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By Nicholas J. Grant, William H. Ferguson, Bill C. Giessen

Ta-lr alloys have been examined over the complete range of compositions using metallographic and X-ray techniques. The terminal solid-solubility limits, solidus temperatures, and intermediate phases were determined. There are four inter-mediate phases: o, tetragonal, analogous to a (Fe-Cr); 0,. orthorhombic; az, tetragonal; and a TaZr,, cubic, AuCu, structure. Of these, o and a, melt peritecticaLly, a, decomposes peritectoidally, and a TaIrs has a congruent melting point. Three peri-tectic and one eutectic reactions occur. 1 HE Ta-Ir phase diagram has not been treated in the literature. Intermetallic phases and terminal solid solubilities have been described and estimated.'-4 The previous findings have been confirmed in this work. A complete diagram with additional phases and solidus curves is presented. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by the National Research Corp., Cambridge, Mass., and iridium powder of 99.9 pct purity, supplied by the Bishop Co., Malvern, Pa. Both powders were -200 mesh. Table I lists the analyses as given by the suppliers. A standard procedure was employed in making the alloy buttons, which was described in detail in Refs. 5 and 6, and which included repeated arc-melting of powder compacts and determination of the composition by the weight-balance method. This is especially justifiable due to the similar vapor pressures of tantalum and iridium. In the critical parts of the diagram, a spacing of 1/2 at. pct was used, based on premelted master alloy material. The observed structures and X-ray spectra were consistent with the composition sequence of the alloys. Table II lists the final alloy atomic percentages with the calculated percent error of composition. Cross sections representative in grain size and composition were selected for the study, as described in Ref. 5. Based on prior experience, no contamination from the tungsten electrode was considered. Temperature measurements were obtained using a Leeds and Northrup optical pyrometer and have been described extensively in Refs. 5 and 6. All heat treatments were made in the high-vacuum tantalum tube furnace mentioned in Ref. 5. Samples annealed in tantalum containers cooled from 1800" to 1000"~ in 5 sec; those annealed in ceramic crucibles cooled over the same range in 15 to 30 sec. The thermal treatments are listed in Table 111. All specimens were homogenized at 1735°C for 24 hr. Tantalum-rich compositions were treated in tantalum buckets. Iridium-rich compositions were annealed in tantalum buckets below the eutectic temperature of 1950°C; up to 2200°C, tungsten-lined tantalum baskets were used; and above 2200°C thoria crucibles were used. It was found that refractory oxides (in early stages of the investigation alumina crucibles were used up to 1800°C and thoria crucibles were used to 2400"~) give off minute amounts of oxygen and thereby influence the microstructure considerably, or react directly with the alloys.

Jan 1, 1963

By N. A. Zeigler

GRaphitization phenomena occurring in solid cast iron have principally been studied from the angle of the reactions taking place during annealing of white castings in the manufacturing of malleable iron. The selected bibliography at the end of this paper presents the high spots of the published information in this field. Graph-itization of gray iron upon reheating has received much less attention, primarily because only on rare occasions is this material subjected to any kind of industrial heat-treating. Moreovcr, articles made from gray iron are seldom used commercially at temperatures when any graphitization can take place. When used in such conditions, it is assumed that the articles can be replaced at frequent intervals, which can be afforded because of the low cost of gray iron. However, there is at least one commercial process in which articles made from gray iron, during their manufacturing processing, are subjectcd to rather high temperatures; that is, manufacturing of cast-iron enamelware, which is glazed at about 1600° to 1700°F. (870' to 930°C.) From practical experience, it has been found that one of the convenient and economical compositions of gray iron suitable for enameling is, in round figures, as follows: Si, 2.50 per cent; Mn, 0.35; S, 0.07; P, 0.80; T.C., 3.35; C.C., 0.70. Since this iron usually is cast into thin-walled sections, the percentage of com- bined carbon in it is relatively high. Upon heating in the enameling furnaces, this combined carbon graphitizes, which causes permanent dimensional changes of the articles. Obviously, from practical considerations, it is desirable to maintain these dimensional changes as constant as possible. In the course of experimentation with this iron, two series of experimental heats were prepared in which the manganese to sulphur ratio of the standard cupola metal was offset by ladle additions of: (I) progressively larger amounts of sulphur, and (2) progressively larger amounts of manganese. Each one of these ladle charges was cast into experimental plates 8 by 4 in. and about 5/16 in. thick. All told, 13 ladle charges were thus treated. All of them are listed in Table I, together with their chemical analyses. It may be noted that the manganese to sulphur ratio in these samples ranges between 1.2 and 30.2. Every one of these compositions was subjected to thermal allalysis, using an automatic, self-recording differential dila-tometer. The specimens used in this instrument are 50 mm. long and 4 mm. in diameter. During the dilatometer cycle they are kept under a vacuum of about 3 microns. Each one of them was subjected to a thermal cycle by heating it to I830°F. (1000°C.) in 3 hr. and cooling to room temperaturc in 5 hr. Figs. I, 2 and 3 present three automatically recorded dilatometer curves for irons: Serial No. I (normal composition), Serial No. 6 (high sulphur), and Serial No. 13 (high manganese). All three of these figures are

Jan 1, 1945

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 Yves Dardel

THE literature concerning the remelting of aluminum and its alloys is very rich. Unfortunately the greater part of the papers about this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification1,2 are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges and the atmosphere of the furnaces bring into the bath during the successive remeltings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, .. , if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H2, 02, H2O, C02, CO, CH4, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of Sieverts3 as a function of its partial pressure PH2 in the atmosphere [m = K _%/PH, [I]] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Röntgen and Braun4, Röntgen and Möller5, Bircumshaw6 and Winterhager7 have rendered it possible to determine the value of K, when the temperature is inferior to 1.000°K. One obtains: [log K = - 4,702.5 + 0.238 [2]] Besides its usual signification, the term PH2 represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is, when no gas exchange occurs between the two phases, the pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary occurs, the quantity of H2 should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature lowers, the internal pressure of H2 increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a maximum depending on the hydrostatic pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However, even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1947

By Haydn H. Murray

The term clay is somewhat ambiguous unless specifically defined because it is used both as a rock term and as a particle size term. Actually most persons using the term clay realize that it has a double meaning and in most instances define it. As a rock term, clay is difficult to define because of the wide variety of materials that compose it so that the definition has to be general. Clay is a natural, earthy, fine-grained material composed largely of a limited group of crystalline minerals known as the clay minerals. Many definitions state that a clay has the property of plasticity when wet, but some clays are not plastic, i.e., halloysite and flint clay; however, most clay materials are plastic when wet. As a particle size term, clay is used for the category that includes the smallest particles. The maximum size particles in the clay size grade are defined differently on some grade scales. Soil investigators and mineralogists generally use 2 microns as the maximum size. The Wentworth scale' defines clay as material finer than approximately 4 microns. Grim' has found it convenient to use the term clay material for any fine-grained, natural, earthy, argillaceous material and in this way can include clays, shales, or argillites, and some soils if they are argillaceous. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, still the term is generally understood by all who use it. Clay is an abundant natural raw material and has an amazing variety of uses and properties which will be discussed in this chapter. In order to understand better the relationships between the clays and their uses, a brief discussion of the structure, chemical composition, and identification of the clay minerals is given. Mineralogical Composition of Clays Clays are composed of certain groups of hydrous aluminum, magnesium, and iron silicates that may contain calcium, potassium, and other ions, which are called the clay minerals, and other minerals of variable composition, which are nonclay minerals. Both clay minerals and nonclay minerals influence the properties of a clay material. In order to understand the relationship between clay minerals and the properties of a clay material, a short summary of the structure and composition of clay minerals is necessary. Any scheme of classification tends to impose a certain rigidity and as new and additional data become available it is necessary to revise classifications. Brindley3 has discussed the classification and structural mineralogy of clays in very lucid fashion and chose a classification based on structural features and chemical composition. Grim2 proposed a tentative classification which is based on the structural attributes of the various clay minerals. This classification is relatively simple and workable, and is shown as follows: I. Amorphous Allophane group II. Crystalline A. Two-layer types (sheet structures composed of units of one layer of silica tetrahedrons and one layer of alumina octahedrons). 1. Equidimensional Kaolin group kaolinite, dickite, nacrite 2. Elongate Halloysite group

Jan 1, 1960

By W. A. Dickinson, H. F. Hendershot

THIS paper is a brief discussion of the past and present methods employed by the Huntington Works of The International Nickel Co., Inc., in the production of nickel and high nickel alloy seamless tubing. The various operations for both hot and cold processing will be considered in their natural sequence, together with the processing characteristics of the high nickel alloys and some descriptions of the equipment used. The tools and lubricants currently in use will be described. This discussion will relate primarily to nickel, Monel,† and Inconel,† since these are the most common of the many alloys processed into tubing at the Huntington Works. The nominal compositions of the materials are shown in Table I. CONVERSION FROM SOLID BILLETS TO TUBE SHELLS History The commercial production of seamless nickel and high nickel alloy tube shells is a comparatively recent development, the first nickel shells having been produced in 1922, Monel in 1930, and Inconel in 1931 on rotary-type piercing mills. Rolled or forged billets, ranging from 3 ½ - to 7 ½ in. diam, were pierced to produce shells ranging' in size from 4 3/8 in. OD X 0.180 in. wall to 8 3/8 in. OD X 1.0 in. wall. After piercing, the shells. were further processed by hot rolling, reeling, and sizing. Subsequent to these operations the shells were either supplied to the trade as "hot finished" tubes, or were processed by cold drawing to smaller sizes at the Huntington Works of the International Nickel Co. The extrusion of nickel and high nickel alloys also may be classed as a relative newcomer to the field of hot-forming methods, for it was not until 1928 that the commercial extrusion of these alloys was begun on a 600 long ton vertical extrusion press installed at Zenith Works of Henry Wiggin and Co., Ltd., Glasgow, Scotland. This press did considerable pioneer work and the results were so favorable that in 1937 a -2200 long ton horizontal press was installed. The quality of the inside surface of the tubing produced on this press was superior to that produced by piercing on a rotary-type mill and, as a result of this experience, a 4000 ton horizontal extrusion press was installed at the Huntington Works in 1943. Billet Preparation The first step in the extrusion, process is the selection of ingots with good hot malleability, as indicated by the test described by Martin and Bieber.1 Ingots then are forged into rough rounds which are machined to the desired billet diameter on a "bar peeler." This machine consists of a rotary head which carries the cutting tools and is driven by a 200 hp, dc motor. The feed mechanism consists of hydraulically driven input and output carriages on the respective sides of the cutter head. The diameter of the forgings used and the machined size or "billet diameter" that corresponds to the four different sizes of

Jan 1, 1951

By G. E. Warner

This paper presents a review and analysis of a highly stratified Burbank sand waterflooding project in Osage County, Okla. Permeability values in this reservoir range from less than 0.1 md to nearly 3 darcys, and 90 percent of the permeability capacity is contained in approximately 26 percent of the reservoir volume. To date, the project has recovered 103 bbl/flood-acre-ft since waterflood initiation, which represents 50 percent of the total preflood cumulative and 12 percent of the original stock-tank oil in place (OSTOIP). The outstanding feature of this project has been the economical recovery of a sizable quantity of oil at water-oil ratios higher than those normally considered prohibitive. Nearly 70 percent of the recovery to date has been achieved at water-cut values greater than 95 percent. An ultimate waterflood recovery of 138 bbl/flood-acre-ft, or 67 percent of the preflood recovery and 16 percent of the OSTOIP, is predicted. The ultimate primary and secondary recovery will be 302 bbl/acre-ft and approximutely 40 percent of the OSTOIP. The actual performance is compared with the predicted performance by both the Stiles and the Dykstra-Parsons methods, and applicabiliry of these methods to this particular reservoir is evaluated. The performance of this project indicafes highly stratified reservoirs can be successfully and economically waterflooded when either reservoir or economic conditions preclude the use of mechanical and chemical means of mdbility control. Introduction The concept of the stratified reservoir has been used by reservoir engineers for many years to describe the vertical variations in permeability within a reservoir. Numerous techniques have been advanced to predict the expected waterflood performance of the stratified reservoir, and in most cases they prove reasonably accurate. The advisability of undertaking a prospective waterflooding project is determined, based on these predictions. This paper presents a review of a waterflood project in a highly stratified reservoir that normally would be considered a marginal prospect, at best, when evaluated with any prediction technique properly adjusted for reservoir conditions. This kind of project can be successful if the predictions are used to design a waterflooding system capable of economically recovering an oil cut of 1 to 2 percent. Experience gained in the early stages of the project's development was profitably applied in the later development of the entire reservoir and could prove beneficial to other projects with similar reservoir stratification or fracture characteristics. The East Burbank pool waterflooding operations have been developed in three separate stages, each of which has been a separate project: Mid-Burbank Unit, Flood A, and Stanley Waterflood. When referred to collectively, these projects will be called the Composite Project. The Skelly Oil Co.'s Barber lease — the only portion of the pool not included in the three projects — is operated as a separate facility with a cooperative injection-well agreement. It contains less than 80 productive acres and would not significantly affect the over-all performance picture.

Jan 1, 1969

By R. J. Hafsten, E. S. Davenport, R. A. Grange

THE influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,1 and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely retarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths, Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745°F. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245°F. (675°C.), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarse-grained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite-that is, at temperature levels above about 1000°F. (540°C.)-but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to be presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000°F. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. MATERIAL AND EXPERIMENTAL PROCEDURE The material investigated was a commercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent M0. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

Rates and patterns of gas flow in an experimental blast furnace were investigated by measurements, at three levels, of gas compo-sitions and temperatures and by direct determination of gas transit time by a new method employing mercury vapor as a tracer. Infer-ences were drawn about localized reaction zones and the mechanism of the onset of' channeling. LACK of precise knowledge of the nature of gas movement in the blast furnace has always been an impediment to better understanding of the blastfurnace process as a whole. The effects upon operation of various types of charge distribution are very largely brought about by the modifications to gas flow which they occasion. Intelligent evaluation of these effects demands a better understanding of the factors influencing gas flow and the ways in which the flow pattern is altered by conditions existing in the stock column. The same knowledge is required before a fundamental approach can be made to the problem of establishing optimum lines for new furnaces. An experimental furnace is operated at the Bureau of Mines Central Experiment Station, Pittsburgh, Pa. Advantage was taken of experimental operation to conduct an investigation to develop and evaluate methods of study which could be applied later to industrial furnaces. The gas composition and temperature determinations were made as a preliminary study so far as gas flow was concerned but yielded significant information relating to other processes occurring within the furnace. The direct measurement of gas transit times by the mercury-vapor method constituted the major object of the investigation. Development of the mercury-vapor method was carried out while the data on gas composition and temperature were being collected. A complete description of the principle and development of the mercury-vapor method is beyond the scope of this paper but is available elsewhere. The results obtained and some consideration of the method's effectiveness and its potential value in the study of industrial problems will be treated here. DESCRIPTION OF FURNACE The general lines of the experimental blast furnace are shown in Fig. 1. The hearth diameter was 3 ft at the beginning of the investigation, and this was later enlarged to 3 ft 9 in. and finally to 4 ft to increase capacity. Tuyere to stockline height is 21 ft 4 in. The bosh depth is 3 ft 4 in. over which it opens to a width of 5 ft, and this diameter is carried up for 2 ft in a cylindrical section. The inwall batter of 1/2 in. per ft. is considerably less than in larger installations This may have influenced the movement of gaseous and solid materials. The furnace is inside a laboratory building and is charged from outside by a skip and hoist. Feeding into the first of three bell chambers, the stock is distributed by rotating the upper bell, the other two being used to obtain an effective gas seal. Three water-cooled tuyeres, with a nozzle dia-

Jan 1, 1960

By C. S. Barrett, D. B. Masson

Martensitic transformations have been found in AgCd both upon cold-working at room temperature and cooling to lower temperatures. The crystal structures of the transformation products were found to be close-packed hexagonal in the first case and or-thorhombic in the latter. The transformation characteristics also were studied. Similar treatment of AuZn alloys failed to yield any transformation. THE literature on martensitic transformations of body-centered cubic metals and alloys indicates widespread instability of this structure at low temperatures, a tendency which merits further study. The body-centered cubic ß-phase of CuZn, for example, when it contained less than 42 wt pct Zn, was found by Greninger and Mooradian' and others' to transform on cooling to subzero temperatures to a phase that was tentatively considered to be tetragonal. Further work by Massalski and Barrett" demonstrated that cold work at low temperatures causes a partial transformation of ß CuZn of higher Zn content. The structures of the strain-induced transformation products were found to be different from those induced by simple cooling. Another well-known martensitic transformation among body-centered cubic phases is that of ß AuCd, first studied with X-rays by Olander,' then very thoroughly by Chang and Read.5,6 Here again transformation was found to occur both as a result of cooling and of strain. The alkali metals Li and Na, as well as certain Li-Mg alloys, also undergo transformation from their normal body-centered cubic structure, both on cooling and on cold-working. The phase AgCd, the subject of the present report, should be expected to behave quite similarly to CuZn for a number of reasons. It is the chemical analogue of CuZn, silver being directly below copper and cadmium directly below zinc in the periodic table. The size factors (percent difference in size) of the atoms, possibly a consideration in the stability of the ß-phases, are +3.1 in AgCd and + 4.2 in CuZn. Likewise the relative electronegativities of the two pairs of metals are about the same, CuZn possessing an electronegativity difference of 1.0 and AgCd one of 0.8. These values are from a table of electronegativities given by Darken and Gurry." The phase diagrams of the two systems around 50 atomic percent are similar, both possessing a disordered body-centered cubic phase, ß, at high temperatures and an ordered bcc phase, ß, at room temperature; however, the ß and ß' phases of AgCd are separated by a hexagonal phase, [, stable in the range 220-440oC, which has no analogue in CuZn. There has been confusion in the literature as to the structures of the ß' and [-phases. The phase diagram in the ASM handbook'" has the structures of the two phases interchanged; however, Hansen" reports the correct relative positions and Muldawer" verified that ß', the low-temperature phase, is body-centered cubic. Work by the present authors also

Jan 1, 1959

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By Edmund M. Warner

Any city dweller who has walked alone along a remote mine passageway has to be impressed by the eerie silence-the total absence of noise except for one's own breathing and scuffing of boots on the bottom. An underpound mine can have tremendous contrasts, from complete silence to the ear piercing clatter of percussion drills working in the mine roof. Noise in underground mining machines is both useful and detrimental. Without characteristic noises that are recognizable to miners, operators would have a more difficult job operating their machines. Noise serves as a warning of approaching machinery, and changes in noise give indication that breakdowns may occur. But excessive noise is a health hazard. In recognition of this fact, our congress included noise exposure as a part of the "Coal Mine Health and Safety Act of 1969." As [Fig. 1] indicates, allowable noise exposure is established by specifying a time duration permitted at different noise levels. This is the well known "Walsh-Healey" criteria which govern noise exposure in many industries. In most industries noise exposure is not a constant value. Noise emitted from coal mining machinery varies widely, and therefore interpretation of compliance is not a simple matter. Time, environment, instrumentation and machine productivity, as well as the designed machine characteristics affect the results. It is the purpose of this paper to present the underground coal face machinery noise problem from a manufacturer's point of view. Manufacturers are very much aware of their responsibility to alleviate the noise problem. Not infrequently, orders are received from coal operators that a given new machine must comply with "The Coal Mine Health & Safety Act" noise regulations. Such a request is indicative of the misunderstanding which exists with machine users, while indicating their desire to comply with the law. Obviously, if all machinery could be designed and used at some arbitrary low noise level, it would be possible to simplify the regulations. However, there still remains the pervasive problem of existing machines. Extensive investigation to create practical retrofit kits for existing machines, to substantially reduce noise have been only marginally successful. Certain machine mechanisms are inherent noise makers. The only really good solution is to substitute a quieter mechanism. Such overall new designs have been undertaken, and several examples are mentioned later in this paper. Before describing machine noise problems, it is necessary to define noise values. Noise levels are measured in decibels. The designation "DBA" is decibels measured on the "A" scale, or one in which the frequency sensitivity of the instrumentation is about the same as the human ear. The numbers are often misinterpreted because it is a logarithmic, rather than an arithmetic scale. In comprehending the numbers, it should be remembered that any increase of 3 dB doubles the sound power. In practical terms this means that two noises of equal power at the same distance away increases a dB reading by three. Consider [Fig. 2] showing a simplified case of a worker on a machine subject to

Jan 1, 1980

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By E. S. Davenport, R. J. Hafsten, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By R. J. Hafsten, E. S. Davenport, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.' A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

By Norman P. Goss

What would appear to be a very simple process on paper has proved to be overrun with a multitude of unseen difficulties. For more than 70 years attempts have been made to cast metals in a continuous manner, but it has been only within the last Io years that some degree of success has been achieved.1 Historical Development Bessemer's Experiments—Method I Bessemer was the first to try to cast molten metal in a continuous manner. His method is fully described in U. S. Patent No. 49053, issued in 1865. The patent drawing is shown in Fig. I. In this method the molten metal was poured between a pair of rolls of large diameter, which were cooled by water sprays. Means were provided to prevent moisture from coming into direct coptact with the molten metal. The width of the strip was controlled by the flanges. On paper this should work to perfection, but it is beset with many difficulties still awaiting solution. Bessemer failed to reduce his invention to commercial practice. About 1890 Bessemer's method was revived by Norton and associates (U. S. Patent No. 441375). They formed the Fluid Metal Rolling Co. at Maywood, Ill., and spent $250,000 in endeavoring to develop the technique for this simple method. Finally they had to abandon it. Naturally, they did carry the technical development far beyond anything Bessemer had done, but even so it was far from being a useful commercial success. In recent years it has undergone further development by C. W. Hazelett (U. S. Patent No. 2058447), who has succeeded in obtaining long lengths of copper, brass, aluminum, and even stainless steel. He introduced many' ingenious devices but the greatest obstacle still remained—the disintegration of the roll surface when the surface is heated and chilled in rapid succession. Difficulty is also experienced in maintaining a uniform supply of molten metal to the rolls. The patents pertaining to this method would indicate these to be the major obstacles. Experimental work by Mellen—Method 2 A departure from the method introduced by Bessemer, was tried by Grenville Mellen, of East Orange, K. J., sometime between 1914 and 1920, who obtained a number of patents.2 His method is illustrated in Fig. 2. This method failed to make an impression upon the art; however, it is of value in pointing out the difficulties the inventor ran into and the way in which he tried to meet them. The split mold sections form two endless chains. When going through the center of the apparatus, these sections engage each other to form a complete mold. As the engaged mold section moves downward at a constant speed, molten metal is teemed into it. As this is going on, another set of cooperating mold sections move into position on top of the one being filled. The molten metal is teemed into the mold through a silica tube. According to the teachings of this patent, the level of molten

Jan 1, 1945

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957

By L. T. Stanley

A method is described whereby the behavior of the front is approximated when gas is injected into a thick reservoir having reasonably homogeneous properties. The method is applied to the Abqaiq field of Saudi Arabia. The producing member is the Arab-D, a high-permeability calcarenite which has no continuous betlding planes. Field performance indicates the injected gas to be partially miscible with the reservoir oil because gas volume factors experienced are lower than those predicted by the gas law. Eqlrilibril~m calculations confirnz ihis and also show that the volume factor may vary appreciably, depending on the relative quantities of oil and gas in contact in the reservoir; consequently, volutnetric balances are made for the purpose of determining the behavior of the gas volume factor during injection history. The effect of gravity segregation on position and shape of the gas front is approximated by dividing the producing section into three zones vertically and tracing the movement of the average interface in each zone, with counterflow of oil and gas taking place betweell zones behind the front. This results in a gas front that advances more rapidly along the top of [he formation than along the base, producing an "umbrella" effect in cross section that becomes more pronounced as the front progresses. The calculations cover the gas-injection period of Abqaiq field history through 1958, and the position of the gas front is plotted at one-year intervals. Finally, some comparisotls between the calcrlated fronial position and the gas-oil contact as Measured by neutron logs are made. INTRODUCTION Fig. 1 is a structure contour map of the Abqaiq field. For analytical purpcses, the field has been divided into two areas designated A and B, as shown on the map. Gas injection into Area A was begun in early 1954 into two wells located near the crest of the structure on the north-south axis of the anticline. During the period covered by this paper, the average injection rate has been 122 MMscf/D with a maximum sustained rate of 160 MMscf/D. The reservoir pressure has been maintained at 2,450 psig since start of gas injection. The reservoir originally was undersaturated but, prior to pressure maintenance, the pressure was drawn below the bubble point in most of the Area A section, creating an in-place free-gas saturation of 8 per cent at the crest of the structure. The average critical gas saturation is 13 per cent established by laboratcry core tests. That the entire reservoir remained below critical gas saturation prior to gas injection is borne out by the fact that none of the crestal wells have exhibited high gas-oil ratios during production history. The Area A reservoir is a carbonate section about 200-ft thick having average porosity and permeability of the order of 22 per cent and 500 md, respectively. The productive horizon is the Arab-D member of Jurassic age and is encountered at an average depth of