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By W. M. Raynor

LARGE quantities of "midnight oil" have been consumed by researchers in attempting to develop a process to produce cold ductile zirconium at low cost. The tantalizing facts that zirconium is a bright, silvery, tarnish-proof metal and is 2 1/2 times as abundant in the earth's crust as copper, and thirteen times as plentiful as lead have resulted in much speculation on uses, ranging from automobile radiator grills to kitchen sinks. but unfortunately no low-cost process of producing it has so far been found. In the case of zirconium, we cannot say that "virtue is its own reward" for the principal virtues of the metal, namely, corrosion resistance at ordinary temperatures and ability to absorb gases at high temperature, are the very characteristics that defeat all of the usual recovery methods such as sintering, plating, or direct chemical reduction. The only method giving a pure metal sufficiently low in oxides, nitrides, etc. to be truly cold-malleable is the one developed by Van Arkel and DeBoer in 1925. This process involves decomposition of zirconium tetraiodide in contact with a hot filament and pre

Jan 1, 1947

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By J. P. Matoney, E. J. Sandy, D. A. Dahlstorm

INTRODUCTION Before an understandable discussion concerning coal-dewatering processes can be initiated, it is necessary to define some terms of usage. The many different meanings and interpretations of terms preclude development of standard definitions so that the terms which are defined in this chapter should be regarded mainly as working terms intended to facilitate communication. A coal slurry ' might be defined as a watery suspension carrying particles of fine coal and other assorted material ranging upward in size from the finest clay particles. Some particles may be in the colloidal sue range and exhibit characteristics of suspended colloids. The dilution of the system generally is such that it is in a condition of independent particle subsidence. In some coal mining areas a slurry is regarded as a suspension of fine coal and other materials having a dilution that cannot be economically dewatered by filtration. A coal slime may be regarded as a slurry containing particles of such size range that 50 per cent or more (by weight) will pass a 200-mesh sieve. Slime suspensions generally are difficult to handle without special treatment in conventional sedimentation equipment. A coal sludge is defined as a slurry that has been partly dewatered by sedimentation usually to a thick or viscous consistency where further dewatering can be most readily facilitated by filtration. Culm and silt are terms characteristic of coal-preparation practice which should be defined. In anthracite terminology, culm is the generally coarse residue or waste accumulation of coal, bone and rock from preparation plants most of which are no longer functional. Culm has a wide range of sizes, some rather coarse, and except to differentiate it from silt, the term is of limited interest in this discussion. In anthracite terminology, silt is the accumulation of waste fine coal, bone and slate settled out from preparation plant water in excavated basins. Silt is generally made up of particles ranging in size from 3/32-in. round-opening screen to the very finest sues. Silt is also referred to at times as sludge, fines, slush, and mud and is the partly dewatered derivative of what has been previously defined as slurry. In the terminology of the bituminous coal producing areas, the word culm commonly corresponds to slurry or slime, depending upon the size distribution of the suspended solids. Editor's Note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections authored by each individual as is the case in most chapters of this book.

Jan 1, 1968

By Samuel L. Hoyt

Cemented tungsten carbide, a product of a branch of metallurgy which has never possessed more than a relatively minor interest and importance, has recently commanded the attention of engineers, industrialists, financiers and men of business. New methods, new opportunities, new goals, never before considered, have suddenly been brought within the scope of practical realization. It is these results that attract the interest of the world, but we, as engineers and metallurgists, will have equal interest in the product itself and in that branch of metallurgy from which it comes. It seems appropriate, therefore, to speak today on Hard Metal Carbides and Cemented Tungsten Carbide, as the latter represents one of the outstanding developments of recent date in non-ferrous metallurgy. We are interested in the hard metal carbides as a group of related metallic substances and in cemented tungsten carbide as the leading representative of the metallurgy of this group. The literature of this general field is limited, and, bearing this in mind, it seems advisable to attempt to cover the field broadly and to correlate the subject matter, rather than to present a detailed account of any one of its phases. Our annual lecture lends itself admirably to this plan. The quickened interest in cemented tungsten carbide, once its potentialities were recognized, the many sides to the problem of developing the manufacture and use of this new product, and the desire to economize as much as possible in the time of development, have brought many into this work, both in this country and abroad, notably the Osram Lamp Co. and Friedrich Krupp in Germany and the General Electric Co. in this country. It would be presuming too much to attempt to speak too broadly of the present state of the art and science of the hard metal carbides and my remarks arc guided largely by the work done in the General Electric Co., and by our associates in the Carboloy Co. Even here the activities of many in these two groups have centered around the utilization of cemented tungsten carbide, which is outside the scope of this talk. To those whose work is represented in this lecture, it is my pleasant duty to acknowledge their assistance and advice. To Dr. Zay

Jan 1, 1930

By William F. Boericke

THERE was a time when the selection of fire brick was .left to the judgment of the head bricklayer of the plant, whose choice was not unaffected by a box of Christmas cigars from a friendly salesman. But the days are past when it was generally believed, with complacent philosophy, that bricks were bricks without much distinction, and should be bought on a price basis alone. Gone, too, is the belief that in certain types of industrial work the eventual failure of refractories was assured. Modern metallurgical practice, with its trend toward handling larger tonnages at higher temperatures, demands the use of refractories that cannot be supplied by random guess. The logical development is to inquire into the properties of the brick to be purchased, and this resolves itself into the use of specifications. In 1925, the General Refractories Co., with the active support and hearty cooperation of some of its larger customers, established a laboratory, at its Baltimore plant, for testing and research in refractories. This was the outgrowth of a growing appreciation of the value of research in the refractory field. Since then the work has become more involved' and the aims more ambitious, so that the present laboratory now employs a staff of 11 men working, under the direction of trained refractory technologists, on problems of research as well as the routine control of manufacture. It is believed s that `this type of laboratory is a comparative novelty among refractory manufacturing plants. It handles the testing and research work for all the 15 plants of the organization. Being at one of the works has the advantage of making it possible to carry on large scale plant tests on new products after the preliminary laboratory tests have been successfully completed.

Jan 1, 1929

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By Lester Blackner

THE PROPERTY AND LOCATION THE Ray Consolidated Copper Co.'s mining property is located on Mineral Creek 6 miles north of Kelvin, at Ray, Pinal County, Ariz. (Fig.. 1) . The mining claims now owned by the company consist of 126 lode claims, comprising 2,144.9 acres, containing at the beginning of operations 82,904,368 tons of 2.19 per cent. copper ore. GENERAL CHARACTERISTICS OF THE OREBODY The main orebody is a disseminated deposit in schist and porphyry formed by secondary enrichment. Its existence was proved by churn drilling, and it is at present one of the largest proved copper deposits in the world. The orebody itself covers .205 acres with an average thickness of 121 ft., and occupies a definite belt which has a northwest direction. Its length is approximately 5,000 ft. The width varies, being about 2,000 ft. at the west end and 2,500 ft. at the east, narrowing down irregularly front both ends to a few feet in the center. The thickness of the body varies greatly along the line of lode, ranging from a few feet up to 470 ft. thick. The ore horizon is not constant, but varies, following in a broad sense the topography The body in general dips slightly to the northeast, and is broken up by numerous small faults and fractures. The ore-bearing formations, consisting of mineralized schist and mineralized granite porphyry, stand fairly well and offer no difficulty in mining operations.

Jan 6, 1915

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By S. F. Shaw

THE Sierra Mojada mining district is situated in western Coahuila, about 8 km. east of the Chihuahua state line, and about one-half way from the northern to the southern extremity of the state. It is at the terminus of the Mexican Northern R. R., 125 km. northeast of Escalón, Chihuahua; also about 240 km. due west of Monclova, Coahuila. The altitude is approximately 1500 m. above sea level. The Sierra Mojada valley is about 10 km. long, from east to west, with a width of 1 to 2 km. It is approached from the east through the Puerto del Oro, where the Mexican Northern R. R. enters the valley; the slope from west to east is gentle. The Sierra Mojada, of which about. 300 m. is an almost vertical wall, bounds the valley on the south side; on the north side, the slope to the crest of Sierra Planchada is more gradual, rising only 200 or 300 m. above the valley. Water is relatively scarce in the district, and there are no running streams. The rainy season, usually beginning at the middle of June, lasts through July, and occasionally into August or September. In some years the rains fail entirely. The slope of the ground is such that nearly all the water immediately runs off. The arroyos along 'the flanks of the mountains are not very deep, but in heavy rains, sometimes approaching cloudbursts, a tremendous volume of water rushes down them, carrying large boulders. A certain amount of seepage collects in the agglomerate, lying below the conglomerate, and is retained in the local fractures. Some shallow wells have been sunk in this agglomerate, and one well over 150 m. deep was sunk on, the Volcan ranch, supplying about 76 1. (20 gal.) per min. A considerable supply of water is collected in large earth reservoirs in and below the town of Esmeralda. In ordinary years this supply will last until January or February, after which the Volcan well has to be depended on until the next rainy season.

Jan 8, 1922

By G. Ostberg

OXYGEN has frequently been considered responsible for phenomena in the metallurgy of cast iron which are not sufficiently explained by the presence of other elements. Oxygen and oxides have been regarded as critical factors, particularly for the solidification process, and specifically in the formation of graphite. However, the evidence for an influence of oxygen has mostly only been indirect or qualitative. Furthermore, quantitative data on the oxygen content of cast iron presented in the literature have often been less conclusive as being apparently determined with insufficient regard for the difficulties associated with the sampling and analysis. These problems, experimental and theoretical, have been studied in this investigation. An attempt is made to bring the views on the soluble amount of oxygen in cast iron on a level with the present understanding of the thermodynamics of these types of alloys. Although there are no experimental data on the complete multicomponent cast-iron alloys some conclusions have been drawn from investigations on simpler systems. The order of magnitude of the solubility of oxygen in cast iron is considered in the first part of the paper. The second part deals with the oxygen content actually present under practical conditions. First the possible sources of errors in sampling and analyzing methods are examined. Finally some observations on the oxygen and oxide content of malleable iron during the production process are made. THERMODYNAMICS OF OXYGEN SOLUBILITY When cast iron is saturated with oxygen the saturation phase is essentially carbon monoxide or silicon dioxide depending upon the composition of the iron, the temperature, and the rates of formation of the oxides.* The latter occurs accordiw to the O + C = CO, Kc0 - a COa J 20 + Si = SiO2, Activities are used here instead of weight pct concentrations, since activities are believed to show more sensitively the effects of the interaction of all the alloying elements. Calculations involving activities are, however, seriously hampered by lack of experimental data on the interactions between the components encountered in the multi component cast-iron system Fe-O-C-Si-Mn-P-S- and so on. In order to make an estimate of the oxygen solubility reason-

Jan 1, 1959

By JOHN R. SUMAN

I WOULD like to spend a few minutes describing to you the present condition which exists in the oil industry and then point out some aspects of this deplorable situation in which I think petroleum engineers can be helpful. As you know, the oil business at this time is in a very critical condition, .due to the tremendous potential production in excess of current demand. This is a world-wide condition as well as a national problem, as it is estimated that the surplus production available for the market in foreign countries is of about the same proportion as that existing in the United States. Due to the inability within the United States to hold production within the bounds of demand prices have been slumping for the last four years and at this time have reached the point where the sales value of the average barrel of crude oil in the United States, is far below the cost, of production. In addition to the large amount of potential production available for the market in excess of demand we have in storage in the United States about six hundred fifty millions of barrels 'of oil. Unless something can be done to limit the amount of oil coming onto the market to a point well below the demand, which point will permit the reduction of stocks, it looks as though the 'oil business is facing demoralization.

Jan 1, 1931

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,' It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle's publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By Yap Chu-Phay

Although chronologically the Sb-Bi system was the first one studied by the writer, the theoretical basis of the equations used in this paper is fully discussed in the writer's paper on the iron-carbon system,' because he believed that many would be more interested in the iron-carbon alloys. He suggests, therefore, that the reader consult that paper to familiarize himself with the theoretical aspect of the thermodynamic treatment outlined herein. This paper is divided into two parts: Part 'I deals with the Sb-Bi system and Part II deals with the lead-rich side of the Sb-Pb system. Although the former system has not much practical interest now, it has great theoretical interest in that it is the one system that for a long time was thought to have (and under specific conditions still has) an anomalous solidus, which no amount of physical investigation could adequately account for. The latter system, of course, is particularly interesting in the lead-rich end. It will be shown that the thermodynamic method is capable of predicting reliably the equilibrium position of the solidus, and thus acts as a check on the experimentally derived solidus. PART I.—THE ANTIMONY-BISMUTII SYSTEM In connection with his studies in thermoelectric phenomena,-the writer was naturally interested in the system Sb-Bi. In consulting the International Critical Tables2 he found the constitutional diagram shown in Fig. 1 (not including Ôtani's solidus), essentially after Cook,³ who investigated the system carefully by thermal analysis. Note the isothermal crystallization of alloys varying in composition from about 48 per cent, (by weight) to pure Bi. This is anomalous, because, according to the phase rule, in a binary system when only two phases coexist, there is univariant equilibrium; that is, the composition changes with the tempera-

Jan 1, 1931

By Albert Sauveur

Iron, like other metals, solidifies through the formation of dendritic crystals; iron alloys forming solid solutions, like other solid solutions, solidify likewise through the formation of dendritic crystals. The alloying elements or impurities as well as the inclusions segregate generally in the interstices, or "fillings," between the axes and branches of the dendrites; that is, in the portions last to solidify. This results in dendritic segregation or heterogeneity, which is generally persistent and makes possible the revelation of the dendritic crystallization of the metal through the selective action of a suitable etching reagent.' For this purpose, a cuprie solution, such as Le Chatelier's, is generally used, copper being deposited on the pure, or relatively pure, ferrite present in the axes while the fillings remain free, or relatively free, from copper deposition. The dendritic structure, formed on solidification in a steel containing 0.50 per cent. carbon, 0.37 per cent. manganese, 0.12 per cent. silicon, 0.07 per cent. sulfur, and 0.035 per cent. phosphorus is shown, after treatment with Le Chatelier reagent, in Fig. 1 under a magnification of 8 diameters. Commercial steel always contains inclusions of manganese sulfide, which are located in the fillings of the dendrites. Comstock has shown that boiling sodium picrate imparts a dark coloration to these inclusions. We find that this reagent likewise reveals dendritic segregations in commercial steel, as shown in Fig. 2, under a magnification of 8 diameters. which represents the same spot as that shown in Fig. 1. The fillings have been darkened while the axes remain white, the action being, therefore, the reverse of that of cupric reagents. On closer examination, under higher magnification (Fig. 3) it is found that the picrate blackens the small particles of manganese sulfide, that these are frequently surrounded by a rim of white, or relatively white, ferrite, and that both the ferrite

Jan 1, 1924

By James W. Shaffer

Aluminum is the most abundant metallic element and forms 8% of the earth's crust. Because of its chemical activity it does not occur in nature in a metallic form but principally in the silicates, feldspar, mica, shale, and clay. Bauxitic raw materials-bauxitic clay, aluminous laterite, and bauxite-develop from these aluminum silicate sources. Bauxite and aluminous laterite are naturally occurring mixtures of aluminum hydroxides and mineral impurities, and they are the major sources of aluminum. End Uses Bauxite is the basic ore of the aluminum industry. It is refined into aluminum hydroxide and calcined for feed stock to electrolytic smelters. Over 90% of the tonnage mined is refined and smelted into aluminum. The total tonnage consumed by other industries is small in comparison, but bauxite and alumina are important for the manufacture of refractories, ceramics, chemicals, abrasives, pharmaceuticals, catalysts, cements, dessicants, and flame retardants. Some aluminum-containing industrial products are made from clays and other materials but the majority originate from bauxite directly or from aluminum hydroxide and alumina refined from bauxite. Lateritic type bauxite is also used as building and decorative stone. Geology Mineralogy and Properties Bauxite is a mineral raw material composed principally of one or more aluminum hydroxide minerals and impurities of silica, iron oxide, titania, and other elements in minor or trace amounts. The important aluminum hydroxide minerals are gibbsite, boehmite, and diaspore. Bayerite, nordstrandite, and tucanite are naturally occurring aluminum hydroxides but are rare and not commercially important. Mixtures of gibbsite and boehmite are common, boehmite and diaspore less common, and gibbsite and diaspore rare. Gibbsite is aluminum trihydroxide. Boehmite and diaspore are aluminum oxide hydroxides and have essentially the same composition, but diaspore has a greater hardness and a more tightly bonded and denser atomic structure. Although not technically correct, the commercial terms trihydrate and monohydrate are frequently used to distinguish types of bauxite. If bauxite is all or nearly all gibbsite, it is referred to as a trihydrate ore; if boehmite or diaspore or a mixture of both are the dominant minerals, the bauxite is called a monohydrate ore. If substantial amounts of both gibbsite and boehmite are present, the bauxite is frequently referred to as a mixed ore. Properties of major bauxite minerals are shown in Table 1. Silica, iron oxides, and titania are major impurities always present in deposits of bauxitic raw materials.. Silica impurities usually occur as clay minerals, micaceous minerals, or quartz, but cristobalite and feldspar are found in some deposits. The most common clay minerals are kaolins; however, illites and chlorites are often found in small quantities. Varying proportions of aluminum, iron, and clay minerals make bauxite, aluminous laterite, ferruginous laterite, and bauxitic clay deposits gradational with each other. Hematite and goethite are the common iron mineral impurities in many bauxites. Magnetite and ilmenite occur in deposits derived from basic igneous rocks. Other iron minerals associated with bauxite are maghemite, pyrite, siderite, and marcasite. The titanium minerals found in bauxites are anatase, leucoxene, rutile, ilmenite, titaniferous

Jan 1, 1983

By H. W. Russell, Paul D. MILLER

IT is known that austenitic chromium-nickel steels that have free carbide in the grain boundaries are subject to intergranular corrosion. It is difficult to detect such a susceptible condition in a fabricated article because present test methods require a sample section for examination and in most cases this is difficult to obtain. The question of the nature and prevention of intergranular corrosion in austenitic stainless steels have been ably discussed by Bain and co-workers1-3 and by other investigators.4-10 The present methods of study subject samples to corrosive conditions in such reagents as the Strauss solution, a. mixture of copper sulphate and sulphuric acid. Such tests usually require at least 72 hr. to run. Various methods of measuring the degree of sensitization have been employed, such as the measurement of electrical resistivity, magnetic measurements, measurement of the degree of cracking produced on bending over a mandrel, and microscopic studies. The detection of carbides at the grain boundaries by metallographic polishing and etching methods is tedious and requires a skilled operator. A recent report on such methods of carbide detection is given by the American Society for Testing Materials Subcommittee VI of Committee A-10 11 and by Arness.12 The present investigation was undertaken to develop a simple test procedure for detecting carbide precipitation or susceptibility to intergranular corrosion. The test is designed for use in the plant and for the testing of fabricated structures. Carbide precipitation, the factor leading to susceptibility to corrosion, is produced by heating the alloy in the temperature range 800° to 1600°F., as in welding, in improper annealing or in service where such temperatures are met. The connection between such precipitation and susceptibility to corrosion has been thoroughly discussed, as has been the use of stabilizing addition elements to prevent precipitation. EXPERIMENTAL METHOD A small area of the steel under test is subjected to an anodic treatment in a cell that can be clamped onto a sample or an actual structure. The cell and electrical circuit used are illustrated in Fig. I. The cell C is lead, joined to the steel plate D and insulated from it by a short piece of rubber tubing E. The cell is forced tightly against the steel plate by a spring or clamping device. The seal formed by the rubber against the steel plate is sufficient to retain the liquid bath inside the cell. The spot treated can be made any shape desired, depending on the shape of the rubber gasket. The cell illustrated polishes a circular spot about 3/8-in. diameter. The bath consists of 60 per cent (by weight) sulphuric acid to which is added 5 ml. per liter of Glycyrrhiza extract (U.S.P.). The cell requires about 2 to 2.5

Jan 1, 1941

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.' The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.' The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00' were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-'. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By George S. Rice

MANY studies on ground movement and subsidence have been carried on by members of the Institute during the past year, but only a few papers have reached maturity. Two of the mining schools of this country have continued their interest in ground movement research. At Columbia University School of Mines, Philip Bucky has continued his investigations, employing photoelastic methods and the use of his centrifugal apparatus for testing what he termed "the strength and behavior of mining structures." Helmut Landsberg, of The Pennsylvania State College, has developed a convergence recorder similar in principle to that used by the

Jan 1, 1936

By G. W. Neighbor, M. S. Abrahams

The actice slip plane in InSb is found to be of the {111} type by using the method of two-tmce anulysis. Measurements of the rotation of the tensile axis with increasing plastic shear strain indicate that the tnacroscopic slip direction is a <110>. Recrystal-lization is first observed at a sheav strain of about 70 pct for a crystal deformed at a temperatzcre of 473° C and at a shear strain rate of 2.90 times 10- %ecc-I; the dislocation density corresponding to this value of the strain is 1 x 108 em-&apos;. At a shear strain of about 170 pct, the recrystallization process is complete. This appears to be the fimt time re-crystallization has heen observed in a semiconductor. V HE operation of the {Hi} glide plane in Ge was first noted by Gallagher.&apos; This finding was confirmed by Treuting who also extended the result to Si. Using X-ray techniques, Treuting3 demonstrated that the macroscopic slip direction in Ge was of the <110> type. The choice of the (111) <110> slip system in Ge is exected since in the diamond-type structure the {Ill7 plane is the plane of highest density and the <110> direction is the direction of closest packing.4 There is little reason to expect that the glide elements of InSb are different from those of Ge, since the zinc-blende structure characteristic of InSb is quite similar to the structure of Ge. With regard to InSb, Allen5 has indicated that the glide plane is the {111} type. There appears to be no quantitative determination of the glide direction, however. The present work was undertaken to establish both the glide plane and glide direction in InSb and also to see if recrystallization occurs at large shear strains. EXPERIMENTAL PROCEDURE Mechanical Deformation. The single crystals of InSb used in this investigation were deformed in uni-axial tension. The tensile axis of the specimens was [145] and the periphery was bounded by (111) and (321) planes as shown in Fig. 1. The metallographi-cally polished specimens were deformed in a dynamic atmosphere of He, using an Instron machine. The tensile tests were performed at temperatures in the range of 300°C to the melting point (525OC) and at shear strain-rates varying between 1.94 X 104 sec-&apos; to 1.94 x 103 sec-&apos;. Additional details concerning the preparation and deformation of the specimens have been presented previously.&apos; Analysis of the Glide Elements. The traces of the active slip plane in both (111) and (321) planes were analyzed according to the usual method of two-trace analysis." The macroscopic slip direction was determined by measuring the rotation of the tensile axis as a function of plastic strain,8 These measurements were made from Laue back-reflection X-ray photographs. The X-ray beam was perpendicular to the (111) plane. A given crystal was used for only one measurement of the rotation of the tensile axis after it had been strained to a predetermined value. Therefore, care was taken at all times to insure that the X-ray beam was parallel to the [Ill ] direction of all the samples. RESULTS AND DISCUSSION Glide Plane. After 3.4 pct plastic shear-strain, at a temperature of 369°C and a shear strain-rate of 1.94 x 104 sec-&apos;, the slip traces on the (111) and (3.21) planes appear as in Figs. 2(a) and 2(b), respectively. The results of an analysis of these glide markings demonstrate that the slip plane is (111). The operation of this plane is expected on the basis of the orientation of the specimen, since glide on this plane and in the [I011 direction will result in

Jan 1, 1962

By E. W. Engelmann

A NEW and interesting type of drier has been developed and operated at the Magna plant of the Utah Copper Co. for the past year for the drying of a filtered concentrate in the molybdenum recovery plant of this company. The several units installed have ranged from 12 to 30 in. in width, and from 14 to 30 ft. long. Their economy was immediately apparent after the first one was installed. The machine is not only low in capital cost, but has proved efficient for the drying of fine concentrate at low operating cost. The Utah vibrating drier consists of a steel conveyor trough supported on flexible reeds from a structural steel foundation anchored in concrete. The steel pan, which is also the drying surface, is vibrated by a heavy Utah electromagnetic vibrator fastened either to the head or discharge end of the pan. The vibration thus obtained agitates the material and causes it to be conveyed over the heated surface.

Jan 1, 1938