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By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By Donald W. Scott, L. A. Roe, B. J. Sweo

INTRODUCTION THIS paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizers and organic dyes, and 35 parts of water are added to loo parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder' in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the overspray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1947

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By Donald L. Katz, Marshall B. Standing

Density data are reported on 16 saturated hydrocarbon vapors at Pressures ranging from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. Introduction The densities of natural gases are necessary in many engineering in in petroleum production and utilization, Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 Ib. per sq. in.4 Recent discoveries of pools having Pressures UP to 7500 lb. Per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data On gas density at high pressures. Methods of Computation The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The meth-me-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most- of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir Or while on contact with liquid '''ring flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those consider. ably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions, This paper reports the density of I6 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simpli-fied method of obtaining gas density is presented in the Form of charts, which apply for specific groups of gases.

Jan 1, 1942

By Marshall B. Standing, Donald L. Katz

Density data are reported on 16 saturated hydrocarbon vapors at Pressures ranging from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. Introduction The densities of natural gases are necessary in many engineering in in petroleum production and utilization, Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 Ib. per sq. in.4 Recent discoveries of pools having Pressures UP to 7500 lb. Per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data On gas density at high pressures. Methods of Computation The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The meth-me-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most- of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir Or while on contact with liquid '''ring flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those consider. ably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions, This paper reports the density of I6 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simpli-fied method of obtaining gas density is presented in the Form of charts, which apply for specific groups of gases.

Jan 1, 1942

By J. B. Hess, R. L. Dietrich

IN the mechanical twinning of magnesium on the {1012} planes the crystallographic deformation is such that, in the direction of the hexagonal axis [0001], twinning is possible only under tension stress, while in the directions perpendicular to the hexagonal axis, twinning is possible only under applied compression. Thus in extruded magnesium and magnesium alloys where the extruded textures are best described as either [1010] or [ 1120] fibers,1 the basal planes are all nearly parallel to the extrusion axis and such material is susceptible to {1012 } twinning by compression in the direction of the extrusion axis. In order to explain the results of cyclic stressing in alternate tension and compression upon the tangent elastic modulus in such material, Dorn and Thomsen2 have postulated that, following twinning under applied compression, a retwinning or untwinning occurs as a result of residual microtensile stresses immediately upon removal of the applied compressive force. Recently, Carapella and Shaw3,4 have used this supposition of untwinning in magnesium in discussing their results on indentation hardness and on cold drawing of MI sheet. In trying to confirm this hypothesis by suitable direct experiments, the authors have been unsuccessful in detecting any evidence whatsoever that untwinning follows the release of applied compression and are forced to conclude that this hypothesis is improbable or, at least, that the quantity of material involved is small. For the experiments, small cylindrical specimens 0.040-in. diam. X 0.120- to 0.140-in. long were etched from 0.0625-in. extruded rod. The ends of the specimens were accurately faced off parallel in a jeweler's lathe. The compression jig was simply an ordinary set of micrometer calipers with an anvil interposed between the spindle and the specimen. The anvil was free to move axially but restrained from rotating so that the rotation of the spindle would not introduce a twisting stress on the specimen. With this arrangement the compressive strains could be estimated to 0.0001 in. and X ray pinhole photographs could be taken with or without load as required. Fig 1 is the pattern of an uncompressed specimen of AZ31 alloy, showing the approximate [1010] extrusion fiber. The X ray beam is normal to the extrusion axis; in this position it is particularly sensitive in detecting twinning if one directs his attention to the diffraction ring from the basal plane. Since twinning on {1012} planes produced an 86° reorientation of the crystal lattice, the original basal reflections occur at the 3 and 9 o'clock positions while the (0002) reflections from any twinned material will occur at the 6 and 12 o'clock positions. Fig 2 shows the same specimen compressed 3.0 pct, photographed while still under load. This strain has been just enough to produce a detectible amount of twinning and the sensitivity is roughly indicated by the fact that no alterations were produced in the intensities or maxima of the other diffraction rings. A strain of

Jan 1, 1948

By B. H. Cody

The Morenci concentrator of the Phelps Dodge Corporation is a part of the project that was completed after five years had been spent in development of the open-pit mine, equipment and process testing in the former No. 6 concentrator, and construction of the reduction works. The reduction works, of which the concentrator is a part, is about a mile and a quarter southeast of Morenci, on the highway that leads up Morenci Canyon. The concentrator has a nominal capacity for the treatment of 45,000 tons of ore daily. The original plant, which has a rated capacity of 25,000 tons of ore daily and is now in its fifth year of operation, began production on Jan. 30, 1942. The addition, to increase the capacity 80 pct, began operation on Dec. I, 1943. The equipment of the original plant has been described in Mining and Metallurgy (May 1942). NO changes in equipment were recommended for installation in the concentrator extension and only one major change, forced by a shortage of maintenance labor, has since been made. Metallurgical treatment has been altered in some ways as experiments progressed and as labor and economic conditions dictated. No complete description of the operation of the concentrator has been published, so this paper will record such operating and equipment changes as have been necessary, the operating methods that have been developed and the metallurgical results that have been obtained. Descriptions are given in the order of the processes with a flowsheet and an equipment list of each process for convenient reference. The questions asked by engineer visitors have guided the detail in which operation and maintenance are described. During the period Jan. 30, 1942 to Sept. I, 1946, ore milled has totaled 43,595,253 dry tons, from which 1,643,885 tons of concentrate have been made, containing an indicated production of 783,164,-809 lb of copper. The principal results obtained in operation of the concentrator during the years 1942 to 1945, inclusive, and to Sept. I, 1946 are shown in Table I. A graphic general flowsheet of the plant is given in Fig I. Ore The Morenci ore that is now being treated is a medium-hard monzonite porphyry in which the principal sulphide minerals are chalcocite and pyrite. A minor amount of covellite is present. Chalcopyrite and bornite have been observed under the microscope. The chalcocite occurs mainly as a coating on pyrite. Some of the coatings are so thick that the pyrite presents the appearance of being an inclusion in chalcocite. Some are less than one micron thick and are barely visible at 500 diameters magnification of a polished cross section. Some chalcocite is present as a in in the gangue. Various oxidized copper minerals are present as a result of oxidation in place but they represent a minor proportion of the copper minerals of the ore body. Oxidation

Jan 1, 1949

By Robert B. Fulton

The objective of this chapter is to discuss the interrelationship between industrial minerals and chemical manufacturing. It is intended to supplement rather than duplicate the commodity chapters. Particular emphasis is given to the pertinent chemical element and to market factors. Condensing this broad subject into a few pages of this handbook permits treating only the most important elements derived from industrial minerals. Hydrocarbons, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potassium and nitrogen for fertilizers, and titanium dioxide for pigments. The remaining six elements of major importance are: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Table I (Jones, 1973) affords an overview of the main industrial minerals, the chemical products derived from them, and end uses of the products. Salt brines have particular importance as raw material sources for the chemical industry. Table 2 (Anon., 1967) is a chart of the chemical compounds derived from four types of brines: (1) Owens Lake-type brines, which are sources of boron and sodium compounds; (2) Midland-type brines, from which bromine, iodine, and chlorides of calcium, magnesium, potassium and sodium are derived; (3) Searles Lake-type brines, yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak-type brines, produced mainly for lithium. Market Attributes Some of the important market traits common to industrial minerals used by the chemical industry are listed below. 1. They are international commodities, such as fluorspar and sulfur, which largely move to foreign consumers. 2. Grade, and freedom from deleterious elements are important factors affecting their usability in chemical processes. An example is salt (NaCl) used in electrolysis where ultrapure evaporated salt is required to meet rigid specifications. 3. Purified products take on the characteristics of specialty items and command a distinctly higher price than the basic commodity from which they are derived. 4. In practically all cases, chemical users require some sort of cleaning or beneficiation of the naturally-occurring mineral to bring it to specification, and individual specifications may vary from user to user for essentially the same use. 5. In some instances it is necessary to strike a balance between what the vendor can supply and what the buyer requires, with the result that specifications have to be eased to afford the needed materials in marginal cases. 6. Because they tend to be bulk commodities, low cost for handling and transportation are important and such costs may limit the area from which a chemical user can draw his supply. For example, fluorspar from China and Thailand normally goes to Japan, while South African fluorspar can go either to Japan or to the US. 7. Shipments are usually in bulk and frequently in multiple-car, full-trainload or full-shipload lots to reduce transport costs, which in turn may require large terminal investment facilities.

Jan 1, 1983

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By C. G. Dunn

Many investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal oricntation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.l--3 Furthermore, it is believed that high-stress regions exist in the vicinity of these bands4. and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallizati~n.5,6 Similar evidence has been published for nonferrous metals5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins cxisted prior to recrystalli~ation.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary oricntation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha iron.9 Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involvc more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By Carlton D. Hulin

The usual concurrence in time and space of intrusive igneous activity, favorable structural disturbance and mineralization, which is so manifest in the mineralized district necessarily indicates a close interrelationship between these events. Evaluation of available evidence leads to the recognition that an appreciable time interval exists between the emplacement of the igneous intrusive and the formation of associated ore deposits. During this interval known portions of the intrusive are completely solidified, highly differentiated magma facies are injected as dikes, and important faulting occurs, which may fracture and shatter the solidified intrusive body. The highly differentiated dike types could only have originated in some deep portion of an underlying plutonic body that had reached an advanced stage of magmatic differentiation. Appearing after these dikes, the mineralizing solutions may likewise be presumed to have originated at great depth. Certainly no source for these solutions can be found in near-by portions of the intrusive igneous body. The association of igneous intrusives and clustering ore deposits must be recognized as resulting from structural control. The emplacemerit and the subsequent solidification and cooling of the intrusive set in operation forces that are responsible for the favorable structural disturbances that control the mineralized district. The emplacement of the body of fluid magma weakens the crustal rocks to the extent that failure due to strains originally present in the rock body may occur. Faulting of any type and of any magnitude may be the result. Subsequently, owing to the change of state from fluid magma to crystalline granitic rock, volume decreases approximating 10 Per cent may Occur, with resultant shrinkage and collapse within the rock body. Following solidification, thermal contraction, induced by cooling of the rock body, causes a further volume reduction of 6 per cent. This thermal contraction, extending over a lengthy period of time, results in a succession of minor fault movements. These small fault movements, occurring progressively throughout the period of mineralization, are responsible for maintaining the permeability of the rock body, without which access of the mineralizing solutions and the formation of the ore deposits of the mineralized district would be impossible. Introduction A proper understanding of the causes that have localized our mineralized districts should be of considerable value to geologist and engineer alike. under current conditions the known ore reserves of productive mining camps are being rapidly depleted. Although ore of the future will be derived in part from deposits now known and from Ore bodies that are still to be discovered within the limits of productive mining districts, in part at least it must come from mineralized districts whose existence or importance yet remain to be recognized. The mining geologist is thus faced with two problems of paramount importance: (I) the location of new ore bodies within known mineralized areas and (2) the location of new mineralized districts within whose confines, previously unknown, valuable Ore deposits may occur. Any contribution to our knowledge concerning the causes for the localization of mineralized districts

Jan 1, 1949

By Carlton D. Hulin

The usual concurrence in time and space of intrusive igneous activity, favorable structural disturbance and mineralization, which is so manifest in the mineralized district necessarily indicates a close interrelationship between these events. Evaluation of available evidence leads to the recognition that an appreciable time interval exists between the emplacement of the igneous intrusive and the formation of associated ore deposits. During this interval known portions of the intrusive are completely solidified, highly differentiated magma facies are injected as dikes, and important faulting occurs, which may fracture and shatter the solidified intrusive body. The highly differentiated dike types could only have originated in some deep portion of an underlying plutonic body that had reached an advanced stage of magmatic differentiation. Appearing after these dikes, the mineralizing solutions may likewise be presumed to have originated at great depth. Certainly no source for these solutions can be found in near-by portions of the intrusive igneous body. The association of igneous intrusives and clustering ore deposits must be recognized as resulting from structural control. The emplacemerit and the subsequent solidification and cooling of the intrusive set in operation forces that are responsible for the favorable structural disturbances that control the mineralized district. The emplacement of the body of fluid magma weakens the crustal rocks to the extent that failure due to strains originally present in the rock body may occur. Faulting of any type and of any magnitude may be the result. Subsequently, owing to the change of state from fluid magma to crystalline granitic rock, volume decreases approximating 10 Per cent may Occur, with resultant shrinkage and collapse within the rock body. Following solidification, thermal contraction, induced by cooling of the rock body, causes a further volume reduction of 6 per cent. This thermal contraction, extending over a lengthy period of time, results in a succession of minor fault movements. These small fault movements, occurring progressively throughout the period of mineralization, are responsible for maintaining the permeability of the rock body, without which access of the mineralizing solutions and the formation of the ore deposits of the mineralized district would be impossible. Introduction A proper understanding of the causes that have localized our mineralized districts should be of considerable value to geologist and engineer alike. under current conditions the known ore reserves of productive mining camps are being rapidly depleted. Although ore of the future will be derived in part from deposits now known and from Ore bodies that are still to be discovered within the limits of productive mining districts, in part at least it must come from mineralized districts whose existence or importance yet remain to be recognized. The mining geologist is thus faced with two problems of paramount importance: (I) the location of new ore bodies within known mineralized areas and (2) the location of new mineralized districts within whose confines, previously unknown, valuable Ore deposits may occur. Any contribution to our knowledge concerning the causes for the localization of mineralized districts

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.' These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By E. C. Wright

The bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth edition of "The Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after I9I0 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blastfurnace capacity complementary to bessemer operations, combined with the availability of the' necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the -exense of besskmer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made, in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Re-phosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complee discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955