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By M. B. Bever, A. B. Michael

The solidification of aluminum-rich aluminum-copper alloys was investigated for different solidification rates. The measured amounts of nonequilibrium eutectic were compared with the amounts calculated on the assumption of no diffusion in the solid. The morphology of the eutectic was studied and dendritic spacings were measured. Compositions of the cored primary solid solutions were determined by quantitative autoradiography after activation of the solute copper by neutron irradiation. CONSIDERABLE progress has been made in recent years toward an understanding of the solidification of metals. This is especially true for the factors involved in nucleation, the controlled growth of metal crystals from melts, and various aspects of the freezing of ingots and castings. Many features of the solidification process, however, are not understood adequately and much further work is required. In the research reported here the solidification of a series of aluminum-rich aluminum-copper alloys was investigated. Different degrees of deviation from the idealized case of equilibrium solidification were attained by varying the rate of solidification. Thermal analysis and microscopic examination were supplemented by lineal analysis and autoradiography. The latter required the use of radioactive tracers and was adapted to the quantitative determination on a microscale of concentrations of copper dissolved in aluminum. The tracers were produced in situ by activating the copper with neutrons. These techniques permitted a correlated interpretation of the temperature-time history, the amounts of nonequilibrium eutectic and the general morphology of the alloys, and yielded quantitative data on microsegregation. Nonequilibrium Solidification In the general case of the solidification of a solid solution in accordance with the phase diagram, the composition of the coexisting liquid and solid must change continuously. This change requires diffusion, which at best remains incomplete in the solid during solidification. The resulting inhomogeneity of the solid solution crystals is well-known as coring, dendritic segregation, or microsegregation. The generally accepted analysis of coring assumes that, 1—no diffusion occurs in the solid, 2—diffusion is complete in the liquid, and 3—the composition of the solid formed on cooling through any infinitesimal temperature interval is given by the solidus of the phase diagram. On this basis, In this equation m designates mass, x designates the concentration of solute and the subscripts L and S refer to the liquid and solid phases, respectively; the subscript o indicates the initial state, in which the liquid is identical with the entire system. Eq. 1 or its equivalent has been derived repeatedly'-7 and an analogous equation, known as Rayleigh's equation, has been used for distillation. The assumptions on which Eq. 1 is based do not include an infinitely fast cooling rate as sometimes stated. In fact, Olsen and Hultgren %ave shown by experiment that very high solidification rates suppress coring, presumably by preventing diffusion in the liquid and by the effect undercooling has on the composition of the nucleus. Coring thus occurs at rates of cooling which are too fast for a close approach to equilibrium in the solid and too slow to suppress diffusion in the liquid and to cause marked undercooling. If the liquidus and solidus approximate straight lines, Eq. 1 simplifies to The fraction of liquid present at any temperature during nonequilibrium solidification can be calculated from Eqs. 1 or 2. By the lever relation it is

Jan 1, 1955

By C. D. Woodward

THE subject of electric signals for the despatching off mining cages through shafts has received cousiderable attention recently from various mining companies. The Anaconda Copper Mining Co. has found it necessary to develop a system that is reliable, safe and simple in operation, and easy to repair. The movement of all mine cages or skips is under the direction of a station tender, who rides on the cages when men or supplies are being lowered or raised. When ore is hoisted, he is stationed at a skip pocket for loading and despatching the skips. For the station tender's use, two signal systems are installed in each hoisting compartment, and he is the only employee authorized to use them. One system is known as the "AC" or Station bells, as it is operated from the 110-volt, 60-cycle, power service; the other system, called the "DC" or shafts bells, takes its energy from closed-circuit primary batteries. As a supplement to the two main signals, a buzzer system is installed. The general arrangement is similar to "the main signal, except that there is a mine buzzer at each station. When a signal switch connected into the buzzer system is pulled down, all buzzers are operated, thus notifying the station tender that he is wanted at some particular level. Placed on the station posts, and within easy reach of the men on the cages, are the signal pull switches for the main signals. The station, or "AC," pull switches are furnished with a short rope as shown in Fig. 1, while the shaft, or "DC," pull switches are equipped with ropes that extend down the shaft past the next station. To avoid all confusion in the use of the three signal systems, a standard arrangement has been adopted in all mines for the location of the pull switches. Fig. 2 illustrates the position of the pull switch at the various mine stations for the main signal systems, but it does not show the buzzer pull switch; this is fixed to the roof timbers about 25 ft. back from the shaft. If the skip pockets are a considerable distance below the station, a pull switch for each main shaft compartment is connected to the "AC" system and placed at this point. However, if the distance is short, a light cord is attached to the station pull switches and dropped down to the skip pocket.

Jan 2, 1922

By Sidney Powers

SINCE the opening of the Wheeler oil and gas field in Carter County and the discovery of oil near Lawton, Comanche County, Okla., in 1904, interest has been aroused regarding the origin of the oil in the Permian "Red Bed" region which lies between the Wichita and Arbuckle Mountains on the north and the Red River on. the south. . The later development of the Healdton, Loco, Duncan, Fox, and Graham fields south and west of the Arbuckle Mountains has brought the region into prominence. Recent discoveries of Ordovician and of Pennsylvanian fossils in wells in the Healdton field and of Pennsylvanian fossils in the Fox and Graham fields are of such importance from a scientific and a commercial standpoint that the occurrences and the problems arising therefrom are here briefly described. Producing oil and gas sands in the southern Oklahoma fields, with the exception -of those in the Cretaceous and underlying rocks in the vicinity of Madill, Marshall. County, are associated with the Permian "Red Beds" or with the underlying Paleozoic strata. I n the two fields farthest south of the Arbuckle Mountains, Healdton and Loco, production has been entirely confined to sands at depths of 700 to 1400 ft. (213 to 416 m.) and only recently has a producing sand as deep as 1860. ft. (567 m.) L been encountered. These sands are found near and below the base of the red rocks and were supposed by Wegemann and Heald 2 to belong in large part to the basal Permian,. Wichita formation, or to the immediately underlying formations. Fossils in the blue shales and in the limestones associated with the deeper sands' now prove them to be Pennsylvanian and all-the producing sands at Healdton are found to be of this age. In the fields nearest the Arbuckle Mountains, the Wheeler sands at a depth of about 700 ft. (213 m.) appear to be of Permian age,

Jan 11, 1917

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 V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of 'impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

(SECRETARY'S NOTE.) The following discussion of the papers of Van Hise, Emmons, Lindgren and Weed, read at the Washington meeting, February, 1900, and printed on pp. 282 to 498 of this volume, comprises communications to the Secretary, received at various times before the Richmond meeting, February, 1901, and, for the most part, presented at that meeting. These communications are introduced at this point in the present volume, in order that they may precede the papers of Vogt, hemp, Lindgren, Rickard, etc., presented at Richmond, and therefore not forming part of the material considered in them. Since many of the contributors have mentioned in one communication several of the papers referred to, no attempt is here made to divide their remarks and distribute the fragments under separate headings. In each contribution, however, the several topics are indicated by subtitles. R. BECK,* Freiberg, Saxony : Prof. Veal Hise's Paper.-The paper of Prof. Van use (p. 282) represents a great step of scientific progress, in that the circulation of underground waters has never before been presented with such clearness, ill the light of modern chemical and physical knowledge. The theories of the formation of ore-deposits which follow the author's general survey of the currents and solvent power of atmospheric waters in the earth's crust do not, indeed, seem to be novel, being essentially an amplification of Le Conte's views; but the proofs adduced in their support are in many particulars so original that no one can read without profit this portion of the paper. Entirely new (though largely in agreement with the papers of Emmons and Weed, presented at the same meeting of the Institute) are the sections dealing with the formation of the rich sulphides of the precious metals, and especially the regeneration of normal sulphides, such as galena, etc., in vein-zones immediately beneath the ground-water level. Nevertheless, it appears to me that Prof. Van Hise, in the course of his most instructive exposition of unquestionable, yet still locally limited, phenomena, has been too much biased in favor of the " descensionists." This is indicated by the small importance which he attaches to the intimate genetic relation between epigenetic deposits and the plutonic hearths of the earth's interior.

Jan 1, 1902

By S. A. Montague

Mica can claim a considerably greater importance than would be assumed from its comparatively small dollar volume, which came to about $37,000,000 for the United States industry as a whole in 1957. Mica is one of the strategic minerals. We must depend on imports from distant sources for virtually all of our requirements of high grade block and all of our mica splittings. Mica is essential and indispensable for vacuum tubes and high-performance condensers, two electronic components which are vital military necessities besides being nearly indispensable to civilization today. Composition and Properties Mica is the general name for a group of some nine different minerals, two of which, muscovite and phlogopite, are the minerals used by the mica industry as its raw material. Several of the other varieties are commercially useful-vermiculite, * used for heat insulation in expanded form, and lepidolite, used as an ore of lithium while the others-biotite, roscoelite lepidomelane, paragonite and zinnwaldite have little or no commercial importance. Biotite frequently occurs as an undesirable impurity in muscovite. Table 1 lists various properties and other data concerning muscovite and phlogopite. Chemically, mica is a complex silicate of sodium, potassium and aluminum. Most varieties of muscovite are higher in sodium, and of phlogopite in magnesium. There are no important uses of mica where the chemical analysis is important, except that in some uses of ground mica, the content of iron oxide present as an impurity must be kept to a very low limit. Muscovite occurs in a range of color from the so-called India "ruby" which is more closely a pinkish brown, to light and dark green, with numerous other intermediate shades. Ruby color is usually preferred by industry, especially in the better qualities. When split very thin the color in most [ ] micas disappears. Muscovite mica is frequently found containing black and red "stain" as a homogeneous part of the books or sheets. In most cases this stain or impurity is magnetite

Jan 1, 1960

By Clark B. Risler, Walter E. Thomas

MILL planning must include electrical drives and a system to supply them. These should be considered at the time metallurgical and mechanical plans are being made. Because it is convenient, flexible, reliable, and economical, electricity is the accepted source for powering mill concentrating equipment. Ore-treating mills have grown to the point where a single mill has been built using 360 motors ranging from 1 to 1000 hp and totaling 50,000 hp. Such a system of electrical drives can be scattered over a square mile and employ 4000 to 220 v. Drive Motor Characteristics: Since ore processing is predominantly a continuous operation, very few of its drives require wide speed variation after initial adjustment. Consequently squirrel cage, wound rotor, and synchronous alternating current motors are most often used.

Jan 5, 1957

Jan 4, 1953

By R. B. Sosman

INTRODUCTION IT is well known that ferric. oxide, Fe.-,03, is paramagnetic, while magnetite, Fe304, is classed among the highly ferromagnetic substances. But magnetic data on oxides intermediate in composition between Fe-03 and Fe304 have been almost completely lacking. Fe203 and Fe304 form a solid-solution series, according to present evidence.' In this series the properties change continuously from Fe203 toward Fe304, as the percentage of FeO increases from zero toward 31.03, which is the percentage in magnetite. It is possible that there is a break in the series near Fe304, but it has not yet been possible to establish the existence-of such a break experimentally. The occurrence of solid solution ill this series is shown by the dissociation pressure, or oxygen pressure in equilibrium with the oxides, which falls continuously over the range from Fe203 to Fe304. The oxygen-pressure curves at 1,100° and 1,200° are shown in Fig. 1. The existence of solid solution is also demonstrated by the continuous change in optical properties from Fe203 over to a composition containing about 18 per cent. FeO, at which point the opacity of the oxide becomes so great that it is im-possible to obtain measurements at higher percentages of ferrous iron. Natural oxides of iron intermediate in composition between Fe2O3 and Fe304 are much more common than is generally supposed. If a mineral oxide is not strongly attracted by a small hand magnet and if it gives a red streak, it is usually labeled "hematite." If it is strongly attracted by the hand magnet it is usually labeled "magnetite" without further tests. As we shall show later, oxides containing from 1 up to 31 per cent. FeO can be thus erroneously lumped together as "magnetite." It is a fact, nevertheless, that the great hulk of natural oxides of iron lie fairly near either Fe203 Or Fe304 in composition. The reason will be

Jan 6, 1917

By R. E. Hook, R. L. McGaughey, A. M. Adair

The initial yielding characteristics of a vacuum-melted iron have been measured as a function of thertnal history after slow cooling or quenching from a 700°C recrystallizntion anneal. A thermal history favoring the segregation of interstitials to grairz boundaries results in a material having high values of upper and lower yield stress and long, irregutar Luders' plateaus, wheueas specimens treated to minimize grain boundary segregation have significantly lower values of these yielding characteristics. The struc- ture of typical grain boundary areas as revealed by electron transmission microscopy is consistent with these findings. The grain boundaries in iron are considered to be principally responsible for the release of dislocations during macroscopic yielding and it is suggested that strong locking results when a substantial amount of grain boundary segregution is present; it follows that weak locking results from a more random distribution of interstitials to grown in dislocations. RECENT years have seen an increased emphasis placed on a more quantitative study of the influence of grain boundaries on the yield behavior of bcc metals. The earlier picturk of dislocation pileups at grain boundaries building up a sufficient stress concentration to unlock dislocations in neighboring grains1

Jan 1, 1967

By W. R. Ingalls

In choosing the unusual title given to this paper, in which the term "cyclic " might be substituted for "intermittent," my idea has been simply in respect of precision. We might say old method vs. new method, but that antithesis implies something of substitution that has not occurred and perhaps is not in sight. We may say horizontal retorts vs. vertical, but none of the older retorts are truly horizontal, and there are three different types of vertical retorts. Other complexities might be suggested. There is, however, a broad distinction between distilling that is accomplished in a periodic cycle, generally daily; and distilling that is accomplished continuously, irrespective of whether it be done in the vertical retorts of the New Jersey process or in the retorts of the Trollhät-tan process. In offering a summary of the present state of the art with the intermittent process, I shall not have any idea of exemplifying it through descriptions of any single plants, but shall rather divide among the main steps of the process and outline what is best developed among them. In pursuing this thought, it will manifestly be impossible to make a composition that will exemplify the acme of good practice, for the latter will always be a function of the cost of labor, fuel, etc., which are widely variable. As of 1929, in respect of labor we might generalize the average plant wage in the Pittsburgh-Wheeling district of the United States at $5 per day; in Oklahoma at $3; in Great Britain at $3; in Germany at $1.75-$2; in Belgium and France at $1. With high labor costs the metallurgist will naturally use means of the nature of mechanization that with low labor would be uneconomical when capital charges are taken into account. Nor may we from records of performance safely make positive deductions in respect of the efficiency of different types of furnaces unless they have been tested comparatively under identical conditions in the same works. We shall find gas-fired regenerative furnaces showing coal consumption from 1.2 tons down to 0.7 per ton of roasted ore, which may be ascribable to difference in the thermal value of the coal that is used or to differences in proportions of the parts of the furnace, which is something quite distinct from the principle of the furnace. Thus, we have

Jan 1, 1937

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By Henry U. Ross

The behaviour during reduction of iron-ore pellets and sinters was investigated. Several methods for the preparation of agglomerates and their reduction were tried. Commercial agglomerates from world-wide sources as well as experimental samples were tested. The effect of coke additions to pellet and sinter plant feeds was given special consideration. An analysis of the test results has helped to explain many of the phenomena associated with the reduction of iron-ore agglomerates such as swelling, loss in strength and wear resistance, changes in porosity, changes in mineralogy and the formation of metallic iron and slag. A double-layer pellet with all of the coke concentrated in the core proved particularly interesting. Although large quantities of coke showed that partially reduced agglomerates containing metallic iron could be produced in the laboratory, the problem of producing reduced pellets and sinters by the existing agglomerating processes still remains.

Jan 1, 1977

By Y. Nakada, B. Chalmers

The work-hardening behavior of surface layers of aluminum and gold single crystals was investigated by alternately deforming and then removing a thin surface layer by electropolishing or by etching. Aluminum crystals exhibited lower flow stresses after the surface removal; gold crystals did not. Abrasion of surface eliminated easy glide in both gold and aluminum crystals. By alternately deforming and removing the surface layer, it was shown that the abraded crystals work-harden preferentially under the abraded layer. It is suggested that this phenomenon is caused by the difficulty of propagating dislocations through the abraded layer. It has been demonstrated in numerous cases'-3 that the plastic behavior of metals in either single-crystal or polycrystal form is sensitive to the environment and to the condition of the surface; it has also been reported4-6 that single crystals of some metals, when deformed in tension, exhibit more work hardening near the surface than in the interior. A third type of effect that has been attributed to the special part played by the surface in plastic deformation is the influence of the dimensions of the specimen on the various parameters that define its plastic-deformation characteris- tics.?-'' Many of these experiments were made on aluminum, on which an oxide film is always present under available experimental conditions; many of the effects have been attributed to the oxide film, either in terms of its higher elastic moduli, which would cause local stress redistribution, or its higher strength, which would oppose the escape of dislocations at the surface of the metal. On the other hand, it has been suggested II,12 that the mere presence of a surface should be sufficient to produce the observed results. A rigorous examination of this question could, in principle, be carried out by comparing the behavior of aluminum with its oxide film with that of the same material without oxide. This experiment would present great difficulties. The most practical alternative is to compare aluminum with gold, which has no crystalline surface film at room temperature, and to study the effects of various surface treatments on gold. The experiments described in this paper fall into two groups, the objectives of which were to determine 1) whether single crystals of gold shared the property of aluminum that the removal of a surface layer after some plastic deformation reduced the flow stress for further deformation and, since the result of this was negative, 2) whether a surface treatment could be found that caused gold to behave in this way. I) EXPERIMENTS AND RESULTS All the tests described below were carried out on single crystals of about 6 by 6 mm cross section and of sufficient length to provide a gage length of about 10 cm.

Jan 1, 1964

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

Jan 1, 1918

By J. H. Wernick, J. E. Kunzler

HIGHLY pure metals are needed for low-temperature electron transport studies in progress. Recent improvements in purification techniques, such as zone refining, have made it possible to obtain metals with improved purity. For some metals, the improvement has been to the extent that ordinary analytical techniques are inadequate and special methods are needed.1 For other metals purification is more difficult, so that simple but rapid analytical methods are desirable as an aid in evaluating the effectiveness of purification procedures. Furthermore, it is desirable to be able to determine the impurity level of the sample or ingot with the minimum of physical disturbance of the material. In order to aid in the preparation of purer metals, techniques involving the measurement of electrical resistance at liquid-helium temperatures have been devised for studying impurity distributions in zone-refined ingots and other bulk samples without destroying the ingot or its geometry. The method yields information on the variations in purity along the length of the ingot or sample and provides a measure of the overall purity of the material. Compared with ordinary analytical methods, the resistivity method is rapid, sensitive, and does not require significant physical disturbance of samples with reasonable shapes. It has the disadvantage that resistance measurements are not specific, i.e., they do not identify the impurity. However, this disadvantage is offset by the advantage of being able to establish a measure of the overall purity so far as electrically active" impurities are concerned. METHOD AND ITS BASIS The method is based on the well-known fact that the resistivity, at Liquid helium temperatures, of a reasonably pure metal containing no regions with additional phases decreases with increasing chemical purity or a decrease in the number of physical defects. It is convenient to separate the total resistivity into three parts: where is the resistivity due to the scattering of the conduction electrons by the lattice vibrations or phonons, p is the contribution due to physical defects, and originates from the effect of chemical impurities in the metal. Insofar as Matthiessen's rule is obeyed,2 pphys and pchem are independent of temperature. Except possiblyin the very purest metals, ptherm is negligible at liquid helium temperatures and For zone-refined metals, which normally are well annealed and consist of large grains, at the chemical purity levels thus far attained the available data indicate that pphys is negligibly small or at least constant throughout the ingot. Assuming that the effect of physical defects is negligible for isotropic metals, This assumption appears consistent with most of

Jan 1, 1959

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962