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By I. M. Roberts

THE war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-furnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to. meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19 ¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. COKING CHARACTERISTICS OF COALS Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By J. L. Bray

IT is well known that iron markedly improves the physical properties and casting characteristics of aluminum bronzes. The use of 1 to 4 per cent iron as the principal modifying addition has become common practice in many foundries melting aluminum bronzes. Although the beneficial effects of iron are unquestioned, there is some uncertainty regarding the structural changes caused by it in the basic copper-alumi-num system. It is agreed that a new constituent appears in abundance when the iron content reaches 2 to 4 per cent. This constituent, which frequently occurs in shapes resembling clover leaves, is sometimes assumed to be an aluminum-iron intermetallic compound. If this were correct we might expect a change in the structural relationships of the matrix in the direction of decreased aluminum content. On the other hand, it has been reported that iron has a negligible effect in altering the fundamental relationships of copper-aluminum alloys1. Others2,3 have reported an additive coefficient. Apparently it will be necessary to know the equilibrium relationships between the phases of the copper-aluminum-iron alloy system to establish any such theory as fact. When this has been done it may very well be that a further revision in the structural relationships may be necessary to describe the changes to be expected in commercial cast alloys. It was with this latter problem before them that the authors attempted to

Jan 1, 1936

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3' of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:' basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,'-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6'7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5' of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By Theodore B. Comstock

a. Boundaries of the District.—The district here considered comprises that portion of Colorado commonly known as " the San Juan Country." In order to bring the principal geological features of this region within the scope of a map of convenient dimensions upon a suitable scale, I have found it desirable to mark off boundaries near the parallels of 37O and 38O 10', and the meridiaus of 106' 30' and 108' 30' (West Longitude from Greenwich). This area of (approximately) 9400 square miles includes all the formations which we should have to discuss if our territory were greatly enlarged, excepting such as are distinctly characteristic of adjoining areas with independent orographic genesis. By limiting this review to these confines we miss very little of the geology of the eight counties of the San Juan region, viz.: Dolores, San Miguel, Ouray, Hinsdale,

Jan 1, 1887

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By T. Egleston

THE direct process for the manufacture of iron which is principally used in the United States, in New York and New Jersey, is called the Jersey forge, the Champlain forge, the Catalan forge, the Bloomary forge or fire, and sometimes a Forge fire. Dr. T. Sterry Hunt, who has discussed the process as applied to the beach sands of Canada as well as to ores, in the Report of the Canadian Geological Survey for 1867-69, has shown that the name of Catalan forge is incorrect, as this process in no way resembles the Catalan, but is really the old German bloomary modified by long use in this country. Dr. Hunt gives the probable history of the introduction of the process into the United States, and a series of historic citations of great interest relating to it. Not¬withstanding the improvements which have been made in the construction of the furnace and its greater output, the process to-day, in all its essential features, is carried out as Karsten described it. It should now be known as the American Bloomary. The name of Jersey or Champlain forge or fire is not sufficiently distinctive. The name of Bloomary, by which the process is usually distinguished, is objectionable, not because it is incorrect but because it is indefinite, as the Knobbling fires, which are a very slight modification of the Walloon process, for making blooms either from pig iron or by sinking scrap, are also called Bloomaries, and although Knobbling fires are only used in a few localities where charcoal pig is made, and special grades of charcoal-refined blooms are required, one does not, without an explanation, know whether the blooms are being manufactured from ore or pig. The name Forge fire is equally indefinite, as it might just as well apply to any of the five direct methods of making blooms which have been in use in Europe, but which have now mostly gone out of date. The Dame of American Bloomary, however, is the one which most completely describes it, and is the one least open to objection. The names of German, Jersey, and Champlain bloomary are too local, and these adjectives are thought unnecessary by those who use the process, and we shall not therefore describe it under any of these names, but as the American Bloomary process. * Read at the Montreal meeting, September, 1879.

Jan 1, 1880

By T. Egleston

The direct process for the manufacture of iron which is principally used in the United States, in New York and New Jersey, is called the Jersey forge, the Champlain forge, the Catalan forge, the Bloomary forge or fire, and sometimes a Forge fire. Dr. T. Sterry Hunt, who has discussed the process as applied to the beach sands of Canada as well as to ores, in the Report of the Canadian Geological Survey for 1867-69, has shown that the name of Catalan forge is incorrect, as this process in no way resembles the Catalan, but is really the old German b1oomary modified by long use in this country. Dr. Hunt gives the probable history of the introduction of the process into the United States, and a series of historic citations of great interest relating to it. Notwithstanding the improvements which have been made in the constrnction of the furnace and its greater output, the process to-day, in all its essential features, is carried out as Karsten described it. It should now be known as the American Bloomary. The name of Jersey or Champlain forge or fire is not sufficiently distinctive. The name of Bloomary, by which the process is usually distinguished, is objectionable, not because it is incorrect but because it is indefinite, as the Knobbling fires, which are a very slight modification of the Walloon process, for making blooms either from pig iron or by sinking scrap, are also called Bloomaries, and although Knobbling fires are only used in a few localities where charcoal pig is made, and special grades of charcoal-refined blooms are required, one does not, without an explanation, know whether the blooms are being manufactured from ore or pig. The name Forge fire is equally indefinite, as it might just as well apply to any of the five direct methods of making blooms which have been in use in Europe, but which have now mostly gone out of date. The name of American Bloomary, however, is the one which most completely describes it, and is the one least open to objection. The names of' German, Jersey, and Champlain bloomary are too local, and these adjectives are thought unnecessary by those who use the process, and we shall not therefore describe it under any of these names, but as the American Bloomary process.

Jan 1, 1880

By Gilbert E. Doan, William C. Schulte

An extensive program of investigation is being carried out at Lehigh University in the study of arcs and arc welds of high-purity iron1, sponsored by the Engineering Foundation. The part of that program reported in the present paper deals with welds made of high-purity iron in an argon atmosphere and for comparison with them welds made of the same iron in ordinary air. Welds of commercial steel also were made in argon and in air. The primary purpose of the study is to discover the basic physical constants of iron welds when not contaminated either by impurities in the iron or by the action of oxygen and nitrogen of the air during welding. Upon these constants can be founded such future studies as will determine what effects the various impurities and alloy elements present in steel have upon its welding characteristics, and what influence is exerted by the action of oxygen and nitrogen. The welding of steel involves such a multitude of variables, both of composition and of procedure, that development in the fabrication of this most important metal has necessarily been slow, wasteful, and in many instances discouraging. In the present investigation, the simplest possible condition has been selected; namely, iron practically free from contamination and a nonparticipating atmosphere, the inert gas argon. This simplification reduces the number of variables to a point where more rigid control of the system is possible. Although this study is significant for the contributions it makes to the science of steel fabrication, yet it is hoped that it will not be without value also in increasing knowledge of the. nature and behavior of iron and steel in general. From the standpoint of open-hearth practice, and to some extent from the standpoint of electric-furnace practice also, the conditions of melting and casting iron in this investigation are extraordinary. The casting temperature is high, the mean temperature of the metal probably reaching 2000' C. (3600' F.)? The rate of chilling of

Jan 1, 1936

By William C. Schulte, Gilbert E. Doan

An extensive program of investigation is being carried out at Lehigh University in the study of arcs and arc welds of high-purity iron1, sponsored by the Engineering Foundation. The part of that program reported in the present paper deals with welds made of high-purity iron in an argon atmosphere and for comparison with them welds made of the same iron in ordinary air. Welds of commercial steel also were made in argon and in air. The primary purpose of the study is to discover the basic physical constants of iron welds when not contaminated either by impurities in the iron or by the action of oxygen and nitrogen of the air during welding. Upon these constants can be founded such future studies as will determine what effects the various impurities and alloy elements present in steel have upon its welding characteristics, and what influence is exerted by the action of oxygen and nitrogen. The welding of steel involves such a multitude of variables, both of composition and of procedure, that development in the fabrication of this most important metal has necessarily been slow, wasteful, and in many instances discouraging. In the present investigation, the simplest possible condition has been selected; namely, iron practically free from contamination and a nonparticipating atmosphere, the inert gas argon. This simplification reduces the number of variables to a point where more rigid control of the system is possible. Although this study is significant for the contributions it makes to the science of steel fabrication, yet it is hoped that it will not be without value also in increasing knowledge of the. nature and behavior of iron and steel in general. From the standpoint of open-hearth practice, and to some extent from the standpoint of electric-furnace practice also, the conditions of melting and casting iron in this investigation are extraordinary. The casting temperature is high, the mean temperature of the metal probably reaching 2000' C. (3600' F.)? The rate of chilling of

Jan 1, 1936

By John Fritz

TROUGH it is not a condition of the Award, the fact is that the John Fritz Medal never has been given to an engineer who had not already received one or more similar awards. This "medal for medalists," on the evening of April 20, was presented to Daniel C. Jackling at a special dinner held at the Union League Club in New York. The citation read "For notable industrial achievement in initiating mass production of copper from low-grade ores through the application of engineering principles." The present award recognizes the same accomplishment-the launching and guiding to the port of marvelous success of the Utah Copper Co., first of the so-called "Porphyries"-as did the award of the William Lawrence Saunders Gold Medal by the A.I.M.E. in 1930, and before that the Award of the Gold Medal of the Mining and Metallurgical Society of America in 1926. Following the custom a biography of the Medalist had been published in a small pamphlet as a supplement to the John Fritz Medal Book. T. A. Rickard was the au¬thor of the sketch of Mr. Jackling, an innovation being the placing of a copy of the booklet at the place of each of the diners. The committee in charge of the dinner consisted of two past-presidents: R. E. Tally, of the A.I.M.E., who was chairman; Bancroft Gherardi, of the A.I.E.E.; and Thaddeus Merriman, director of the A. S. C. E., the John Fritz Medal being a joint award of the four societies. Frederick M. Becket, President of the A.I.M.E., as chairman for the occasion, briefly stated the purpose of the dinner. He stressed his satisfaction that the award was symbolic of the cooperative professional activities of the four great national organizations of engineers. He introduced Francis Lee Stuart, past-president of the A.S.C.E. and now chairman of the John Fritz Medal Board of Award. Mr. Stuart outlined the history and purpose of the Medal established in 1902 in memory of John Fritz, of Bethlehem, Pa., one of the great pioneers of America's iron and steel industry, metallurgist, and president of the A.I.M.E. in 1894. Mr. Stuart called the roll of former John Fritz Medalists, three of whom, Ralph Modjeski, J. Waldo Smith, and Ambrose Swasey, were present to do honor to Mr. Jackling. He then introduced George Otis Smith, whose privilege it was to present the Medalist for 1933. Dr. Smith was the senior of the four A.I.M.E. representatives on the Board that last year selected Mr. Jackling for the honor. His speech follows in full.

Jan 1, 1933

By J. E. Burke, C. W. Mason

IN attempting to study precipitation from a tetragonal lattice using solid solutions of bismuth in tin, it was found that although a Widnmanstatten pattern is observed 1 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process MICROSCOPICAL STUDIES Alloys were made from Chempur tin (Standard samples 42b and 42c, National Bureau of Standards), and bismuth (Kahlbaum C P ) by melting neighed quantities together under palm oil, stirring well, and casting in a heated graphite mold The polishing and etching techniques employed largely govern the visibility of the structural changes The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through BehrManning 3/o abrasive papers, lubricated by a solution of paraffin in kerosene A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution, repeated etching and polishing served to remove disturbed metal For high-power examination better preparation was necessary It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a Heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use A better procedure was as follows The metal lap was warmed slightly, and a 4-in circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C was poured over it, allowed to stand for 1 to 2 min and then washed off It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample The cloth was then charged with a paste of the relevigated alumina in water Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deteriorates after about 24 hr This is not serious, because a new lap can be prepared in about 5 min, and only small pieces of cloth are used Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer For the final etching, the most satisfactory reagent was that of Taffs,7 the formula for which is FeC13 6H20, 2 grams, HC1, 5 c c , H2O, 30 c c , C2H5OH (95 per cent), 60 c c This etchant reveals differences in com-

Jan 1, 1941

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By Heihachi Kamura

The reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe2O3 + 3CO = 2Fe 4- 3CO2 2Fe2O3 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of earbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing equation, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also on the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium. Chemical Equilibrium of Iron, Oxygen, and Carbon Investigations concerning the equilibrium between iron, oxygen, and carbon have been carried out by E. Baur and A. Glaessner,1 who deter-

Jan 1, 1925

By E. C. Truesdale

IN recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part II of the paper the attempt is made to review all of the pub-lished work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data

Jan 1, 1935

By R. H. McLean

Velocity, kinetic energy and shear in crossflow beneath three-cone jet bits may influence cleaning of the bottom of the borehole and the teeth of the bit. Laboratory investigation shows that each of these parameters is a function of the diameter of the borehole and the product of the volume rate of flow and velocity through the nozzles (QVn). Increasing QV, or decreasing the diameter of the borehole increases each parameter. These functions provide means of predicting the magnitude of each parameter and of scaling the cleaning forces. INTRODUCTION In drilling operations using conventional jet-type rock bits, the impinging jels create an important flow mechanism. Called crossflow, this flow mechanism originates in the impact area of the jets, spreads across the bottom of the hole and supplies the principal source of energy to clean the teeth of the bit and most of the bottom.' Besides providing the means of cleaning cuttings from the bit and the hole bottom, crossflow may also have other, less direct, effects on the rate of penetration. The shear stress generated on the bottom by crossflow will inIluence the thickness and permeability of any filter cake of mud solids or crushed material which forms on the bottom.' These factors may affect the rate of penetration. A previous pulblication introduced some fundamental concepts of crossflow.' Crossllow was shown to occur in a thin layer adjacent to the bottom, and to cover the bottom completely. The maximum velocity in the crossflow above any position on the bottom was found to be directly proporlional to the square root of the product of the volume rate of flow and velocity through the nozzles—the jct QV,,—and inversely proportional to the diameter of the borehole. This information indicated that the effectiveness of crossllow in scavenging the bottom can be improved by maximizing the jet QV. The investigation reported herein amplifies the definition of crossflow. Complete velocity profile data above a representative position on the bottom are analyzed. These data better illustrate control of the capacity of crossflow to scavenge the bottom, and also relate shear stress on the bottom to known, controllable parameters. The conclusion reached in the previous publication that maximization of the jet QV. produces the maximunl cleaning beneath current jet bits is unchanged by these new data; rather, it is strcngthened. Data presented here show that the kinetic energy flux above a representative position on the bottom is maximized by maximizing the jet QV. The shear stress on the bottom will also be shown to be maximized in the same manner. Since the functions relating the jet QV. to velocity, shear stress and kinetic energy also involve the diameter of the borehole, means of equating, or scaling, these quantities in different sizes of boreholes will be illustrated. EXPERIMENTAL EQUIPMENT AND TECHNIQUE JET BIT MODEL Data were recorded from the same laboratory model as used in the aforementioned investigation of the flow around a jet bit.' The model consisted of a 43/4-in. three-cone, jet-type rock bit in a smooth, flat-bottomed borehole constructed of lucite. The bit had a shape and nozzle placement closely resembling larger three-cone jet bits commonly used in field operations. Fig. 1 illustrates the impact area on the bottom of a jet from this bit. Details of the orientation of the jets may be found in the previous publication. TECHNIOU'E OF MEASUREMENT Measurements of the crossflow were made by inserting a very small Pitot tube through the bottom of the simulatetl boreholc. Extreme thinness of the layer of crossflow necessitated accurate measurements of the height of the Pitot tube above the bottom to achieve close definition of the velocity profile. A cathetometer, which could be read to the nearest 0.005 cm, was used to make this measurement.

Jan 1, 1966

By G. Y. Chin, W. L. Mammel

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain has been analyzed by Taylor and by Bishop and Hill. The Taylor analysis is based on a principle of' virtual work, and involves finding, among numerous cotnbinalions of slip systems that satisfy the imposed strain, the combination in which the sum of the glide shears is a minimum. Previously, Taylor has treated the case of axisymmetric flow when slip occurs on (111)(110) (or {110)(111)) systems only. His analysis has now been extended by computer methods to the cases of slip on {112}(111) and {123)(111) systerns and of mixed slip on {110), {1 12), and (123) planes with a common (111) slip direction, all of which are important in the deformation of bcc crystals. The results are computer-plotted as contours of the ratio of the floe strength to the critical resolved slzea-r stress for slip, for axial orientations distributed throughout the standard stereographic triangle. Implications of the computer results to texture develop,merit, texture hardening, and dislocation theories oj work hardening are discussed. WhEN a single crystal is extended in the usual tension test, the lateral dimensions can change relatively freely. In this case, the glide shear produced by slip on a single slip system is sufficient to accommodate the (tensile) deformation. Since slip is governed by a critical resolved shear stress law (the Schmid law'), the single active slip system is one for which the stress, resolved on the slip plane and in the slip direction, is the highest among the several equivalent slip systems. This amounts to saying that a value M = U/t = y/~ is a minimum among the equivalent systems, where M is the inverse of the familiar Schmid factor (a and E refer to tensile stress and strain, and T and y refer to resolved shear stress and shear strain). A grain embedded in a polycrystalline aggregate, on the other hand, cannot freely change its shape due to constraint from its neighbors. In this case, slip from five independent slip systems (to accommodate five independent strains) is generally required.' Based on the principle of virtual work and assuming that the critical resolved shear stress for slip is the same for all systems, Taylor hypothesized that, among all combinations of (five) slip systems which are capable of accommodating the imposed strain, the active combination is that one for which the sum of the absolute values of the glide shears is a minimum. Again, this is equivalent to saying that the value of M = CjlyjI/ is a minimum, in analogy to the single slip case. Taylor aminimum,analyzed the case of {111)(110) slip for fcc metals, and applied the analysis to crystals undergoing axisymmetric flow, that is, the same macroscopic shape change as the poly crystalline aggregate under uniaxial tension (or compression). For the twelve equivalent {111}( 110) slip systems, there are 384 independent combinations of selecting five systems to satisfy the five independent linear equations of imposed strain.4 Taylor calculated the value of M for each combination* and obtained the active com- *A number of the independent combinations were omitted from consideration in Taylor's original work (see Ref. 5). bination (minimum M) for a number of axial orientations distributed throughout the standard stereographic triangle. Later work by Bishop and Hill*'8 showed that Taylor's least-shear hypothesis was equivalent to a maximum work principle which they advanced. Using the simplified Bishop and Hill method for {111)(110) slip, Hosford and Backofen' obtained detailed contours of constant minimum M for the same axisymmetric flow case. In contrast to {111}(110) slip in fcc metals, slip in bcc metals is generally described as occurring on {ll~)(lll), {112)(111), {123) (111) systems as well as mixed slip composed of all three. Since the direction cosines of the slip plane normal and the slip direction enter as a product in the Taylor analysis, the Taylor solutions of ,M for {110)(111) slip are identical to those for { 111} 110) slip. The other three cases of slip, however, have not been solved. In view of the numerous combinations of slip systems involved in the calculations, the Taylor analysis is clearly oriented toward computerized solutions. THE TAYLOR ANALYSIS In order to obtain the active combination of (five) slip systems by solving for the minimum value of M = we first express the (small) strain components E,, with respect to the cubic axes 1, 2, 3 ([loo], [010], [001], respectively) of the crystal, in terms of the sum of the glide shears yj from slip systems j: where n, and n,j refer to direction cosines of the slip plane normal, and dri and dsi to direction cosines of the slip direction, of slip system j, all referred to the cubic axes. In practice, the strain components are given with respect to the specimen axes X, y, 2. These components are readily converted to ers through the tensor transformation where irk and 1,~ are the direction cosines between the two sets of coordinate axes.

Jan 1, 1968

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By R. W. Snyder, W. H. Guilinger, B. S. Gottfried

Two numerical methods are presented JOT solving the equations Jor one-dimensional, multiphase /low in porous media. The case oF variable physical properties is included in the Formulation, although gravity and capillarity are ignored. Both methods are analyzed mathematically, resulting in upper and lower bounds for the ratio of time step to mesh spacing. The methods are applied to two- and three-phase waterflooding problems in laboratory-size cores, and resulting saturation and pressure distributions and production histories are presented graphically. Results oJ the tuo-phase flow problem are in agreement with the predictions of the Buckley-Leuerett theory. Several three-phase flow problems are presented which consider variations in the water injection rate and changes in the initial oil-and ujater-saturation distributions. The results are different physically from the two- phase case; however, it is shown that the Buckley-Lez~erett theory can accurately predict fluid interlace velocities and displacing-fluid frontal snturations for three-phase flow, providing the correct assumptions are made. The above solutions are used as a basis JOT et~aluuting the numerical methods with respect to machine time requirements and allowable time step for a fixed mesh spacing. INTRODUCTION Considerable progress has been made in recent years in obtaining numerical solutions of the equations for two-phase flow in porous media. Douglas, Blair and Wagner2and McEwenll present different methods for solving the one-dimensional case for incompressible fluids with capillarity (the former using finite differences, the latter with an approach based upon characteristics). Fayers and Sheldon4 and Hovanesian and Fayers8 have extended these studies to include the effects of gravity. West, Garvin and Sheldon, l4 in a pioneer paper, treat linear and radial systems with both capillarity and gravity and they also include the effects of compressibility. Douglas, Peaceman and Rachford3 consider two-dimensional, two-phase, in compressible flow with gravity and capillarity and Blair and Peaceman1 have extended this method to allow for compressible fluids. No one, however, has examined the case of three-phase flow, even for the relatively simple case of one-dimensional flow of incompressible fluids in the absence of gravity and capillarity. In obtaining a numerical technique for simulating forward in situ combustion laboratory experiments, Gottfried5 has developed a method for solving the one-dimensional, compressible flow equations with any number of flowing phases. Gravity and capillarity are not included in the formulation. The method has been used successfully, however, for two- and three-phase problems in a variable-temperature field with sources and sinks. This paper examines the algorithm of Gottfried more critically. Two numerical methods are presented for solving the one-dimensional, multi-phase flow equations with variable physical properties. Both methods are analyzed mathematically, and are used to simulate two- and three-phase waterflooding problems. The numerical solutions are then taken as a basis for comparing the utility of the methods.

Jan 1, 1967

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954