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By Alphonse C. Van Besien, Arcy A., L. T. Larson, D&apos Shock, J. W. Peters, Ted H. Eyde, Dermot Ross-Brown, David L. Campbell, W. W. Dudley, John P. Bunch

Over the last several years, unfavorable economic and political pressures on open-pit mining have placed the industry in a generally defensive position. As a consequence, there have been changes in the traditional organizational and production methods to increase operating efficiency. For example, staff groups that were once used almost exclusively for production support are now being organized as mining/environmental specialists. These specialized groups are responsible for obtaining mining permits and insuring compliance with existing permit requirements. Permit issurance and renewal continues to grow as a major budget item in open-pit operations.

Jan 2, 1977

By Thomas Fraser, H. F. Yancey

BefoRe a new coal-washing plant is installed, or an existing washery is remodelled and improved, considerable experimental work on the coal to be washed should be done. A thorough examination of a coal, to determine whether it can be washed successfully and the best and most economical process for securing a satisfactory grade of washed coal, calls for mine sampling, analytical work, and experimental coal-washing tests which may require several months' time and the expenditure of considerable money. Having collected the required data on the characteristics of the coal and the results secured with different types of machines under different sets of conditions, it is necessary to decide what method of treatment should be used. The interpretation of the experimental data is no small part of the problem. The first step in the investigative work is to determine from the characteristics of the coal and the manner of occurrence of the impurities whether it is possible to separate the dirt from the coal and produce a washed coal of the required quality. Then it is necessary to select the type of washer or the system of treatment that will produce the greatest amount of washed coal of this grade for the least cost. To secure this information, tests may be made at laboratories operated by consulting or contracting engineers, at the testing plants of machinery manufacturers, at commercial washeries, or in an experimental washery erected on the site of the proposed plant. Such tests will produce figures in which every factor, including analyses of raw coal and washed coal and yield of washed coal, may vary widely. To reduce these results to a common basis for comparison is very difficult. A number of plans

Jan 1, 1923

By Thomas Fraser, H. F. Yancey

BefoRe a new coal-washing plant is installed, or an existing washery is remodelled and improved, considerable experimental work on the coal to be washed should be done. A thorough examination of a coal, to determine whether it can be washed successfully and the best and most economical process for securing a satisfactory grade of washed coal, calls for mine sampling, analytical work, and experimental coal-washing tests which may require several months' time and the expenditure of considerable money. Having collected the required data on the characteristics of the coal and the results secured with different types of machines under different sets of conditions, it is necessary to decide what method of treatment should be used. The interpretation of the experimental data is no small part of the problem. The first step in the investigative work is to determine from the characteristics of the coal and the manner of occurrence of the impurities whether it is possible to separate the dirt from the coal and produce a washed coal of the required quality. Then it is necessary to select the type of washer or the system of treatment that will produce the greatest amount of washed coal of this grade for the least cost. To secure this information, tests may be made at laboratories operated by consulting or contracting engineers, at the testing plants of machinery manufacturers, at commercial washeries, or in an experimental washery erected on the site of the proposed plant. Such tests will produce figures in which every factor, including analyses of raw coal and washed coal and yield of washed coal, may vary widely. To reduce these results to a common basis for comparison is very difficult. A number of plans

Jan 1, 1923

By J. H. Nead, J. W. Halley

The new low-alloy high-strength steels are obviously here to stay. With 75 per cent higher yield strength and 50 per cent higher tensile strength than plain carbon structural steel, they permit 20 to 40 per cent weight savings and 10 per cent or more increase in pay load in the construction of railroad cars, buses, trucks, and a great variety of material-handling equipment. Their cost is low enough so that the extra cost of the new lighter construction over that with carbon steel offers an attractive self-liquidating investment; in some instances new construction with these low-alloy steels may even be as cheap as with plain carbon steel. A considerable and rapidly growing demand for the low-alloy steels has already sprung up. The many steel compositions that have appeared on the market lately18, 27, 28, 29, 30 to meet this demand would seem to indicate that no single composition is uniquely fitted for the purpose. However, no doubt some compositions are more suitable than others. The purpose of this study was, therefore, to compare the effects of the various alloying elements that might be used in the low-alloy steels in order to choose the metallurgically most logical composition, paying due regard, of course, to the economic aspects involved. Properties Desired in Low-alloy Steel A distinction between the new low-alloy steels and the common alloy steels is that the latter are generally used in the heat-treated (that is, quenched and tempered) conditions, whereas the new low-alloy steels are not only not heat-treated but are not susceptible to heat-treatment in the ordinary sense of the term. In this lies one of their chief advantages. Their properties can be obtained in the as-rolled, air-cooled, or annealed condition, just as with mild plain carbon structural steel. There is no need for heat-treating. Such steels can be readily formed hot or cold, and their properties are not appreciably changed by hot

Jan 1, 1936

By J. H. Nead, J. W. Halley

The new low-alloy high-strength steels are obviously here to stay. With 75 per cent higher yield strength and 50 per cent higher tensile strength than plain carbon structural steel, they permit 20 to 40 per cent weight savings and 10 per cent or more increase in pay load in the construction of railroad cars, buses, trucks, and a great variety of material-handling equipment. Their cost is low enough so that the extra cost of the new lighter construction over that with carbon steel offers an attractive self-liquidating investment; in some instances new construction with these low-alloy steels may even be as cheap as with plain carbon steel. A considerable and rapidly growing demand for the low-alloy steels has already sprung up. The many steel compositions that have appeared on the market lately18, 27, 28, 29, 30 to meet this demand would seem to indicate that no single composition is uniquely fitted for the purpose. However, no doubt some compositions are more suitable than others. The purpose of this study was, therefore, to compare the effects of the various alloying elements that might be used in the low-alloy steels in order to choose the metallurgically most logical composition, paying due regard, of course, to the economic aspects involved. Properties Desired in Low-alloy Steel A distinction between the new low-alloy steels and the common alloy steels is that the latter are generally used in the heat-treated (that is, quenched and tempered) conditions, whereas the new low-alloy steels are not only not heat-treated but are not susceptible to heat-treatment in the ordinary sense of the term. In this lies one of their chief advantages. Their properties can be obtained in the as-rolled, air-cooled, or annealed condition, just as with mild plain carbon structural steel. There is no need for heat-treating. Such steels can be readily formed hot or cold, and their properties are not appreciably changed by hot

Jan 1, 1936

By N. Jaffe, J. E. Dorn

This investigation is concerned with the possibility that the creep resistance of metals might be reduced as a result of recovery at the creep temperature when the applied stress is reduced. For this purpose the effect of stress on the recovery of the creep behavior of pure polycrys talline aluminum was investigated in the cross-slip temperature range where the activation energy for creep is 28.000 cal per mole. Before recovery all specimens were given the same substructure by creeping them under a stress of 7800psi to a strain of 0.218. Recovery was then accomplished by holding the specimens at the creep temperatures of 327" and 337°K under a series of reduced stresses for various periods of time. When the original stress was reapplied the specimens crept more rapidly than when the original stress was first removed, illustrating that recovery did take place. The extent of recovery could be indexed in terms of the UNDER certain conditions of test, the creep rate decreases over the primary stage of creep often by as much as a factor of 10~B. Since the external variables of stress and temperature are held constant, such pronounced and significant changes in the creep rate must be attributed to various substructural modifications that are introduced as a result of creep itself. At the secondary stage of creep, over which the creep rate remains constant and the substructure no longer changes, a balance must be achieved between the rate of increase in creep resistance due to creep straining and the rate of recovery of the substructural modifications. The general validity of these concepts on substructural changes has already been shown,' including the corollary that a more creep-resistant substructure is introduced under a more rapid creep rate arising from a higher applied stress.' In spite of these well-documented facts, very little progress has been additional strain undertaken by the recovered specimen to achieve the same strain rate as the unrecovered specimen. It is significant that the higher recovery stresses gave the most rapid rates of recovery. Over the high range of reduced stresses, where some creq took place during recovery, the activation energy for recovery equaled that for creep, namely 28,000 cal per mole. But for stresses during recovery below 0.80 of the original creep stress, no creep was detected during recovery and an activation energy for recovery of about 72,000 cal per mole was obtained. Whereas the activation energy of 28,000 cal per mole suggests that cross-slip of dislocations is responsible for this recovery, the mechanism for the 72,000 cal per mole process is not known. This activation energy, however, is about twice that for self-difhsion. made in determining, in satisfactory detail, precisely what substructural changes so effectively modify the creep rate.' Up to the present, electron microscopy has failed to uncover, in a satisfactory quantitative manner, the mechanistic processes involved. Since, however, creep, at least at moderate and high temperatures, arises from one or more types of dynamic recovery processes, it should be possible to shed additional light on the total problem by investigating the recovery of creep resistance. The importance of such an investigation becomes apparent when the fact is recognized that there has yet been no direct experimental proof that the rate of softening due to substructural changes as a result of recovery equals the rate of hardening due to creep-induced substructural strengthening over the secondary stages of creep. Furthermore the problem of what happens to the creep-strain induced strengthening when the material recovers either at zero or some reduced operating stress has significant engineering consequences. It was for these reasons that the present investigation on the recovery of creep behavior was initiated. Inasmuch as a substantial background has now developed on the creep of high-purity aluminum, this material was again selected for the current investigation. Furthermore extensive evidence is now

Jan 1, 1963

By R. C. Gould, A. M. Skov, L. F. Elkins

Comparison of long term decline in oil production during cyclic waterflooding or pressure pulsing of part of the Driver Unit with steady injection-imbibition flooding in the Tex Harvey area led to large expansion of flood in the Driver Unit on the steady injection basis. While the flood has been successful, the major problem has been attainment of satisfactory oil production rates in most of the wells. Large volume fracture treatments of low capacity wells were unsuccessful in achieving sustained increases in production. A two-section area in the Driver Unit has already recovered 620 bbl of oil per acre by waterflood but other areas have not performed so well. Sun Andres water containing 300 to 500 ppm H,S is sweetened to 0.5 to 1 ppm H,S by extraction with oxygen-free flue gas. This prevents contamination of gas produced in the area and apparently it has reduced corrosion in minimum investment, thin-wall, cement-lined water dktribution systems. Cement-lined tubing in injection wells has mitigated corrosion as effectively as thick polyvinyl chloride films have, and at less cost. Introduction As reported in the literature the Spraberry field of West Texas has presented unusual problems for both primary production and waterflood ing. Earlier information from the Spraberry Driver Unit included conception and evaluation of cyclic waterflooding or pressure pulsing in a nine-section pilot test as an aid to extraction of oil from the tight matrix rock and as a boost to normal capillary imbibition forces An additional 5 years' operation in that area, and performance of expanded steady injection water-flood, now covering a total of 68 sq miles, are reported herein. In addition, since the Driver Unit is one of the largest waterfloods in areal extent in the U. S., many operating experiences are presented for the benefit of engineers concerned with operation of other Spraberry floods or with other waterfloods where this reservoir technology and/or water handling technology may be adaptable in part. These include: (1) attempts to improve producing well capacity through large volume fracture treatments, (2) long-term performance of water treating plants utilizing oxygen-free flue gas to extract H,S from sour San Andres water, (3) performance of thin-wall cement-lined pipe in water distribution systems including comparison between those sections carrying raw San Andres water and those carrying treated water, and (4) comparison of performance of various lining materials and subsurface equipment in water supply and water injection wells. These experiences are reported without regard to whether results are good, bad or indifferent. Since the operations reported are limited to the techniques, materials, and equipment actually used in the Driver Unit, no comparison is possible with results of other approaches used in other Spraberry floods or in waterfloods generally under different conditions. However, an attempt is made to quantify these experiences as much as possible in the space available to permit other engineers to select those parts applicable to eheir problems. Background The Spraberry, discovered in Feb., 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members—a 10- to 15-ft sand near the top and a 10- to 15-ft sand near the base, having permeabilities of 1 md or less and porosities of 8 to 15 percent. Extensive interconnected vertical fractures permitted recovery of oil on 160-acre spacing from this fractional-millidarcy sandstone, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 percent of oil in place, with most wells declining to oil production of a few barrels per day when reservoir pressures are still in the range of 400 to 1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low production rates at these relatively high reservoir pressures. In 1952 Brownscombe and Dyes proposed that displacement of oil by capillary imbibition of water from the fractures into the matrix rock might significantly increase oil recovery from the Spraberry, overcoming otherwise serious channelling of water through the fractures." A pilot test conducted by the Atlantic Refining Co. during 1952 through 1955 indicated technical feasibility of the process; but low oil production rates averaging I5 to 20 bbl/well/D failed to create significant interest in large-scale waterflooding at that time." Humble Oil & Refining Co. conducted a highly successful 80-acre pilot test during 1955 through 1958 with

Jan 1, 1969

Discussion of the papers of Benjamin Talbot. E. A. Beck, Emil Gathmann, Sir Robert A. Hadfield, and P. H. Dudley, presented at the New York Meeting, February, 1913, and printed in this Bulletin (No. 76, April, 1913). CHAIRMAN JAMES F. KEMP :-I call upon Prof. Albert Sauveur to open the general discussion on the subject of sound steel ingots. ALBERT SAUVEUR, Cambridge, Mass. :-I believe that I have the privilege, this instant, of opening one of the most important, significant and far-reaching discussions ever held before this Institute. I believe that our talk this morning will be heard far and wide, not only on this side of the water, but also on the other side. Everywhere, in short, where steel is manufactured. I welcome the opportunity of expressing my mind in regard to the production of sound steel ingots, a subject about which I entertain some very decided opinions. I shall not attempt to discuss the relative merits of the various processes that have been described. I shall, on the contrary, confine myself to a general consideration of the important questions before us. So intensely do I feel regarding the production of sound steel ingots that I have put my remarks on paper in my desire to present my Views.

Jan 4, 1913

By Theo B. Comstock

Since 1892 the writer has published several articles in the Engineering and Mining Journal concerning the relations of the

Jan 1, 1901

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,' a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By M. G. Corson

Until recently, the characteristics of cast copper have seldom been studied and such study as has been made has been inadequate. The prevailing idea seems to be that since pure copper is infrequently used in the cast stlate, there is no reason for trying to establish precise data regarding the properties of the metal in that condition. On the other hand, wrought copper either in the shape of sheets or wire rarely fails in service, except as a result of the action of reducing gases at the annealing temperatures, so there is little incentive to study the properties of the cast shapes —cakes, bars, ingots and billets—for the sake of tracing the causes of failures of the wrought metal to the cast stock. However, about a decade ago, wirebars of American origin often cracked badly while being hot-rolled in mills in Germany. This Icd to four investigations: by E. Seidl and E. Schieboldll by P. Siebe12 by 0. Bauer and G. Sachs,3 and by G. Welter.4 These authors came to the conclusion that failures in hot-rolling were due essentially to the presence of a wide zone of columnar crystals between t'he thin layer of fine crystal5 near the surfaces of the bars and the large but more nearly equiaxed grains of the central core. This macrostructural defect was explained in turn by the probable upward deviation in the temperature of the metal while it was being poured into the molds of the castling machine. More recently, cast shapes of copper were investigated by X. 1'. Allenh and by C. Blazey. Allen examined vertically cast wirebars and hori-zontally cast wedge cakes of electrolytic tough-pitch copper, but only for the distribution of densities; i.e., porosity. Blazey was interested mainly in the mechanism of the variations in electrical conductivity due to cold-work and anneal, but gave introductively an account of the composi-tion and average densities of the tough-pitch horizontally cast Wirebars used. As far as the present writer can tell, no investigation mas under-taken for the sake of presenting a picture of the distribution of mechanical characteristics in the wirebars of copper, or otherwise.

Jan 1, 1938

By M. G. Corson

Until recently, the characteristics of cast copper have seldom been studied and such study as has been made has been inadequate. The prevailing idea seems to be that since pure copper is infrequently used in the cast stlate, there is no reason for trying to establish precise data regarding the properties of the metal in that condition. On the other hand, wrought copper either in the shape of sheets or wire rarely fails in service, except as a result of the action of reducing gases at the annealing temperatures, so there is little incentive to study the properties of the cast shapes —cakes, bars, ingots and billets—for the sake of tracing the causes of failures of the wrought metal to the cast stock. However, about a decade ago, wirebars of American origin often cracked badly while being hot-rolled in mills in Germany. This Icd to four investigations: by E. Seidl and E. Schieboldll by P. Siebe12 by 0. Bauer and G. Sachs,3 and by G. Welter.4 These authors came to the conclusion that failures in hot-rolling were due essentially to the presence of a wide zone of columnar crystals between t'he thin layer of fine crystal5 near the surfaces of the bars and the large but more nearly equiaxed grains of the central core. This macrostructural defect was explained in turn by the probable upward deviation in the temperature of the metal while it was being poured into the molds of the castling machine. More recently, cast shapes of copper were investigated by X. 1'. Allenh and by C. Blazey. Allen examined vertically cast wirebars and hori-zontally cast wedge cakes of electrolytic tough-pitch copper, but only for the distribution of densities; i.e., porosity. Blazey was interested mainly in the mechanism of the variations in electrical conductivity due to cold-work and anneal, but gave introductively an account of the composi-tion and average densities of the tough-pitch horizontally cast Wirebars used. As far as the present writer can tell, no investigation mas under-taken for the sake of presenting a picture of the distribution of mechanical characteristics in the wirebars of copper, or otherwise.

Jan 1, 1938

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

INTRODUCTION IN a series of papers, the authors and their associates have shown the influence of four important factors on the technical cohesion limit.3-16 By "technical cohesion limit" is meant the technically determinable resistance to fracture. The four important factors are the stress system, plastic deformation, temperature, and the strain rate. The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. The previously-mentioned series of papers contains ample evidence that plastic extension increases the fracture stress of any polycrystalline metal. In a recent paper of the series,15 moreover, it has been shown that the effect of plastic deformation on the fracture stress cannot be attributed to reorientation of internal flaws but is a work-strengthening effect, similar to the effect on the flow stress.[$] Plastic deformation of steels, however, may not only cause work hardening, but may result in additional hardness because of strain aging. Some evidence that strain aging affects not only the flow stress but also the fracture stress, has been presented in a recent paper.14 In that paper, a study is made of the influence of plastic deformation at room temperature on the fracture stress of ferritic steels at -188°C. The study is based on the results of two-stage tests. In the first stage each specimen was extended a predetermined amount at room temperature; in the second stage the specimen was tested to fracture in liquid air. In most of these tests the specimen remained in the testing machine during the interval of about one hour between the first and second stages, it was kept under a tensile load of about 500 lb and maintained at liquid air temperature. The effects of various amounts of plastic deformation on the fracture stress were thus determined and curves were obtained to represent the influence of plastic deformation at room temperature on the stress at brittle fracture in liquid air.14 Two specimens of ingot iron, however, were removed from the testing machine at the end of the first stage and several days elapsed before the specimens were tested to fracture in liquid air. As shown in Fig 8 of that paper," the points representing fracture of these specimens are far above the curve representing the results of two-stage tests without a rest interval between the stages. The evidence thus indicated that the fracture stresses of these two specimens were increased not only by the work-strengthening, but also by strain aging. The present paper presents results of further investigation of the influence of strain aging on the fracture stress. There are two kinds of aging of steel.

Jan 1, 1948

By Roy Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced1, at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces1. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe-rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1936

By E. H. Jr. Dix

OF all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations had been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 5.25° C. to about 1 per cent. at 300° C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540° C., and that this amount decreases to about 3 per cent. at 20° C.

Jan 2, 1926

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

GOD the Almighty has all things well ordered; in G particular, the effects and attributes of the seven planets whose reign and course (by the grace of God) determine for the most part not only our own life and death but also the growth and decay of vegetable and mineral life, so that the aforesaid planets generate and develop in a wondrous way the ores of gold and other metals in minerals, rocks, and earths. Specifically, the Sun develops the ores of gold, the Moon the ores of silver, Venus the ores of copper, Saturn the ores of lead, Jupiter the ores of tin and bismuth, Mars the ores of steel and iron, and so on. Since, however, no ore is made alone but each is made and wrought so that it is associated with other ores, it is necessary to know the art of separating the thus-made ores after they have become metals; as for instance, silver from lead and copper; gold from silver, and so on. [2]* If this is to be done usefully, you must be able to assay and must understand everything that is needed in connection therewith. It is obviously true and clear as light of day that some kinds of copper contain silver and some kinds of silver contain gold. In order that you may be able to separate them, so that each is obtained by itself and can be worked with profit and re ward you need first of all a true assay for the values of such metal. The assay, by revealing how great they are, whether the pure has been obtained separate from the worthless matter, and what the admixture is, advises you whether it would be worth the expense and the effort to start mining operations. Assaying also indicates how much silver there is in a centner of ore or how much copper and lead there are in

Jan 1, 1949

DISCUSSION, G. Derge and D. J. Girardi presiding N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—While the authors present very interesting results on the effect of sulphur upon the solubility of oxygen, they have not established convincingly the lines of two-fold saturation (the valleys in Fig. 2) and the ternary eutectic point. Their contention that sample S-7, upon melting at

Jan 1, 1954

Jan 1, 1923