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By R. M. Hudson

Equilibrium constants have been determined for the jeaction C (in steel) + H2O = CO + H2 as a function of carbon content (0.013 to 0.74 ujt pct) and temperature (1200° to 1800°F) by using a flow system in which the water-vapor content of various gas mixtures containing hydrogen, carbon monoxide, and nitrogen was systematically controlled. The equilibrium partial-pressure ratio K1 = PcoPH2/PH2O was obtained for two low-carbon steels and four Fe-C binaries from a series of runs made at each temperature. By comparison of Ki with the analogous ratio for the reaction C (graphite) + H2O = CO + H2, the activity of carbon in steel (ac) was comDuted for each temperature and carbon content studied. From these data values of the equilibrium constants for two other carburization-decarburiza-tion reactions of importance were estimated. The chemical compositions of the two steels and four Fe-C binaries used are given in Table I. Specimens of Steel E were cut from a 0.035-in.-thick commercially box-annealed and temper-rolled lot of a low-carbon low-metalloid steel. Steel F was a commercially hot-rolled rimmed steel that was cold-reduced at the Laboratory to a 0.059-in. thickness. Fe-C binaries A, B, C, and D were vacuum-melted and poured, hot-rolled, pickled, and cold-reduced at the Laboratory to furnish specimens 0.035 in. thick. Sheet specimens were cut from all lots to approximately 3/4 by 3 in. by gage and were vapor-degreased with trichlo-roethylene and weighed before heat treatment. Heat treatments were carried out in a hinged-top Hevi-Duty electric furnace with a Vycor-glass tube. When the furnace was at the desired

Jan 1, 1965

By Lo-Ching Chang, K. M. Goldman

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By K. M. Goldman, Lo-Ching Chang

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.' The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country's annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg'ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

By William Metcalf

IT is the object of this paper to oppose unnecessary changes, and the introduction of new and confusing terms. From the earliest times of which we have any record on the subject, iron has been divided into general classes. Whether iron was first known in the form of wrought iron or of steel, is a matter of no importance; but at the time when cast iron first became a prominent article of commerce, wrought iron and steel were old products¬steel, at that time, being generally made from wrought iron by the process of cementation. As steel was then properly defined as iron containing more carbon than wrought iron, so cast iron was appropriately defined as iron containing more carbon than steel. Until the year 1776, when Huntsman first began the manufacture of a new kind of iron by melting wrought iron and steel in crucibles, the above definitions were all that could be desired. At first, probably, owing to imperfect appliances, only a highly carburized iron was melted in crucibles, and this led to its being called cast steel. If our ancestors had found a name for this material not involving the use of the word steel, we would have been saved the trouble of the present discussion. As the arts developed, new uses were found for steel, and the products of the crucible were varied, until at the present day it is quite common to find steel containing no more carbon than average wrought iron, and other steel containing nearly or quite as much carbon as some cast iron. All of these various products of the crucible have retained, or received, the name cast steel, usually abbreviated to the simple word steel, without causing any confusion among producers or consumers in regard to terms or their meaning. In 1855, twenty-one years ago, the Bessemer process was introduced ; this was followed in a few years by the Siemens-Martin process, and the products of both were at once, and have ever since been, called steel, from the fact that they were identical in chemical and physical properties with crucible cast steel. At the present time, then, we have three subdivisions of cast steel, viz.: Crucible cast steel, Bessemer cast steel, and Siemens-Martin,

Jan 1, 1877

By M. A. Hunter

CHAIRMAN M. A. HUNTER. UP to this time our stress-corrosion sessions have been concerned with stress-corrosion cracking in brass. In the succeeding sessions a variety of other products which are susceptible to stress-corrosion cracking are to be considered and this afternoon's session is to be devoted to stress-corrosion cracking in light metals. The problems you have had to deal with up to now in brass have been very simple ones. From this time on the complexities become greater. You have already learned in the preceding sessions, that copper is not susceptible to stress-corrosion cracking and when you begin to alloy it with 3 per cent or larger proportions of zinc, then stress- corrosion cracking ensues. You apparently have few complications in the copper alloys you make. There is apparently no precipitation on the grain boundaries in the brass, and no precipitation within the metal itself. So, on the whole, the problem is a simple one. Yet it has been with the brass people for a very long time and it is apparently not yet settled from the fact

Jan 1, 1945

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By N. Tiner

The mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed com-rnercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques,1"4 and Achenbach, Nippcr and Piwowarsky,% ased principally on thermal analysis, ascribe the grain-refilling action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the cffect of superheating on grain size of magilesium alloys. .ittempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. Thc preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. Preparation of Samples and Grain-size TestiNg The alloys investigated in this paper were taken from ingots made by Permanente the Or or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1946

By F. S. White, E. L. Kinsella

THE solids fluidization process brought out by the Standard Oil Development Co. in the early forties for catalytic cracking of petroleum enabled rapid transfer of large quantities of heat from gases to solids under closely controlled temperature conditions. As the technique developed, it was natural that applications for the process outside the petroleum industry would be sought. The calcination of limestone to ' quicklime requires the transfer of a large quantity of heat at high and closely controlled temperatures. For these reasons, this possible application was one of the first to be investigated. Laboratory work conducted by the Dorr Co. indicated that lime produced by solids fluidization would be of exceptional quality. Calculation of theoretical heat balances showed that savings in fuel could be expected. Accordingly, a pilot plant of 10 tons per day capacity was erected by the New England Lime Co. at Adams, Mass., to substantiate the process. Operation of the pilot plant, previously described,1 showed that excellent lime could be produced with a saving in fuel. The work also indicated the necessity of preparing feed to remove the finer fractions if dust losses were to be held to a tolerable level. A single-stage fluidized solids drier-stripper was developed to accomplish this sizing.2 Subsequently a commercial lime reactor was erected at Adams, beginning operation in June 1949, followed by air sizer facilities completed in November 1951. This paper will describe these two applications of solids fluidization. The raw material for preparation of lime by the fluidizing process is a high calcium crystalline lime stone having the approximate chemical composition shown in Table I. The stone is first prepared by crushing and grinding in conventional equipment to pass a 6-mesh sieve. After crushing, the material is sent to the FluoDry unit for drying and dedusting. Fluidized Drying and Sizing As shown in Fig. 1, the FluoDry unit consists of a 1/4-in. cylindrical steel shell, 9-ft ID by 22-ft 6-in. overall height. Attached horizontally at the bottom is a 6-ft diam combustion chamber, approximately 7 ft 6 in. long. A refractory constriction dome, consisting of first-quality fire brick shapes, partitions the inside into two sections. The lower section is called the windbox and the upper the bed compartment. The vertical wall of the shell is lined with 6-in. first-quality rotary kiln blocks. In the bottom of the windbox a hoppered section is formed with castable refractory to permit the windbox to be readily cleaned via a 6-in. screw conveyor. The combustion chamber is similarly lined with refractory shapes. On the 6-in. diam section, 4 1/2 in. of insulating brick, HW-26, are used. The inner combustion chamber is lined with 4 1/2-in. Korundal brick to withstand the high flame temperatures encountered. An 8-in. steel feed pipe, entering vertically through the top and fitted with an air-operated cone valve,

Jan 1, 1952

By H. C. H. Darley

The influence of particle size and concentration on the development of chip hold-down pressure (CHDP) was studied in an apparatus designed to measure the change of filtration rate during the first second of the filtration process. CHDP is controlled by the "bridging" particles (i.e., particles in the 50 to 0.2 micron range), whereas filter loss is controlled by the colloid fraction. The results indicated that a fast drilling fluid with a low filter loss could be obtained if the concentration of bridging solids and the viscosity were kept very low. A novel group of drilling fluids, which we have named colloid emulsions, was developed to meet the above requirements. These colloid emulsions are made by dispersing art oleophilic colloid in oil and emulsifying about 5 per cent of this dispersion in water or a dense brine. Good results have been obtained in field trials with emulsions which use asphalt as the oleophilic colloid. INTRODUCTION In recent years it has been found that fast rates of penetration can be maintained in hard formations by using "clear" water as a drilling fluid. In some cases, however, water cannot be used because the very high down-hole filter loss creates various difficulties in drilling, in logging, or in producing the well. It then becomes necessary to "mud up", which results in a decrease in drilling rate. The reason that mud decreases drilling rates is a complex subject which has been well covered by such authors as Garnier and van Lingen, Cunningham and Eenink,' and van Lingen.3 One of the principal factors involved is the tendency of the drilling fluid to develop a filter cake on the bottom of the hole. The pressure differential which develops across this filter cake opposes the action of the bit in dislodging chips from the rock. This pressure differential is referred to by Garnier and van Lingen' as the chip hold-down pressure, which is denoted by the initials CHDP in this paper. The work described in this paper was undertaken to develop a drilling fluid which would minimize CHDP but which would still have a low filter loss—in other words, a fluid which would deposit a filter cake on the sides but would lay little or no filter cake on the bottom of the hole. EVALUATION OF CHDP EXPERIMENTAL Conditions governing the growth of filter cake on the sides of the hole are obviously different from those on the bottom of the hole. On the sides of the hole, cake will form continuously but at a decreasing rate, until eventually the rate of growth will equal the rate of cake erosion by the mud stream.' On the bottom of the hole, each time a bit tooth dislodges a chip the cake is removed, a fresh rock surface is exposed, and the filtration process must start over again. Thus the CHDP is determined by the amount of cake which can form in the interval between successive tooth strikes at a particular spot, normally a fraction of a second. Our first step therefore was to study filtration rates over the first second or so of the filtration process. These tests were conducted in the simple type of dynamic filter cell shown in Figs. 1 and 2. In this cell the mud was filtered through a train of rock cores while rotating blades kept the mud flowing over the surface of the core. The procedure was to evacuate the cores to 0.05 mm of mercury, saturate with brine, and assemble in the holder under brine. The permeability of the core train was then determined. A plastic seal was placed on the face of the core train, and a rip cord was attached from the seal to one of the blades. At the start of the test, 500 psi was applied to the mud, and the meniscus in the capillary measuring tube was adjusted to zero. When the blades were started, t,he seal was ripped from the face of the core, and filtration began. The filtration rate was at first measured by photographing the advance of the meniscus in the capillary tube. Using

Jan 1, 1966

By Gerald Sherman

LARGE part of the mining industry is still under the shadow of the depression, and unwilling to undertake changes in plant or methods of operation that require large preliminary expenditures of money. Certain metals command fair prices: nickel, tin, and molybdenum. The precious metals, gold and silver, have been given greater values by natural processes of economics or by proclamation, but are of so much less importance in industry, in total value, and number of men employed, that they have not greatly raised the average for the mining business. The increased value of gold which was established in 1933 has stimulated .the search for new deposits, and aided efforts to revive some of the old mines 'Where it is hoped to find quantities of marginal ore now become profitable. The higher price did not increase production very much for 1934, but two discoveries of major importance, and others yet to be proved, will help later. The two referred to are the Lupa gold field in Tanganyika Territory, and the Silver Queen mine on Soledad Mountain near Mojave in California. The first was recently discovered, and is being developed by the East African Goldfields, Ltd. Uncompleted explorations of the croppings early in the year had exposed for measurement and sampling to a shallow depth, three ore shoots as gregating 7400 ft. in length and 6 ft. in width, containing 0.375 oz. of gold per ton. In the Silver Queen. an ore-

Jan 1, 1935

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of' copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C'. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.' As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."'- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

By M. R. Todd, J. Szekely

THE mechanism of carbon oxidation in steelmaking processes has attracted considerable attention in recent years. The generally accepted model postulates that the reaction between carbon and oxygen occurs at the surface of CO bubbles that originate at the suitable nucleation points and subsequently rise through the metal bath.1-4 Although this model describes adequately the behavior of open-hearth type operations, it is not a satisfactory representation of carbon oxidation in oxygen steelmaking processes since it cannot account for either: i) the very high rate of oxidation per unit bath area,or ii) the commonly reported shapes of the curves showing the dependenie of the oxidation rate on the carbon concentration. The very high decarburization rates commonly encountered in oxygen steelmaking processes need no further elaboration; some typical plots of the rate of carbon removal against carbon concentration, taken from a publication by Li, Dukelow, and smith,' are reproduced in Fig. 1. It is seen from the curves that the decarburization tends to decrease from a peak or a plateau once the carbon concentration falls below a certain value; in the experiments reported, this critical value ranged from 1.2 to 0.2 wt pct C. The apparent dependence of the decarburization rate on the carbon concentration indicates that within this region phenomena associated with the transfer of car- bon must play an important if not predominant role. Since the concentration of oxygen in molten iron at steelmaking temperatures (removed from the immediate impact zone) is only about 0.1 wt pct,6 it is clear that simple simultaneous diffusion of carbon and oxygen to the surface of CO bubbles could not account for the rate of carbon transfer being the controlling step at carbon concentrations as high as 1.0 wt pct. The purpose of this communication is to present an alternative model which may explain at least qualitatively the apparent anomalies mentioned and may stimulate further experimental work. The Physical Model. It is suggested that the principal mechanism of decarburization is the reaction between CO bubbles and an emulsion consisting of molten iron and molten iron oxide particles in the vicinity of the "slag-metal interface9'.* This mech-

Jan 1, 1968

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By Wllliam D. Davis

C OMMERCIAL production of oil in northeastern Oklahoma began in 1897 and in the next two decades this area became one of the greatest oil districts of the time. Its importance is now secondary, but thousands of wells in this area have produced uninterruptedly for more than thirty years. They are now classified as stripper wells. By means of what is known as water flooding their L. production can be considerably in- creased. This practice consists in injecting water under pressure into the sand surrounding an oil well, thus displacing the oil in the pores of the sand and forcing it into the oil well.

Jan 1, 1940

By H. L. Ames, P. H. Jennings, R. W. Stanley

A process has been developed for leaching copper, lead and calcium from molybdenite concentrate. The leachant is a solution containing an oxidizing chloride (e. g., CuC12, FeC13) and an alkaline earth metal chloride (e. g., CaC12). Cupric chloride and ferric chloride, in the presence of 20-30% calcium chloride, are effective oxidants for chalcopyrite and galena. Calcium chloride, in addition to promoting the rate of leaching, serves to lower the solution pH and raise the boiling point. Leaching for two hours at 110'~ with a 1 % CuC12-10% FeC13- 30% CaC12 solution results in the extraction of up to 98% of the copper in molybdenite, 98% of the lead, and 79% of the calcium. Less than 0. 5% of the molybdenum is dissolved. The leach solution can be rapidly and effectively regenerated with gaseous chlorine and recycled. Build-up of copper and lead in the leach solution is controlled by discarding about 30% of the leach solution each cycle.

Jan 1, 1973

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By William E. Ford, Edward Salisbury Dana

5. Crystallography. - The subject of Crystallography includes the description of the characters of crystals in general; of the various forms of crystals and their division into classes and systems; of the methods of studying crystals, including the determination of the mathematical relations of their faces, and the measurement of the angles between them; finally, a description of compound or twin crystals, of irregularities in crystals, of crystal- line aggregates, and of pseudomorphous crystals. 6. Definition of a Crystal.- A crystal * is the regular polyhedral form, bounded by smooth surfaces, which is assumed by a chemical compound, under the action of its intermolecular forces, when passing, under suitable conditions, from the state of a liquid or gas to that of a solid. As expressed in the foregoing definition, a crystal is characterized, first, by its definite internal molecular structure, and, second, by its external form. A crystal is the normal form of a mineral species, as of all solid chemical com- pounds; but the conditions suitable for the formation of a crystal of ideal perfection in symmetry of form and smoothness of surface are never fully realized. Further, many species usually occur not in distinct crystals, but in massive form, and in some exceptional cases the definite molecular structure is absent. 7. Molecular Structure in General.- By definite molecular structure is meant the special arrangement which the physical units, called molecules, assume under the action of the forces exerted between them during the formation of the solid. Some remarks are given in a later article (p. 22 et seq.) in regard to the kinds of molecular arrangement theoretically possible, and their relation to the symmetry of the different systems and classes of crystals.

Jan 1, 1922

By John T. Norton

FoR many years the copper-bearing steels have been of considerable interest to the metallurgist because of their corrosion-resistant properties. More recently the discovery of their definite age-hardening characteristics has focused attention on them again. In a recent paper, Smith and Palmer(l)† have given an admirable description of the behavior of a considerable number of steels of this type and a study of their results suggests two questions of a more or less fundamental sort. In the first place, it has been plainly shown that the hardening effect of added copper does not increase up to the maximum solubility of copper in iron as given by earlier investigators, but reaches its greatest value considerably below this point. This fact suggests that either the solubility is not so great as previous investigators have stated, or that the age-hardening mechanism is not the simple precipitation phenomenon that has been postulated. In the second place, the nature of the aging mechanism in this particular system should be determined. Recent developments in the study of age-hardening processes have shown that the increase of hardness is often, but not always, accompanied by precipitation and the action of a particular system is not predictable on the basis of its components or type of phase diagram. It would be of considerable interest to study the aging of the iron-rich iron-copper alloys in detail. One would like to know whether the aging mechanism is different at high and low aging temperatures, and whether the extreme sluggishness of the system may perhaps represent some new type of aging process. The experiments to be described were carried out in an endeavor to answer these questions. Obviously, in such experiments it is important to confine the hardening effect to the single element, copper, so that iron and copper of high purity must be used in the preparation of specimens. An observation of lattice changes during the aging process, correlated with the hardness changes, seems to be the best available method of

Jan 1, 1935