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By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By C. W. Arnold, H. L. Stone, D. L. Luffel

The purpose of this research is to determine (I) the efficiency of small banks of enriched gar driven by methane in displacing oil from a porous medium and (2) the effects of variation in bank size and composition of that efficiency. Most of the experiments were conducted in a sand-packed tube 20-ft long and 1/2-in. in diameter. The hydrocarbon system generally used was methane, butane and decane at 2,500 psia and 160°F. The results of these experiments indicate that, in the regions contacted by the gas, a small bank of an oil-miscible gas driven by methane can displace all of the oil in a piston-like manner. If the enriched gas is of such composition as to remain immiscible with the oil, displacement of oil is less efficient than for the miscible case, and the gas bank travels through the sand with a velocity less than that of the driving gas. These data along with theories discussed imply that smaller banks and less total gas are required when the enriched gas and oil are miscible. INTRODUCTION Widespread application of enriched-gas drive to the recovery of oil rests upon a key factor — the use of limited quantities, or "banks", of enriched gas. At the present time, the value of liquefied petroleum gas or other enriching agents discourages their use in a continuous injection technique, or even in a large bank, except in a few isolated reservoirs. If small banks of enriched gas driven by methane were as effective in displacing oil as is continuous injection, the enriched-gas drive process might be applied to a larger number of reservoirs. Previous research on the mechanics of the enriched-gas drive process reported by Stone and Crurnpl and by Kehn, Pyndus and Gaskell has utilized continuous injection of enriched gas. This work has shown that two types of displacements occur. With gases containing sufficient intermediates. the oil is displaced misciblv and complete recovery is obtained from the regions swept. When gases are used which contain insufficient intermediate hydrocarbon for miscible displacement, oil is displaced immiscibly. In the latter type, selective solution of the intermediate hydrocarbons causes a swelling and reduction in viscosity of the oil and leads to an increased recovery over that obtained by dry-gas (methane) drive. The size of the enriched-gas bank necessary for efficient displacement of oil is determined by those factors which cause deterioration of the bank. A differentiation may be made between those factors which operate on a microscopic scale and those which act on a macroscopic scale. On the smaller scale, the enriched gas mixes in the direction of flow by diffusion and convection with the fluids immediately preceding and following it. On the larger scale, the gas may by-pass the oil by flowing through permeable streaks, by overriding the oil because of density difference, or by fingering because of unfavorable viscosity ratios. In such cases, the enriching material tends to mix with the oil both laterally and in the direction of flow. The increase in effective area available for diffusion and dispersion of the enriching components leads to a faster degradation of the bank and a need for a larger bank than is necessary for those cases in which no by-passing occurs. The effects of such macroscopic factors in the deterioration of enriched-gas banks have been reported in a separate paper by Blackwell, Terry and Rayne. The present study was confined to the factors which operate on the smaller scale, in particular to the behavior of banks of enriched gas in sands uniformly swept by the gas. Experiments were designed to answer the following questions. 1. Can small banks of enriched gas driven by methane be used to secure oil recoveries comparable to those obtained by continuous injection of enriched gas? 2. What is the optimum bank size (the minimum bank size necessary to obtain a recovery comparable to that obtained by continuous injection of the same enriched gas)? 3. How many total pore volumes of gas must be injected to obtain the maximum recovery when the optimum bank size is used? 4. What is the effect of varying the number of enriching components in a gas bank? This report describes the experimental investigations and discusses the results in terms of their significance to reservoir behavior.

By P. G. Nahin, A. Grenall, R. S. Crog, W. C. Merrill

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By W. C. Merrill, P. G. Nahin, A. Grenall, R. S. Crog

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By C. K. Leith

THE purpose of these conferences has been to find some basic principles to guide us in the chaos which confronts us, to arrive at elements of a national policy. None such exists, nor, as a matter of fact, have there been any concerted efforts by the public or the mineral industry to evolve one. In the absence of such a policy the administrative agencies of the government can hardly be expected to be consistent or really effective in their handling of mineral problems, domestic or foreign. Basic Facts MINERAL reserves are unequally distributed among the nations. The principal world supplies are grouped around the north Atlantic, and nearly three-fourths of the world's total is controlled politically and commercially by English-speaking people. No one nation has a complete supply of the minerals necessary for modern industry; specialization, reciprocity, and large-scale movements between the nations are inherent in nature's unequal distribution of them. The principal sources of supply are relatively few compared with the nations to be served-a fact which determines broadly certain natural outlines of the world flow. National isolation with regard to minerals can be accomplished only through backward steps in industry and lower standards of living even in the nations possessing the most of the mineral supplies. A certain measure of unified commercial control, international in scope, is a natural consequence of the limited number of the large sources of supply. Mineral supplies for the world as a whole are so large that there is little need for concern about early exhaustion, but every nation has important problems of early exhaustion of particular minerals, which must affect their policies.

Jan 1, 1933

There are no data available of shipments until 1858, and then estimated, when railroad service became available. By reason of the iron made in the county, and the large amounts of salt, the tonnage used locally was quite large, and until 1860 these are estimated from the probable salt and iron production. After 1859 the tonnages shipped by rail are partly estimated from the total shipments of the Allegheny Valley Railroad from four counties. It is believed that the totals are below, rather than above, what the actual production was. While considerably larger for the same years than figures given by the Secretary of Internal Affairs and census reports, these data were always too low in those days, partly because of lack of facilities for gathering them, but more largely because of the strong prejudice existing in those days against furnishing such data to any governmental agencies.

Jan 1, 1942

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By N. H. Mannakee

SINCE the publication of the paper of Mr. Scholz, The Effect of Humidity on Mine-Explosions,' I have undertaken a study of the meager available data of barometric and temperature conditions it times of mine-explosions, and have arranged these data in a manner which may be of interest to other students of mine-explosions. This study covers the period from 1898 to 1909, during which an ever-increasing percentage of collieries has been ventilated by fans giving air-currents of high efficiency. Previous to 1898 this percentage was smaller than at any time since. The vari¬ous States have become, from time to time, more exacting in their demands upon poorly-ventilated mines. This general im¬provement in ventilation throughout the Appalachian field has undoubtedly brought about a condition which is annually the cause; .or a very important attendant, of the high percentage of fatalities in mine-explosions, through the daily passage of from hundreds to thousands of gallons of water, invisibly suspended in the air, carried out of the mines by the ventilating-currents during the existence of certain temperature- and humidity-conditions. There is a wide-spread opinion that these conditions exist from November 1 to March 31; but it is more likely that they have a much wider range, which varies from year to year. Certain years show an increase or decrease of rain-fall from the mean ; the daily temperature may fall far below or rise far above the mean established by a record of a period of years; and the daily humidity varies likewise. If mine-explosions are influenced by a lack of moisture in the mines, certainly it may be expected that the influence will be felt at times when the

Nov 1, 1909

By R. W. Nash, A. E. Schwaneke, V. R. Miller

The Bureau of Mines developed a detector for controlling sorting devices to separate the copper-bearing fragments from the barren portion of Michigan native copper and western prophyry copper ores. A successful sorter could be used to preconcentrate the ore and eliminate costly hoisting or hauling of waste. An induction balance unit was developed and used in sorting tests on crushed sized - 2.5 + 1. 3-cm (- 1 + 1/2- in.) ores from the Kingston (0.9% Cu) and Centennial (1.6% Cu) mines of Upper Michigan. Concentrates of 4.0% and 7.5% Cu, respectively, were obtained at recoveries of 85 and 80% of

Jan 8, 1978

By Franklin H. Sharp

The operation of the Magmont Concentrator located on the New Lead Belt of Southeast Missouri is described. Ore characteristics affecting lead-copper-zinc separation are enumerated, and the cur- rent methods of separation are detailed.

Jan 1, 1976

By Chikao Nishiwaki

INTRODUCTION The Japanese dependency for mineral raw materials from foreign sources increased rapidly within the 20 years since the Korean war. During this 20 year period Japan has attempted to industrialize and develop her economy while depending mostly on heavy import of nearly all kinds of mineral raw materials. She has fabricated them using energy generated mostly by mineral fuel that are also imported. Fabricated goods are either used domestically to accelerate more fabrication industry or exported after adding more refinement or fabrication. In this paper iron ore as a major raw material for the Iron and Steel industry, three major base metals, copper, zinc and lead, and petroleum as a major energy source have been selected as examples to represent the general features of various kinds of mineral raw materials that are imported. Among other important mineral commodities for which Japan dependa upon foreign sources are: Aluminium, nickel and cobalt, potash and phosphorous 100 percent dependent and tin, tungusten, chromium and molybdenum over 95 percent dependent. IRON ORE Statistics for the important iron and steel raw materials, namely iron ore, coal and scrap iron are shown in Tables 1, 2 and Fig. 1. Iron ore is by far the most important and basic among these three commodities. There has been practically no steel or iron imported as a metal into Japan during this period. Iron ore, including aggregate such as pellets, and metallurgical coal are mostly transported in large ore cargo boats to the port where very efficient port facilities unload them directly at the steel mill site. As a result

Jan 1, 1976

By Jean-Jacques Prompsy, J. S. Rinehart

Some time ago a study was initiated at the Colorado School of Mines in an effort to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. The study has been divided into three phases involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, a range commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a region in which the dynamic effects are greatly exaggerated and made more identifiable. The ultimate objective is to provide basic data which will enable the mitigation through judicious design of the frequency and severity of these transient concentrations of intense stress, thereby prolonging and increasing drill efficiency. This paper presents results of the third phase of this study — the development of a better understanding of the dynamics and mechanics of failures caused by transient stress-wave interactions. The impulsive loading or transient waves in these experiments were generated by detonating small explosive charges placed on the ends of Plexiglas cylindrical rods terminating in truncated cones. Under such intense loading, dynamic effects are greatly exaggerated and, hence, made more identifiable. The explosion generates a high-intensity transient stress disturbance which moves through the rod, reflects from surfaces which lie in its path, and establishes momentarily narrow regions of high concentrations of stress where failure of fracture may occur. The peregrinations of these waves, their interactions and their effects have already been described in the literature (see, for example, Refs. 1 and 2). The locations and extent of the regions quite apparently are strongly dependent on specimen shape, making it possible through judicious shaping of specimens to relocate the highly stressed regions, minimize their extent, or eliminate them entirely. These experiments were designed, first, to identify more clearly the vulnerable regions in geometries relevant to drill-bit design and, then, to modify these regions in a predictable way by changing specimen shape. Through this latter process, it is anticipated that better bit design might evolve. The specimens used in the experiments were cylindrical rods, 1 1/2 and 1 1/8 in. in diameter, ended by a truncated cone, with the cone angles ranging from 45° to 130°. Upper cone face diameters were 1/2, 3/4, or 1 in. A small plastic-covered electric blasting cap detonated on the axis of the specimen produced the spherical shock wave. The detonators used were Olin Mathieson No. 6, which induced into the rod a transient saw-toothed stress disturbance of about 3-microseconds duration, corresponding to a wave length of 0.3 in. in the Plexiglas. Five distinct systems of fracture were observed: (1) along the axis of the rod, a lower system of fractures, the cracks focusing around one point for specimens having cone angles of 80° and 90° and, as the cone angle was increased, spreading downward; (2) just above these fractures, an upper system of fractures composed of horizontal cracks observable in some specimens but not of any appreciable extent; (3) a third system of axial cracks still above the latter, observable in the small cone-angle specimens; (4) in the upper part of the specimen, a system of radial fractures extending from the blasting point; and (5) circular spalling due to reflection of the wave on the boundary of the cylinder. Only the first three systems, the axial fractures, are examined here. LOWER TENSILE FRACTURE SYSTEM The first, lower system of tensile fractures, shown in the photograph of Fig. 1, was observed in almost all of the specimens. It was due to the reflected tensile wave coming in from the boundary of the cylinder as shown in Fig. 2. The reflected wave was cylindrically convergent and focused

By Benjamin Webber

MANY of the auriferous placers of the arid Southwest differ widely from the standard types of stream and eluvial deposits of more humid regions, although exhibiting some of the features of each. This diver-gence in characteristics is of geological and economic importance and appears sufficient to warrant the consideration of these placers as a class distinct from both stream and eluvial deposits. It is hoped that the consideration of these auriferous gravels as a distinct type of deposit will facilitate recognition of morphological and economic features that might remain obscure if these deposits were viewed in the light of stream or eluvial placers whose type locality is a more humid environment. "Bajada placer" is proposed as the designation for this type of placer deposit. Bajada is the Spanish term for slope and is used locally in the Southwest to indicate the lower slope of a mountain range, the portion consisting of rock debris and standing at a much lower angle than the rock slope of the range proper. It has been used in a geologic sense by Schrader1 and others. The type locality of bajada placers is the Sonoran Desert,2 where they occur on the bajada or rock debris slope of desert ranges. Stream placers are represented in the Southwest, but most of them lie within the mountain topographic province, the Mexican Highlands2 section of, the Basin and Range physiographic province. Eluvial placers may occur in the mountainous semiarid Mexican Highlands but are almost unknown in the extremely arid Sonoran Desert, as mountain slopes are generally too steep to permit the accumulation of any considerable mantle of residual debris. Since their salient distinctions are almost wholly the result of formation under conditions of extreme aridity, bajada placers are largely confined to the Sonoran Desert, although a few occur in the adjacent Mexican High-lands. They may be modified by the action of ephemeral streams, in which case the placer gravels of these arroyas approach stream placers in type and habit of occurrence, but their relation to an arid environment and the bajada type is usually apparent.

Jan 1, 1935

By Gilbert E. Doan

IN a technical civilization, that is. one whose major difference from past civilizations is its enormous development of technology, in transportation, communication, labor saving, centralized control, and mass production, it is natural that the most critical problems should be those that arise out of technologic advances; it is natural also that a. man who understands these advances should be chosen as the leader to meet these problems. This was done in the selection of Herbert Hoover as President of the United States. Mr. Hoover was a good, and perhaps a great President. But he was not a great politician and that ensured his defeat when a crisis came.

Jan 1, 1939

By Stanley Rajnak, John E. Dorn

The saddle-point activation energy for the nu-cleation of a pair of kinks is estimated as a function of the applied stress, the lattice constants, and the height and shape of the Peierls' hill by employing the line-energy model of a dislocation. The kinetics of disloration motion by the Peierls' mechanism are discussed and the microscopic dislocation velocities and macroscopic strain rates are formulated by the Arrkenius type of approach in terms of the activation energy for the formation of pairs of PEIERLS was the first to illustrate that a straight-dislocation line has its lowest energy when it lies in a potential valley parallel to lines of closest packing kinks. The log of the dislocation velocity is found to be approximately proportional to the log of the local applied stress. It is also shown that the low-temperature mechmical properties of several bcc metals might be explained in terms of the Peierls mechanism, good agreement being obtained between theory and experiment for the flow stress us ternperature, activation energy vs stress, and activation volume us stress curves for these metals. of atoms on the slip plane. When such a straight dislocation is moved rigidly from one valley toward the next, the atoms in the vicinity of the core of the dislocation change their positions and bond angles, causing the energy of the dislocation to increase. Midway between two adjacent valleys, the disloca-tion energy reaches a maximum value and any additional small displacement will cause the dislocation to fall down the hill into the next valley. The maximum shear stress necessary to promote such

Jan 1, 1964

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919

By Henry Mackay

THE interesting paper recently submitted by Messrs. Tobelmann and Potter' shows that chemical problems have developed which are of great interest in this new and important branch of metallurgy. Those who realize what a process of this kind really involves will agree that it deserves a better name than "leaching process." The word leaching conveys the idea that the copper is simply leached out of the ore with acid and then precipitated on iron; the chemistry of such a process would be of little interest. As, however, during the first year's operation of this plant 24,400,532 lb. (11,067,837 kg.) or about two-thirds of the produce, was electrolytic copper, while 7,992,033 lb., or about one-third, was cement copper, it would seem more appropriate to term the process electrochemical. It further appears, from the particulars given, that efforts have been made to have the entire production in the form of electrolytic copper. -This could be done if the chemistry of the problem were kept in balance, so that it would not be necessary to discard any solutions that carried copper and acid of commercial value. A process, such as that under consideration, in which the copper is precipitated from solution by electrolysis, the solvent being at the same time regenerated, is one that requires special chemical and electrochemical knowledge and experience if all the -copper in solution that has been extracted from the ore is to be successfully and economically produced as electrolytic copper. The object of this paper is to discuss, from the practical and theoretical standpoints, the chemical and electrochemical problems involved in the working of a process of this kind, and' which must be solved to keep it in chemical and electrochemical equilibrium. In such a process, if the chemical balance is maintained, a solution can be used alternately as a

Jan 9, 1919

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