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By Gordon I. Gould

The treatment of quicksilver ores to extract the metal, for centuries one of the fundamentally simpler metallurgical operations, has undergone few if any material changes during the past iew decades other than improvement and change of type of equipment used. Of almost universal application and as the seldom deviated from process, the roasting method is still considered superior to chemical metallurgy. Likewise, roasting of the crude ore without previous beneficiation continues to be standard practice, although some successful operations have employed concentration prior to roasting. The roasting process has been carried out in a variety of equipment, devised for different tonnage capacities, to treat "special" ores, and to satisfy an inventive notion of the particular builder, but during the past 25 years there has been one outstanding change in roasting equipment. This change, though neither originating in nor confined to the United States, has probably been developed and applied to a far greater extent in this country than in any other mercury-producing country of the world. The change from manually or gravity operated furnaces, mostly huge brickwork affairs justified largely by simplicity, lack of power and mechanical requirements, and occasionally by excellent metallurgical results, to mechanical furnaces, began actively during World War I under the stress of requirements for in- creased production, a shortage of labor, 2nd other factors to be brought out later. During the twenties the change to mechanical furnaces became nearly complete at American mines with the development of several types, the rotary furnace predominating. During the thirties, and the period of low prices in the early part of this period, few changes were made other than mechanical improvements and an almost complete acceptance of two types: the rotary furnace and the hearth or Wedge furnace. These two types have been developed to a high degree of metallurgical efficiency, have proved to be mechanically simple and have far greater flexibility and lower operating costs than pre-World War I furnaces. Of the two types the rotary is the more popular, about 30 rotaries having been in operation in the United States in 1943 as compared with about six hearth-type furnaces. The units of smaller capacity for roasting mercury ores have almost without exception been indirectly fired, such distinction being commonly accepted as the difference between retorts and furnaces, which are fired directly. The difference between indirect and direct firing obviously permits of quite different conditions surrounding the ore being roasted in relation to the chemical reaction to take place. In the indirect-fired unit the ore is contained within the body of the retort in a stagnant if not completely oxygen-impoverished atmosphere. In the direct-fired furnace the ore is in contact with the gases of combustion, which may easily (if not too easily) be supplied with an excess of

Jan 1, 1944

By Karl L. Fetters

In the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime arc required for phosphorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantitative relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composition encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and arc more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By J. L. O’Brien, M. Suenaga, K. M. Ralls, V. F. Zackay

The effecls of aging a1 400°C on tile resistive transition at 4.2°K of a superconducling 70Zr-30Nb alloy are reporled. Microstrclural changes were studied by critical temperature, resistiue critical field, residual resistiuily, and microhardness measurements and by X-ray diffraction, optical microscoby, ad replication electron microscopy. The result of the aging treat- A defect-free Type 11 superconductor in a magnetic field above Hc1 cannot sustain a transport current runt is a fine array of w-phase pavticles with a mean center to center interparticle spacing of about 800A. At an aging time of 300 hr the maximum onset critical current density is rcached. The particle size at the maximum current density if about 4202. At times longer than 300 hr effective particle impingement leads to lower onset critical current densities. perpendicular to the applied field without power loss in the sample.'-3 This power loss is due to flux line motion caused by the Lorentz force and is manifested by a longitudinal voltage.4-6 When defects are present in the material, flux lines are pinned until the Lorentz force exceeds the "pinning force". That is, it is thought that flux lines reside in free-energy wells existing at the defects, and the critical Lorentz force is that which when integrated over distance will supply the free-energy difference necessary to move the flux

Jan 1, 1968

By F. W. Miller

A brief history of byproduct coking in Alabama with short general descriptions of plants and the state's production of beehive and byproduct coke. PRIOR to the Civil War, there were several small charcoal furnaces for smelting the brown limonite ore that is found, in comparatively small bodies, throughout the central and north-central portions of the state. During the Civil War, these furnaces furnished charcoal iron to the Confederate Government. No attention was paid to the large bodies of lime-bearing hematite ore that now supplies the bulk of the ore used in the various blast-furnace plants of this district until the latter part of the 19th century. Red Mountain, which is the southernmost and one of the smaller ranges of the Appalachian Chain, lying immediately south of the Birmingham and Bessemer, is the principal source of this ore. The orebody outcrops on the northern face, extends through the mountain, and underlies Shades Valley on the southern side. When it was found that these ores could be worked satisfactorily in the blast furnaces, there was a comparatively rapid growth in the blast-furnace industry in the Birmingham district. As these ores are far more refractory than the limonite ores, this blast-furnace development was accompanied by the construction of beehive ovens to carbonize the coal, in order to supply the necessary fuel. The state's production of bee-hive coke in 1880 was 60,781 tons; ten years later this had increased to 1,072,942 tons; and, in 1897 the production had reached 1,443,017 tons. In 1898, the first byproduct oven built in the state was put in operation. This plant consisted of 120 horizontal-flue Semet-Solvay ovens, three flues in height by thirty flues in length with an average width of 16 in. The plant was constructed by Semet-Solvay Co., for the Tennessee Coal, Iron & Railroad Co., and was located adjacent to the blast-furnace plant of that company at Ensley. Coal was delivered from the Pratt mines, by gravity tracks, directly into bin's of the ovens after having

Jan 9, 1924

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4'5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.' The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495' in hydrogen was found to pro-

Jan 1, 1970

By G. H. Rowe, A. N. Stroh, D. P. Gregory

The magnitude and variation with strain of the parameters activation volume, V*; activation energy, H; and frequency factor, A, in the Arrhenius equation for strain rate are determined for colunlbium single crystals and polycrgstals. Comparison of dislocation structures in deformed columbium crystals as determined by transmission electron microscopy with the rate IF deformation of a metal crystal is a thermally activated process, rate theory can be used as a powerful tool in the study of dislocation mechanisms. seeger1 develops the following expression for plastic deformation governed by a single thermally-activated theory results suggests thai formation of lattice vacancies at jogs in screw dislocations is responsible for thermally activated deformation of poly crystalline columbium. Single crystals appear to deform by a different mechanism. Work hardening in fully recrystallized fine grain columbium is found to result from simultaneous decrease in activation volume and in the number of mobile dislocations with increasing strain. Work hardening in recovered polycrystals is found to result from decrease in activation volume with strain only. dislocation mechanism. His equation for strain rate is where N is the number of mobile dislocations per unit volume held up at energy barriers, v is the frequency with which the dislocations "try" the energy barriers, b is the Burgers vector, a is the area a dislocation loop sweeps out after overcoming a barrier, V* is the activation volume which will be defined more completely later, and t* is the thermal component of stress equal to (Ta-Ti), where Ta is applied shear stress and Ti is internal stress of the dislocation network17' given by

Jan 1, 1963

By Laurence Delisle

The aim of this paper is the description of a technique to be applied to the study of sections of metal powder particles, less than 20 microns in diam. with the electron microscope, by the replica method, using for replica a material such as formvar or parlodion. This work originated with the study of particles of tungsten powders. Such particles were too small to be examined in sufficient detail with the light microscope. On the other hand, examination with the electron microscope of the powders dispersed in the supporting film was not found satisfactory because: 1. It did not permit differentiating between single particles and aggregates. 2. It did not show the true outlines of the particles but only the projection of a whole surface. 3. No details appeared. For that reason it was attempted to make replicas of sections of the particles imbedded in a mounting material suitable for polishing and etching. The method proved satisfactory for the examination of tungsten powder and was then extended to car-bonyl nickel and carbonyl iron powders. Procedure Several mounting materials commonly used in ordinary metallography were investigated. The problem consisted in finding a mounting material

Jan 1, 1950

By Elmer W., Pehrson

NOT much serious consideration was liven to the military aspects of raw materials before World War 1. Following the outbreak of war in Europe in 1914, however. this situation was promptly changed. Disruption of allied shipping and German submarine warfare soon cut off a substantial part of the material the United Staten was accustomed to receiving from overseas. At the same time, raw material requirements rose rapidly as the tempo of industrial preparedness was stepped up in anticipation of war. By April 1917, when we entered the war, serious shortages threatened and consideralde attention was being given to our "deficcient" raw materials. The term "war mineral," began to appear after we became active combatants. But there is no evidence that "strategics" and "critical." as now used, had entered the lexicon of our raw materials experts during the last war nor were there apparently any officially recog¬nized list or definitions of what con¬stituted war materials. According to G. A. Roush in his book, `'Strategic Mineral Supplies," C. K. Leith, while serving as mineral advisor to the War Industries Board. compiled the first unofficial list of deficient minerals in 1917.

Jan 1, 1944

By J. Tarwater

The torsional testing of cylindrical medium-carbon steel specimens, heat treated to a high strength level, revealed a stress-strain relationship that was dependent on the direction of torsional plastic pre-strain. This Bauschinger effect was observed in prestrained specimens both with and without subsequent elevated-temperature strain aging. Yield stresses in strain-aged specimens exceeded those of simply prestrained specimens and the difference in stress was greater when the prestrain direction opposed the test direction. This behavior is discussed in terms of the classical dislocation pile-up using Cottrell's equation, A plastically prestrained strain-hardenable member, loaded in a direction opposite to the direction of prestrain, produces a stress-strain relationship differing appreciably from the curve representing reloading in the prestrain direction. This phenomenon, referred to as the Bauschinger effect, will be discussed in terms of the stress differences ob- served at a specified strain. The effect, dating back to the 1880's, was first attributed to grain boundary stresses. When later work revealed that the effect was also present in single crystals, revised theories attributed the diminished applied reverse stress to assistance from internal long-range stresses. These stresses have been associated with dislocation pile-ups or with dislocation arrays having analogous stress patterns. The stress patterns are subject to alteration by interaction with interstitial solute atoms and acceleration of the interaction may be accomplished with elevated-temperature strain aging. As discussed herein, the interaction showed a directional effect with regard to the applied stresses necessary for small plastic strains. Aside from the rigorous Bauschinger stress-strai relationship, which compares prestrained members, it is interesting to compare the stress-strain curve of a member being prestrained with that of a prestrained member being reverse loaded. For small strains which are a fraction of the prestrain deformation, the applied stresses of the reverse reloaded member are smaller. However, as the reverse strain approaches the prestrain value, the stresses approach equivalence. It has been reported1 that the stress required to return a prestrained specimen to its initial "zero" position generally exceeds the prestrain stress because of the work hardening occurring on potential slip systems during prestrain.

Jan 1, 1963

By C. W. Hill

FLUXES, in general, may be classified according to their use as soldering, foundry or casting, and metallurgical and the chemistry of their action follows quite closely this division. The term foundry or casting fluxes, as used here, refers to the substances added to molten metals, preparatory to casting into molds or ingots, with the object of removing small amounts of impurities that have been introduced in handling or melting the metal, which was placed in a fair state of purity by the previous refining or metallurgical processes. The sources of these impurities are the oxide coating on the surface of the ingots, material extracted or mechanically removed from the crucible or furnace wall, and those formed by the reaction of the molten metal with the heating gases or furnace atmosphere. As commonly used, the term fluxes is applied to such materials as ammonium chloride, zinc chloride, salt, borax, and boric oxide. A second class of materials, usually called deoxidizers, includes substances, such as metallic phosphides, sub-oxides, carbides, and bo-rides, that reduce the metallic oxides present in the metal. A third class includes various compounds that are molten and non-volatile at the temperature of the molten metal and are used primarily to protect the surface of the metal from the action of the furnace or exterior atmosphere; to this class belong such mixtures as lime and fluorspar, lime and soda ash, various minerals, etc. In some cases these protective layers may act in a manner similar to the metallurgical fluxes and dissolve or unite with the oxide impurities of the metal, but as generally employed this latter action is negligible since there is little opportunity for the coverings to come into contact with more than the surface of the metal, and hence they are without action on the body of the molten mass. The use of fluxes is the result of factory experience and tradition, but an extensive study has not been made of the chemical, and physical actions that occur or the effects of these actions on the properties of the metal. It would seem necessary in any successful study of metal fluxes

Jan 10, 1920

By B. S. Blakeney, E. P. Abrahamson II

The effect of the transition elements in binary solid-solution additions upon the recrystallization temperature of iron has been investigated. All these elements immediately raised the temperature, the majority having their greatest effect in less than 0.10 at. pct. A correlation is noted between the rate of change of recrystallization temperature with atomic percent solute and the electron configuration of the solute element. THE work of Abrahamson and rant' on binary chromium-base alloys indicated that a correspondence existed between the effect of each solute element on the brittle-to-ductile transition temperature of chromium and the ground-state electron configuration of the element added. This was felt to be a bonding phenomenon and would be expected to be observed in measurements of other properties involving the breaking or exchange of atomic bonds. From this work it was postulated that a like correspondence should be found for other properties of binary alloys, such as recrystallization. This study is an effort to check this postulation using binary solid-solution iron-base alloys. Previously, the majority of recrystallization studies were carried out on steels. However, Tammann2 investigated the recrystallization of iron as effected by Co, Ni, Si, Mn, Mo, and Cr and stated that elements with the same crystal structure at room temperature as iron appeared to be more effective in raising the recrystallization temperature. Austin, Luini, and Lindsay3 studied the effects of Ni, Cr, Mn, Co, Si, and Mo on cold rolling and annealing, but noted no trend. Abrahamson and rant,' in their work on the effect of both substitutional and interstitial elements upon the brittle-to-ductile transition of chromium, have shown that the outer electron configuration in the ground state of the solute element appears to be the prime determinant of the transition temperature. PROCEDURE All alloys were made using 99.95 + pct Fe with 0.02 wt pct 0, 0.004 pct C, and 0.001 pct N. All alloying elements were 99.9 + percent pure. Metal-lographically the alloys, out to at least 0.1 at. pct, appeared to be in solid solution. Though several published phase diagrams tend to dispute this.4 All alloys were arc melted six times and cast into square 400-g ingots under an argon atmosphere.

Jan 1, 1961

ASIDE from being the youngest of the Porphyries-from a producing, not a geologic standpoint-Andes probably presents the most finished piece of engineering, considering the enterprise as a whole: The various units of the mining and reduction works are well designed and efficiently operated, but that is true also at most of the other properties. Some mills or smelters may be superior to those at Andes; but as a complete mechanism for the exploitation of a big copper orebody, the Andes plant stands in a class by itself in many respects. Chuquicamata and Braden, as well as the properties in the United States, grew piecemeal. Capacities were increased and new plants were built as expansion progressed. Andes, on the other hand, existed on paper essentially as it is today before a start was made on actual construction of the reduction plant. More than $35,000,000 had been spent in developing and equipping the mine, and in building the concentrator and smelter, before the first ton of blister copper was produced on January 14, 1927. And another $12,500,000 was spent during the next two years in building the leaching plant and completing other construction. The orebody had been fairly well developed and tentative plans for the erection of reduction works had been made when the post-war depression descended on the copper industry and dictated deferment of the construction of a plant. This delay, however, gave the engineers opportunity to study the problems thoroughly in preparation for the design of the reduction works. The task was performed at Anaconda, Montana, under the direction of Frederick Laist, metallurgical manager, and Wilbur Jurden, chief designing engineer, of the Anaconda Copper Mining Company's staff. More than $1,150,000 was spent on

Jan 1, 1933

By B. F. Buie

Included in the general category of clays is a large and varied assemblage of nonmetallic silicate minerals which characteristically occur as fine-grained particles having flaky, sheetlike, or rod-shaped form. Most, though not all, are hydrous aluminum silicates. Amount and kind of impurities vary greatly, and these strongly influence the uses of the various clay types. Clays occur in a wide range of geological situations: as bedded sedimentary deposits composed of the weathering products of feldspar and other minerals; as alteration products of igneous, sedimentary, and metamorphic rocks weathered or hydrothermally altered in place; and, to a more limited extent, as hydrothermally introduced materials. TYPES AND MARKETS On the basis of chemical composition and crystal structure, two major groups of clay minerals recognized are the "kandites" or kaolin group, and the "smectites" or montmorillonite group. Another major type is illite, particularly important as a constituent of shales. Two additional mineral species having economic importance are attapulgite (palygorskite) and sepiolite. For present purposes, however, a classification based on utilization is more appropriate. The U.S. Bureau of Mines recognizes six types of clay: kaolin, ball clay, fire clay, bentonite, fuller's earth, and miscellaneous clay. Kaolin The kaolin group of minerals consists of the mineral species kaolinite, halloysite (metahalloysite), dickite, and nacrite, although the latter two are not being produced commercially. Kaolin, also called china clay, is a high-purity white material. Perhaps it is best known as a principal ingredient in the manufacture of chinaware, porcelain, and other high-quality ceramic products. However, by the mid-1970s very close to 50% of the kaolin produced in the United States was going to the paper industry for use as a filler and coating material. Manufacture of refractories uses about 12% of U.S. production. Kaolin is also used in plastics, in the rubber industry as a filler in footwear, electrical cable, and similar products, and as a conditioner of rubber for automobile tires to add strength and abrasion resistance. Smaller amounts are used in printing ink, paint, and adhesives; as insecticide carriers; in the production of catalysts for the petroleum refining industry; and in many other industrial and commercial applications. Production and use of kaolin in the United States doubled in the ten years from 1946 to 1956, and doubled again by 1966. Growth continues at a rate of about 7 % per annum.

Jan 1, 1976

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9'10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By Michael A. Toole, O&apos

INTRODUCTION The tremendous capital investment required to produce a low grade ore deposit demands a reliable answer to the question: "How much does it cost to drill a well to produce the uranium that geologists have indicated is there in the ground?" However, you will find the answers given will be many and varied, depending on whether they come from the operating company, the drilling contractor, a geologist, a reservoir engineer, purchasing agent, or whoever. Each generally considers only a limited area of the total operation. The operating company usually depends upon the drilling contractors, service companies, and consultants to supply expertise. Because it is often difficult to see the "whole picture" or even to agree upon what the "whole picture" is, planning a well program and its costs is often done piecemeal. Frequently, costs "saved" in one area of the program are needlessly spent in another, because the effect of one area upon the other was overlooked. Since the drilling fluid is such an influential part of the drilling program, it should be given utmost consideration when planning the overall program. As W. D. Lacabanne wrote in 1954: "The drilling fluid system is understandably called the heart of the rotary oil drilling rig. Any other type of rotary rig.... should benefit by the incorporation of mud fluids in the drilling scheme." And G. R. Gray mentions that "The driller recognizes the drilling fluid as one of the useful tools available to solve drilling problems." However, in minerals drilling, only in recent years has the drilling fluid been considered as more than a tool to get through special problem areas. Although there are many similarities between drilling for oil and gas and drilling for minerals, the differences in the drilling equipment used justifies designing specific fluids for the minerals drilling industry. NL Baroid/NL Industries, Inc. has been a leader in introducing such fluids and in providing technical know-how to the minerals drilling industry. The purpose of this paper is: (1) to discuss the selection of drilling fluids to meet specific drilling conditions during both exploration and production and (2) to show the interrelationship among factors present in the exploration and production phases that influence total well costs. DRILLING FLUIDS FOR DRILLING PROBLEMS The drilling fluid is a tool that can be used to improve drilling performance by improving hole cutting, cleaning, stability, and formation productivity. Properly formulated and maintained drilling fluids enable the drilling operation to be carried out with increased efficiency and lower total (overall) costs. However, it should be noted that not all drilling problems can be solved by even the most carefully prepared and maintained drilling fluids. Of the many possible drilling problems encountered in a well before reaching target depth, this paper will discuss only those most likely to be present in the shallow [61 to 610 m (200 to 2000 ft)] drilling operations in South Texas. LOST CIRCULATION Loss of circulation is the most common problem encountered in drilling. Because the losses occur under varied conditions, it is often difficult to determine the exact causes. "Lost circulation" or "lost returns" means the partial or complete loss of drilling fluid to voids in the formation. "Loss of water" while drilling with water may take place into any permeable section and should be distinguished from "water loss" or filtration of fluid through the filter cake of mud solids laid down on a permeable formation. "Loss of water" can frequently be stopped by the addition of colloidal sized clay particles such as high yield bentonites, whereas "water loss" may be controlled with organic polymers. Subsurface conditions that lead to loss of circulation can be classified as: (1) natural fractures, (2) induced fractures, (3) unconsolidated or highly permeable formations (loose gravel), and (4) cavernous formations (crevices and channels). Loss of circulation may occur whenever the borehole pressure exceeds the formation pressure. The greater the differential pressure, the more likely it is that circulation may be lost. To stop loss of whole mud, voids must be bridged so that a filter cake can be laid down on the permeable section. The plugging material must be of the proper size and shape to offer greater resistance to the fluid flow around it than the flow up the annulus. A plugging composition that satisfies these requirements may not be able to be handled by the small rig pump available.

Jan 1, 1979

By Axel Hultgren

IN ingots of silicon-killed carbon steel made without addition of - aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially. In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents arid, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,10,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis17 and their amount to increase from the top downward in the axial region .2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form," by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.15 Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19,20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping' or of refractory material from various sources1,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistance to hydrofluoric acid, imparted by the alumina content. Silicate inclusions, are often referred to as. the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1948

Jan 1, 1939

Jan 1, 1939