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By R. B. Fuller

DURING the summer of 1949, the United Nations Scientific Conference on the Conservation and Utilization of Resources met at Lake Success. As summed up by one writer, the purpose was: "That everyone will try to learn how to feed more people from an acre of land." That objective is a stimulus to the phosphate rock industry as well as other industries.

Jan 8, 1951

By E. S. Bumps, W. F. Craig, M. Baeyertz

Metallurgists have looked at fractures macroscopically for many years and have evolved a vocabulary in which such words as "cleavage," "brittle," "shear," "ductile," "granular," "fibrous," and "silky" are used to describe the appearance of the fractured surface; but the meaning of these words in terms of metal structure is not well established. Observations of the structural meaning of "brittle" and "ductile" fractures in plate steels have been made, notably, by Kramer and coworkers1 and by Tipper.2 Grossman3 has studied the fracture of tempered martensite and combinations of ferrite and martensite. Notwithstanding these and other less concerted attacks on the problem, present understanding of fracture rests more on assumptions and logic than on experiment. It is the purpose of this paper to add a little to the growing fund of experimental observations of the nature of fractures in steel. The particular fractures to be described were obtained in conventional impact testing of an ordinary structural steel shape. In impact tests of the Charpy type, the specimens fail in a characteristic manner that depends on the steel and the temperature of testing. With ordinary structural and many other steel products, an appropriate range of testing temperature will cause a considerable change in the energy absorbed before fracture. This change is known as the energy transition and is accompanied, more or less closely, by alteration in the appearance of the fracture. At testing temperatures below the transition, the terms "brittle," "cleavage," or "granular" are used to describe the fracture; above it, "ductile" or "shear" are often used. Within the transition, the fracture changes from "brittle" to "ductile" by a progression in appearance, wherein the "brittle" portion of the fracture becomes restricted to a smaller and smaller central area of the fracture, as the testing temperature is raised and the "ductile" type of fracture is approached. All this is well known to metallurgists. The specimens under consideration are of the conventional V-notch Charpy type. They were taken from a structural steel shape of the following analysis: C Mn P S Si 0.17 0.46 0.009 0.029 0.03 Both longitudinal and transverse specimens were tested and examined. Fig 1 shows the energy values plotted against testing temperatures in the usual way. The curves for both longitudinal and transverse specimens show an energy transition, although the maximum energy absorbed at testing temperatures above the transition is greater in the case of the longitudinal specimens. Fig 2 illustrates the changes in the macroscopic appearance of the fractures that are associated with the energy transitions shown in Fig 1. Macrographs of the fractured surfaces of the specimens have been identified with the fracture ratings at intervals on each fracture curve. The numerical fracture rating on the ordinate of Fig 2 indicates the percentage of the area of each fracture that was considered to be "brittle" on macroscopic observation. Such rating of the fracture type in impact tests is now customary in many laboratories. Hereafter the specimens will be identified by reference to Fig 2 as 90 pct "brittle," 80 pct "brittle," and so on, in accordance with this macroscopic evaluation of the appearance of the fractured surface. The discussion of the fractures is divided into three parts. The first two are concerned with the mode of fracture and its relation to general structural features. As the same metal-lographic features occur in both longi-

Jan 1, 1950

By William H. Emmons

The problem of the metalliferous veins has always been an outstanding one in the science of ore deposits. In recent years interest has been stimulated by Spurr, who maintains that veins have consolidated from magmas that have densities as great as the densities of ordinary rocks. Lindgren published a noteworthy paper1 in 1926, in which he supports the theory that veins are deposited chiefly by hot waters. Lindgren's paper was discussed by Singewald, Spurr, Kemp, Anderson, Colony, Bateman, Porter and others. The discussion, in the main, was centered on the interpretation of fragments that are included in veins. This paper also treats the problems of fragments in veins and includes a reply to a review by Spurr2 of a bulletin by Larsen and myself3 published by the United States Geological Survey on the geology and ore deposits of Creede, Colorado. Mineral veins containing fragments of the wall rock are common. At many places the fragments are completely isolated, one from the other, and are entirely surrounded by vein matter. It has been stated that the vein matter around the fragments was heavier than the fragments and that the latter were floated in a magma. J. E. Spurr, who is the leading advocate of this hypothesis, 4 urges that normal mineral veins were deposited by solutions heavy enough to float fragments of the country rock, and it is mainly on this relation that he bases his theory that veins are deposited by solidification of magmas. If it can be shown that vein-forming solutions have a specific gravity greater than rock (2.77), one is justified in regarding them as true mag-matic solutions. It is shown later in this paper, however, that at Lead, S. D., water not more highly concentrated than ordinary drinking water is depositing vein matter around fragments of schist and of steel in such a manner that the fragments are completely isolated and completely surrounded by the mineral cement.

Jan 1, 1928

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank' standardized by the American Society for Testing Materials. Although this method of classification has been an American stand¬ard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1944

By Michael Perch, Charles C. Russell

Nearly 95 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69,9, and in 1938 it was 61.3, To produce a net ton of pig iron 1959 lb. of coke was required in ,1940 and 1760o lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By A. P. Anderson, J. H. Jensen, W. E. Breckoff

Bromine is the intermediate member of the halogen family of elements between iodine, a solid, and chlorine, a gas. The name is derived from the Greek "bromos," meaning stench. Bromine is the only nonmetallic element that is liquid at room temperatures with a melting point of -7.2° C and a boiling point of 58.78º C. Reddish brown in color, it dissolves easily in water to yield a red solution. Bromine volatilizes at ordinary temperatures to a red vapor that is very irritating to the eyes, nose, and throat. Density of the liquid is 3.12 and gas weighs 7.59 gpl at standard conditions. As the element is highly active, it exists in nature only as bromide compounds. Bromine was discovered by Antoine Jerome Balard in seawater bitterns in 1826 and first prepared in quantity in 1860. Distribution Bromine is widely distributed in nature and compounds occur in solution in natural brines, in seawater, saline lakes, oil and gas well brines, and in evaporite chloride minerals. The concentration of bromine salts ranges from 60-65 ppm in seawater to several thousand ppm in oil well brines and saline lakes. The distribution of bromine in marine evaporite minerals and in the solutions from which they crystallized was determined many years ago by H. E. Boeke (1908). Theoretical aspects regarding the geochemistry of bromine have been published in numerous papers (Raup and Mite, 1969). Bromine occurs in solid solution in carnallite and sylvite associated in potash deposits; in halite in salt beds; salt in oil shales; and in trona deposits. Its presence is useful as a guide in geochemical exploration. The analysis of small amounts of bromides in the presence of large amounts of chlorides is discussed by W. Schwerdtner (1963). Manganese, iron, and iodine may interfere with the determination. Other analytical methods are discussed at length in the literature (Stenger and Atchison, 1964). Sources and Reserves The sources and reserves of bromine, given in Table 1, appear ample to meet present and foreseeable requirements in all producing countries. With the occurrence of bromine salts in seawater and other brines, the potential for bromine production is worldwide. It has been estimated that 99% of all commercially recoverable bromine is in the ocean. However, actual subterranean brines having a higher bromine content than seawater will continue to be the preferred sources of bromine for the foreseeable future. [ ]

Jan 1, 1983

By Robert F. Shurtz

When an ore deposit is evaluated on the basis of core sampling, questions always arise as to how much weight should be given the various sample grades and how the deposit should be divided into specific volumes assigned to corresponding grades. For a tabular deposit it is customary to use the so- called zone-of-influence. This zone is usually de- fined as the polygon in the plane of the deposit having corners halfway between a given core drill intersection and each of the nearest neighboring intersections. The volume of the ore in this polygon is assigned the analysis obtained from the drill core taken at the intersection. In massive or irregular deposits, volumes of various shapes may be defined with respect to the locations of drill core samples. These volumes may be regarded as three-dimensional zones-of-influence; the theory involved in assigning the values of the central analyses to the ore in the volumes is the same as that used in the case of a tabular deposit. The zone-of-influence method was used in evaluating one of the magnesite deposits at Gabbs, Nev.1-3

Jan 10, 1959

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By A. S. Richardson

VENTILATION of the Butte mines has long been a rather difficult problem because of the natural high temperature of the rock. With increase in mining depth, higher rock temperatures have been encoun-tered, and this has caused a constantly growing demand for more effective ventilation measures. During recent years the hazards of dust in mine air have been more clearly recognized, and have necessitated the adoption of dust-prevention methods. To meet these ventilation problems in the mines of the Anaconda Copper Mining Co., a mines ventilation department was organized in 1918, to act under the direction of the general superintendent of mines. At the present time, under normal operating conditions, the force employed includes the ventilation engineer, two chief assistant ventilation engineers and eight assistant ventilation engineers. The activities of the department are, briefly: (1) planning and supervising operation of the general ventilation system; (2) planning and supervising the operation of dust-prevention measures, together, with dust sampling and related microscopic work for the quantitation of the dust samples and determina-tion of particle-size distribution; (3) the design and development of air-conditioning methods to meet present exceptionally severe temperature conditions and in anticipation of future requirements. To a large extent the technical features of the ventilation methods have been described in earlier papers by the author. This paper is written mainly to summarize past accomplishments bearing most closely on health and safety, with a somewhat more detailed account of the dust-prevention measures that have been developed comparatively recently.

Jan 1, 1938

By Warren Smith

IT has been 5 years since the writer left the Philippine Islands and while in that country his chief work did not lie in this field, though he has visited all but one of the localities mentioned in this article. The principal field studies relating to oil were made by his colleague, Mr. Wallace E. Pratt. The writer's investigations dealt with the general stratigraphy and paleontology of the Philippines. With the exception of the investigations made by Mr. Pratt and the writer very little information on this subject is available. A number of geologists in the employ of large oil companies have visited the Islands from time to time but, following the general rule, the public has scarcely ever been permitted to learn anything of the results. The writer is indebted to the Bureau of Insular Affairs, Washington, for late information regarding recent legislation in the Islands relating to petroleum. All the known oil seeps, petroleum residues, such as ozocerite, and natural-gas emanations are associated with Tertiary sediments. The chief seeps and most promising prospects are located as follows: 1. Bondoc Peninsula (lower end), Tayabas Province, Southeast Luzon. 2. The west coast of the island of Cebú from Alegria north to, and perhaps beyond, Toledo. 3. Central Mindanao not far from Lake Lanao. 4. The ozocerite veins on the Island of Leyte in the northwestern part in the vicinity of the town of Villaba. 5. Natural gas from some deep wells in Tertiary shale formations on the eastern flank of the Cordillera and extending out under the plain on the island of Panay.

Jan 2, 1920

By Dermot M. Ross-Brown

Introduction Slope angles are one of the major factors affecting the shape of the final pit and the location of the walls Due to differences in geology, the optimum slope angles vary from pit to pit and within different parts of the same pit. Indeed, it is not unusual to have different slope angles for the top and bottom portions of the same cross section. The optimization of these slope angles is a major study in itself and this chapter is intended as a general introduction to the subject. It is not intended to be a comprehensive text for the absolute beginner The objective is to put the various aspects of slope stability analysis into relative perspective by describing the vari¬ous analytical techniques available and indicating when each may be most appropriately used References are made to the many excellent texts and papers on slope stability for the reader who does not have a formal training in soil or rock mechanics. In writing this chapter, an assumption has been made that a tentative mining plan has been drawn up, includ¬ing a preliminary estimate of the slope angles. It has also been assumed that all the necessary field and laboratory data has been collected and reduced to a form suitable for input into the stability analyses.

Jan 1, 1979

By H. G. Moulton

THE INCREASING scale of mining operations over the past decade, particularly in connection with the exploitation of large bodies of comparatively low-grade copper ores, has made necessary the study of the behavior of rock under failure. When extractions of as high as 40,000 tons a day are reached in steam-shovel operations and as high as 20,000 tons per day in underground mining operations, it is evident that excavations soon become of such size that the behavior of the rock will often be dependent on fundamental principles applicable to more or less homogeneous materials under stress, rather than on weathering or local planes of weakness. In the ordinary rock excavations encountered in civil-engineering practice, such as excavations for subways, highways, railroads, etc., rock faces are not carried to depths sufficient to develop any pressures, or consequently any failures, except those due to loose masses resulting from local planes of weakness. When, however, orebodies whose tonnage is measured by hundreds of thousands are to be extracted by steam-shovel operations in open pits, it is necessary to determine if possible in advance the slopes that the sides of the pits will assume, for these slopes influence the shape of the excavations and thereby the amount of ore that may be extracted by the open-pit method. When large orebodies are mined underground at depths of 300 to 500 ft. (91 to 152 m.) by caving methods, the surface subsiding as the ore is withdrawn, it is necessary to determine in advance the outermost limits of fracture in the subsiding surface, for on the delineation of these limits depends the location of surface improvements, mills, smelters, etc. and also the location of development work, such as hoisting shafts, main haulage levels, and all other underground openings that must remain undisturbed during the period of ore extraction. Heretofore, in civil-engineering practice, it has been assumed that earth and rock behave differently in failure. For the calculation of earth

Jan 2, 1920

By T. S. Jr. Sligh

OF all the qualities that are essential in a good cigar tobacco none is quite so important as the burn. This term is general and includes many points, the most important of which are evenness of burn, color of ash, firmness and coherence of ash, and fire-holding capacity. The fire-holding capacity refers to the length of time the leaf or cigar will continue to, glow after ignition. Chlorides tend to prevent complete combustion and products are formed thereby that are injurious to the flavor and aroma. On the other hand, the carbonates of the alkalies, particularly of potassium, aid the combustion and increase the fire-holding capacity. Barth1 thought that the harmful effect of the chlorides was due to their fusing and coating the tobacco, thereby preventing complete combustion. Schlosing,2 Nessler,3 and Garner,4 suggested widely different theories to account for the favorable action of potassium salts. In order to study carefully the action of the various salts upon the course of combustion of the cigar a knowledge of the temperature of the burning cigar is necessary. Lehmann5 who seems to be the only investigator who has made any attempt to determine the temperature of a burning cigar gives 480° C. as the maximum temperature which he recorded. It is evident, however, that his measurements were in error, probably on account of the method and apparatus used, since the lowest visible red corresponds to a temperature of about 575° C.

Jan 9, 1919

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By R. H. Hiltz, R. W. Douglass

Large-grain specimens of iodide titanium prepared metal-lographically were stain etched using the technique of New York University as modified by Watertown Arsenal Laboratories. Orientations of grains showing an abnormal response to stain etching were determined by back-reflection X-ray techniques. X-ray results showed that a-titanium grains, oriented such that their basal planes were parallel to the polished surface, have a slower reactivity to stain etching than any other orientation. Grains oriented such that their basal planes made small angles with the polished surface exhibited reaction rates between that of the true basal orientation and the normal rate. As the angle with the surface increases the reactivity increases up to a maximum angle of 14 deg. Basal planes making an angle with the surface of greater than 14 deg show normal reactivity to stain etching. These data, plus work on polycrystalline specimens, indicate that the oxidation rate of titanium might be reduced by correct alignment of crystal planes. ThE earliest observed phenomenon in the micrography of titanium was the occurrence of a grains which exhibited no birefringency. Even though a titanium possesses a hexagonal-close-packed structure and should be optically anisotropic, it can appear optically isotropic, when the crystal is so oriented that its intersection with the polished surface is perpendicular to the axis of symmetry. During the develoment of color staining techniques for titanium: it was noted that the a phase did not stain uniformly. Staining of specimens of commercially pure titanium resulted in a micro-structure of blue-colored grains, among which were randomly oriented a few grains exhibiting colors between the initial yellow and the final blue color. Under polarized light, these off-colored grains appeared to be optically isotropic. More intense study with polarized light, however, showed only the yellow grains to be isotropic. The intermediate colored grains exhibited weak birefringency, which at first glance is not detectable due to the strong birefringency of the surrounding structure. Aminoff2 and Straumanis3 have previously shown that in zinc the basal orientation is less reactive than other orientations. Leidheiser4 showed the same thing to be true for the hexagonal-close -packed configuration of cobalt. Thus, it would appear that the basal-plane orientation is responsible for the abnormality in stained titanium. Later work by Leidheiser5 on cobalt has shown that other planes besides the basal plane exhibited reaction rates slower than the normal rate. Reported planes were the (100), the (1011) and several planes making small angles with the basal plane. The last observance appears not to be due to the reactivity of the reported plane but due to the reactivity of the basal plane which is very close to being parallel to the surface. There are, then, two possible explanations for the range of colors observed in stain-etched a titanium. Since extensive research on the effect of orientation on surface reaction has failed to provide any definite trend, these two explanations are not adequate in themselves. Planes showing the retarded reactivity differ not only for different crystal structures but for metals of the same crystal structure and even for different reactions of the same metal. Tragert,6 Leidheiser,7 Tammann,6 and wagner9 have shown copper to exhibit retarded reactivity on the (111) plane. However, Leidheiser10 has shown that under other conditions the retarded reactivity of copper is associated with the (100)

Jan 1, 1960

By C. G. Rhodes, D. Kramer

The kinetics of precipitation of transient a phase during the transformation in U-16 wt pct Mo between 400° and 550°C were studied using quantitative metallography and electrica1 resistiuity measurements. The volume percent of a phase goes through a maximum in time, corresponding to a critical degree of progress of y' formation. prior to its re-solution after prolonged annealing. The fastest rate of a precipitation oc-cuvs at 500°C with a concomittant lowest peak of 9.5 vol pct a. At 450°C, 14 vol pct a, greatest fov any temperature, was observed after 24 hr witlz an associated slowest rate of formation. a precipitation at 400°C ceases after approximately 160 hr and the amount of a present remains unchanged after long times at temperature; no y' was observed metallographically at this temperature. IN the U-Mo system at 16 wt pct Mo, an ordering reaction takes place below 600°C, see Fig. 1, whereupon the random bcc solid solution, y, transforms to the ordered bct phase, y'."2 The new unit cell is constructed of three old unit cells somewhat distorted. While attempting to study the kinetics of this transformation it was observed that an unexpected phase was precipitating out early during the transformation anneal reaching appreciable amounts before disappearing after long times. The y' appeared in the presence of this new phase and after long times constituted the whole sample. Owing to the high optical activity of this unexpected phase under polarized light, it was suspected to be the a phase. Subsequent X-ray powder pictures confirmed this belief. The kinetics of a phase formation and disappearance is the subject of this paper. EXPERIMENTAL PROCEDURE A) Alloy Preparation. Alloys for this study were prepared by vacuum induction melting normal reactor grade uranium and 99.5 wt pct Mo pellets in thoria crucibles. Two ingots were prepared, and sections of the top and bottom of each ingot were chemically analyzed for uranium and molybdenum content. The results of the analyses appear in Table I. B) Metallography. Samples of 16M were wrapped in tantalum foil, sealed in evacuated (5 X 10"6 mm of Hg) quartz capisules, and annealed at 1110"C prior to being transferred directly to the transformation temperature. They were examined metallographically after increasing times to determine the progress of the transformation at 400°, 450°, 500°, and 550°C. The samples were prepared for metallographic examination by mechanical polishing with diamond paste and electrolytic polishing with a solution of glacial acetic acid and chromic acid. Since the y' phase is tetragonal, its presence can be detected by viewing the sample in polarized light. To increase the contrast between y' plates, the samples were electro-etched in a 10 pct oxalic acid solution. To reveal a phase in bright field (it can be seen in polarized light in the "as-polished" state), the samples were electro-etched in a solution of citric acid and nitric acid. To determine the vol pct a phase, a variation of the one dimensional systematic point count method as described by Hilliard and cahn3 was used. The

Jan 1, 1962

By J. D. Wright

INTRODUCTION The Endako deposit was first explored in 1926, but development waited until the early nineteen sixties. It first came under the control of Placer Development in 1963, and early in 1964 a decision to bring it into production was reached. The deposit is located near the geographic center of British Columbia, and is served by an east-west communication system including a paved highway, mainline railway and good telephone, teletype, and computer facilities. The plant area is shown in Figure 1. The operation is known as the Endako Mines Division of Canex Placer Limited of Vancouver. First production was achieved in June, 1965, at a nominal rate of 10,000 tons per day, but it soon was closer to 15,000 tons per day. In 1967, two new grinding and flotation, sections brought capacity to the present rate of approximately 27,000 tons per day. With mill heads of around 0.15 percent MoS2, production is about 14,000,000 pounds of molybdenum per year. A flowsheet of the operation is given in Figure 2. A legend for this flowsheet is given in Table 1. Published ore reserves are estimated at 214,500,000 tons at an average grade of 0.143 percent MoS2. PRIMARY CRUSHING The 85 or 100-ton haulage trucks dump over a grizzly into a 42 inch x 65 inch C.A.C. (Canadian Allis Chalmers) gyratory crusher. The

Jan 1, 1976

By Erhard Hornbogen

Twins were propagated into large, well-annealed crystals of a, iron-phosphorous and a, iron-molybdenum solid solutions. Strain fields caused by interaction of these twins were made visible by precipitation. These strain fields can be explained by assuming that transmitted and reflected plastic waves are created when a twin strikes an obstacle with high velocity. The twin front itself can be regarded as a shear wave that may be able to develop a one-dimensional shock front. The occurrence of {WO} fracture by the reflected stress is also discussed. The described effects were not found when twins propagated at lout velocity into disturbed crystals, for example, into crystals previously deformed by slip. DEFORMATION twinning leads to shearing of a crystal lattice under external load. The shear appears to be homogeneous over a large number of crystal layers. In a iron, shear occurs on the (112) planes and in the <1ll> directions. The formation of a twin proceeds by the movement of partial dislocations that change the stacking at the twinning plane.l, In the bcc lattice, this partial dislocation can be created by dissociation of a sessile a/2[111] dislocation that lies in the (112) plane: Cottrell and Bilby&apos;s spiral mechanism can explain the homogeneous shear, but has not been proven experimentally. Nevertheless, this mechanism can explain the possible high velocity of formation of a twin. In Cottrell and Bilby&apos;s model, as in other models of twinning or phase transformation, a much higher energy is required to spread the first stacking fault than to add new layers by further movement of the partial dislocations. The dislocations will therefore become accelerated proportional to the difference between the stress, tN, to nucleate and tp to propagate the twin. It has been assumed3,4 that tn is the stress required to make two partial dislocations of apposite sign pass for the first time. After the first layer of new stacking has been formed, the maximum stress is TN=Gb/4pd where G is the shear modulus, b is the Burgers vector of the partial dislocation, and d is their perpendicular spacing so that the amount of shear is S = b/d. From this formula, a value of 25 kg per mm2 has been estimated for twinning in Zn3. The measured values are smaller, but local internal stresses may help to provide the necessary stress. For a iron, a higher value can be expected, mainly due to the higher value of G. That agrees with the observation that "burst" twinning occurs if the yield strength is in-

Jan 1, 1962