one large smelting Works; and it seems hardly likely that a further reduction, large enough to warrant, a change in existing practice, could be made in bessemerizing costs. But the new type of converter here described and the new practice proposed are intended, not so much for the treatment of mattes, as for the extension of, the process to the direct reduction in the copper-converter of pyrite ores

Jan 6, 1914

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE mechanism by which the super-saturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications. 1,2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon {111} matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;3 at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate y but that of a transition lattice ?&apos;. Since this is also platelike in shape and also lies upon the {111} matrix planes with the {110} direction in the matrix parallel to the {11.0} direction in ?&apos;, it seems likely that the original platelet particles are merely ?&apos; in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the {00.0} plane in ?&apos; are identical with those on the {111} matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures ?&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, ? &apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system,2,4 hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructure, Brinell hardness and electrical resistivity of the three alloys. PREPARATION OF SAMPLES AND EXPERIMENTAL PROCEDURE The preparation of the 20.2 per cent Ag alloy has been described.2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent Al and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By J. E. 214-000-000-010 Warren, M. R. J. Wyllie, T. Meidav, L. Scharon, R. Uhley, A. J. deWitte

By considering the stoichiometry of the underground combustion process, an equrztion was derived relating the point velocity of the combustion front as a function of the air flux, fuel content, efficiency&apos; of oxygen uitilization, hydrogen:carbon ratio, and ratio of carbon dioxide In carbon monoxide produced. In addition, an equation for cnlcrllating the amount of injected air necessary 10 produce the oil from I Cu. ft of reservoir space was derived. This equation has a direct bearing on evaluating compression costs for the process. Values calculated from these equations are in good agreement with experimentnlly obscrvcd values obtained from laborator) tube runs reported in the literature. The equations are also u\eful for atlcrlyzinf: experinlental data for inconsistencie.r.. I NTRODUCTION The injection of energy in the form of heat into an oil-bearing formation as a means of increasing the recovery of oil has been the subject of much discussion and experimentation as far back as 1920. The ideas have ranged from the injection of steam to the direct use of electricity as a means of getting thermal energy into a formation. However, most laboratory and field studies have been confined to the process whereby a portion of the crude in the reservoir is burned to generate the necessary heat to increase the mobility of the oil by reducing its viscosity. A recent paper by W. L. Martin, et al.&apos;, described the results of a number of laboratory experiments in which the combustion process was studied in a sandpack. Studies such as this indicate that with the temperatures involved, the oil is partially coked in this process and it is this coke which provides the fuel for combustion. The combustion of this residual coke can be analyzed theoretically by applying simple stoich-iometric principles to the combustion process. It is the purpose of this paper to compare the results reported in these experiments with those obtained from theoretical considerations. The variables studied by Martin, et al, among others, include combustion front velocity, air flux, oxygen utilization, fuel concentration, ratio of carbon dioxide and carbon monoxide in combustion gases, and the hydrogen:carbon ratio of the residual fuel. All these variables come into consideration when the stoichiometry of the combustion process is studied. The experimental conditions and results are tabulated in Tables 3 and 4 of Ref. 1. For purposes of comparison with calculated results, it was necessary to change the units of a number of the variables. UNDERGROUND COMBUSTION STOICHIOMETRY The combustion or oxidation of the carbonaceous residue or "coke" on the sand can be described in terms of the equation: where n is atomic ratio of hydrogen to carbon, m is ratio of moles of CO2 to CO produced, and CH. is taken as the unit molecular weight, realizing that actually the coke has a large range of high molecular weights. Assuming that all the fuel laid down in the sand is burned, the ratio of moles of oxygen consumed to moles of coke can be written as follows. Moles 0MolesMolescoke In terms of moles O2 per pound of coke, where 12 + n is the molecular weight in pounds per mole. If the 0, consumed is measured in standard cubic feet (60°F and 1 atm) and the coke in pounds per cubic foot of formation, 2, then:

By W. P. Sykes

Seven years ago, Dr. S. L. Hoytl presented a masterful discussion of the hard metal carbides and cemented tungsten carbide. His lecture summarized most of the data then available in the field; many of the details relating to the production, properties and structure of cemented tungsten carbide had never been previously published, for, in fact, this information was only then being acquired. During the intervening years, the cemented carbides have assumed a place of real importance in the commercial field, with an ever widening variety of applications due to constant improvement in the control of production technique and the unremitting search for new compositions that might better the performance of the alloys in one or another type of service. The most recent summary of production methods, properties and guides for the successful application of the cemented carbides appears in the 1936 edition of the Metals Handbook. Of necessity, much detailed information relating to structures and physical properties is not included in such a summary, and it is with such details that the present discussion is concerned. Steps in Preparation While the past 25 years have contributed a valuable store of working knowledge in the field of powder metallurgy, many of the process controls are derived entirely from experience and are not as yet finally explained by a specific physical or chemical phenomenon. For most of the cemented carbides such difficulties are aggravated by our lack of knowledge not only of the complex alloy systems involved, but also by the possible changes in structure and even in composition which may accompany variations in temperature, heating time, and furnace atmospheres. The principal steps in the preparation of these cemented carbide alloys are fairly well known, but to supply a foundation for discussion these steps are briefly outlined as follows : 1. Formation of the metal carbide in the form of powder by heating a mixture of carbon and the metal powder or oxide for several

Jan 1, 1938

By C. Atkinson

A method is described for the numerical solution of the diffusion equation with a composition-dependent diffusion coefficient and applied to the radial growth of a cylinder; the radial growth of a sphere, and the symmetric growth of an ellipsoid. Sample applications of the method are made to the growth of particles of proeutectoid ferrite into austenite. RECENTLY&apos; we described a method for numerical solution of the diffusion equation with a composition-dependent diffusion coefficient for the case of the growth of a planar interface. In this paper we extend this method to describe the radial growth of a cylinder, the radial growth of a sphere, and the symmetric growth of an ellipsoid. In the latter case, limiting values of the axial ratios of the ellipsoid reduces the problem to one of a cylinder, a sphere, or a plane depending on the axial ratio. A check on these limiting values is made in the results section. In all of these cases we consider growth from zero size. A natural consequence of this assumption as applied to the sphere, for example, is that the radius of the sphere is proportional to the square root of the time. This is consistent with the condition that the radius is zero initially, i.e., grows from zero size. It may be argued that it is more realistic to consider particles which grow from a nucleus of finite initial size; even in this case the analysis of this paper is likely to be applicable. This can be seen if a comparison is made of the work of Cable and Evans,2 who consider a sphere of initially finite size growing by diffusion in a matrix with a constant diffusion coefficient, with the results of Scriven3 for growth from zero size. This comparison shows that the rates of growth in each case differ trivially by the time the particle has grown to about five times its initial size." This investigation is a generalization of those of Zener,4 Ham,5 and Horvay and cahn6 to the situation often encountered experimentally, in which the diffusion coefficient varies with concentration. First let us consider each of the cases separately. I) GROWTH OF SPHERICAL PARTICLES FROM ZERO SIZE In this case the differential equation in the matrix depends only on R, the radius in spherical coordinates, and can be written: ? 1 <^\ ^13D . , dt U\dRz + R 3Rj + dR dR [ J where C is the composition, t is the time, and D is the diffusion coefficient which depends on c. The boundary conditions will be: c = c, at the moving interface in the matrix, c = c, at infinity in the matrix (and at t = 0, everywhere in the matrix), c = X, is the composition in the spherical particle. Each of the above compositions is assumed constant. In addition there is the flu condition at the moving interface which can be written: , dR0 ~/3c dt \dR/H =Ra where R,, which is a function of t, is the position of the moving interface. We make the substitution q = RI~ in [I] reducing this equation to: & - m - *ws) »i where we have written D = D,F(c) or simply D,F, and Do = D(c,). Thus F[c(q0)] = 1 where q, = ~,/a is the value of the dimensionless parameter q evaluated at the interface. Multiplying Eq. [2] by dq/dc and integrating, we find: where the lower limit of the integral has been chosen so that dc/dq — 0 as c — c,, thereby satisfying the boundary condition at infinity. We require, then, to solve Eq. [3] subject to the condition c = c, when q = q, (this follows from putting R = R, at the interface) together with the flux condition which can be rewritten in terms of q as: Eqs. [3] and [4] together with the condition c = c, at q = q0 enable us to find 77, and the concentration profile c = c(q). Numerical Method. We treat Eq. [3] in the same way as we did the corresponding equation for the planar interface problem&apos; i.e., by dividing the interval c, to c, into n equal steps so that: cr = ca -rbc [5] where r takes the values 0, 1, ... n and we call no,, q1, ... nn the values of n corresponding to the compositions c,, c,, ... c,.

Jan 1, 1970

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By A. B. Cox, L. W. Wark

In the paper on the development of the flotation process at Broken Hill (Australia) prepared by the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy and published in its Proceedings for 1930 (N. S. 80), it is stated that the concentration of ores by flotation has been established on a commercial basis in Australia since 1904 and that differential flotation was practised at Broken Hill in 1912. Since then, progress in flotation practice throughout the world has been rapid, and during recent years the knowledge of the reactions between comparatively modern so-called chemical promoters or collecting agents and the mineral surfaces has been broadened by the published accounts of many investigators, particularly those working in American universities. Because of the benefits the Australian mining industry has derived from the flotation process, it was felt that the industry should take some part in the efforts that are being made to extend the knowledge of the principles on which the flotation process is based. Accordingly, early in 1930, three Broken Hill mining companies—the Broken Hill South, the North Broken Hill, and the Zinc Corporation—together with the Electrolytic Zinc Co. of Australasia, Ltd., and the Mount Lyell Mining & Railway Co., established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation. Subsequently, the Burma Corporation, Ltd., expressed a desire to cooperate. The two authors are directly employed and controlled by these six organizations, and the cost of the investigation is divided equally among them. The research has been carried out under the general direction and in close cooperation with Harry Hey, chief metallurgist for the Electrolytic Zinc Co. of Australasia, Ltd., and the authors desire to place on record their indebtedness to him for his ever willing help and constructive criticism. After an extensive search of the literature, it was decided to determine in a preliminary investigation whether the effect of chemical collectors could be evaluated quantitatively by the "contact-angle" method. This preliminary investigation showed that with the bubble machine of

Jan 1, 1935

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.&apos; This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By Arthur Crowfoot

Page IntRodUction ................... The Round Table in Lake Superior Practice .........420 Early Use of Revolving Round Table in Butte District...... Use oF the Round Table at GREat Falls foR Sand-Slime Feed ., . The Round Table for Fine Slime........,.... Construction of Slime Plant at Great Falls..... &apos;..... 424 Tests on Wood, Linoleum, and Cement Decks.........426 Central Feed Apron Removed ....&apos;......... Re-treatment of Round-Table Tailing........... Determination of Conditions for Round-Table Treatment of Slimcs ... 430 Variation in Slope of Round-Table Deck........ ,... The Steel-Frame Cement-Deck Round Table ........ Tests on Cement and Canvas Dock Surfaces ..: ..... Conoidal Deck Round Tables............. Results with Sand-Slime Feed on Conoidal Deck....... Conclusions from Preliminary Tests on Conoidal and Conical Decks ... 446 Discussion of Results of Four-Day Test on Conical and Conoidal Decks . 452 Discussion of Results of Eight-Day Test.......... Qualitative Sampling of Concentrates Across Conical Deck.... Summary of Slime-Plant Practice............ Suggested Flow Sheet for Slime Classification and Treatment.... Conclusion...................467 Introduction The principal object of this paper is 60 presest, data on the development of the revolving convex round table as a concentrator for the through 0.07-mm. slimes from the ores of the Butte district, although some brief notes on the earliest recorded use of this type of concentrating table in the ore-dressing plants of the Lake Superior region and of the Butte district are also presented. The revolving convex round table belongs to the class of concentrating tables known as film-sizing. tables, these tables using the relative transporting power of a film, or thin sheet of water, as it flows over a quiet inclined surface, to separate the minerals of a sorted product. The grains of heavy mineral move down the slope of the table deck slowly, or, in some cases, not at all, after the initial force of the feed entry VOL. XLIX.—27

Jan 1, 1915

By William Campbell

In the olden days the making of alloys was an art, and the secrete of the craft were jealously guarded. To-day it has become a science, though the old ideas in regard to the secrets and formulæ are dying hard. Modern progress may be attributed to scientific research and testing of materials, and the substitution of chemical analytical control for " cook-book " methods. We know to-day a great deal about the constitution of alloys, the reasons of the change in structure and physical properties by heat and mechanical treatment; and this new knowledge is due for the most part to the physical chemist and metallographist, who have shown us that alloys are simply solutions, and as such obey definite laws. The application of the theories of solutions and of the phase rule tells us what ought to happen when our alloys are in a state of equilibrium. The working-out of the temperature-composition diagram (thermal diagram) for numerous alloys has thrown a light on the structure and constitution which has dispelled most of the darkness in which we labored before the advent of metallography. The work began with the determination of the freezing-point curves, and here the research of Le Chatelier,&apos; Gautier,2 Roberts-Austen,3 and the other pioneers broke the ground. Next the physical chemists, Tammann,4 Rooseboom,5 Bancroft,6 and their colleagues, showed us the complete thermal diagram and its meaning. Then the researches of Heycock and Neville7 on the Cu-Sn series and of Shepherd 8 on the

Jan 1, 1913

By I. R. Kramer, H. Shen, S. E. Podlaseck

The tensile and creep properties of aluminum in vacuum have been investigated. It was found that the general effect of a vacuum environment was to reduce the rate of work hardening. Results obtained from creep tests showed that lowering the test pressure from 2 x 10-4 to 10-7 torr produced a decrease in the activation energy as much as 500 cal per mole. An attempt is made to explain these effects in terms of how the surface-stress field of a specimen may be affected by a vacuum environment during plastic deformation. In a previous paper,&apos; the results were reported of some of our early work on the effect of vacuum environment on the stress-strain curve of aluminum single crystals. This effort has been extended to the studies of the tensile and creep properties in vacuum as a function of various metallurgical parameters. Some of the recent surface-effect studies2&apos;3 have revealed that a region of high dislocation density, the so-called "debris" layer, is formed near the surface of the specimen as a result of plastic deformation. This layer acts as a surface barrier to oppose dislocation movement. The strength of this barrier depends on the surface condition such as oxidation or surface removal. Experimental results obtained from surface-removal work2, 3 indicate that such a surface barrier, which may be characterized by a stress field, affects the applied stress and the rate of work hardening. In the case of aluminum, this stress field was found to be directly proportional to the strain and the strain rate; however, the slope of this curve is independent of orientation of the crystal and may be altered by using different surface treatment. Since the escape of dislocations may be retarded by the presence of an oxide on the surface of a specimen, it is expected that a change in the rate of oxidation in vacuum will affect the process of dislocation accumulation in the debris layer. Consequently, it also affects the plastic behavior of a metal. This paper reports the changes in some of the creep and tensile properties of aluminum in vacuum and discussions of the observed effects in terms of the concept of the "debris" layer. EXPERIMENTAL PROCEDURE Tensile Tests. A sketch of the tensile apparatus is given in Fig. 1. This apparatus was contained in a bell jar (14 in. diam by 24 in. high) connected to a 10-in. vacuum system. The load was applied to the specimen by means of a gear train which was driven by a magnetic clutch located outside the vacuum chamber. The specimen, held by a pair of square shoulder grips, was attached to the load cell at the top and the drive gear at the bottom. A displacement transducer was placed between the two grips as shown in the figure to measure the elongation. Signals of elongation and load were amplified and recorded on an X-Y recorder. The system was capable of detecting loads as small as 0.025 lb and displacements of 0.0002 in. Shoulder-grip specimens of aluminum single crystals, having a nominal square cross section of 1/8 by 1/8 in. and a 3-1/2-in, gage length, were grown by the Bridgeman techniques. The original purity was 99.997 pet. The orientations of the crystals investigated are shown in Fig. 4(a). The crystals were annealed at 600°C for 2-1/2 hr, electropolished, and placed in the vacuum test chamber without any delay. All the crystals were deformed at a strain rate of 4 x 10-5 sec-1 at 24o ± 3°C. A study was made to find whether a chemically passive surface film would give the same effect as a vacuum environment. Specimens of aluminum 1100 (0.187 in. diam with a grain size of 0.1 mm)

Jan 1, 1965