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By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By C. O. Fairchild

ONE of the fundamental principles of efficiency is the use of adequate and permanent records. The rapid increase in the manufacture and use of recording pryometers is a proof of the appreciation of efficiency principles on the part of the manufacturers engaged in the various technical industries. Where recording pyrometers are not employed in an industry in which temperature measurements are necessary, one will generally find that a printed form is used upon which is written, periodically, the temperatures measured by an indicating instrument. It is no serious condemnation of the workman to state that such records are often "doctored," but it is rather a reflection upon the executive who puts such temptation in the way of a workman. One of the well-known "tricks of the trade" is to "force." a furnace so that it will be at the proper temperature during the periodic trips of the foreman or other official. Indicating instruments and recorders may be used together to great advantage. The recorder furnishes .a printed record and a check upon the operator of the furnace, and a record of value in correlating properties of the finished product with the heat treatment. The indicator should be of assistance to the operator in controlling the furnace or oven. Modern practice requires a temperature-recording instrument that is as simple as possible, rugged, reliable, and sufficiently accurate. Of these qualifications reliability is paramount, particularly in cases where the recorder is used for controlling the temperature automatically. By a reliable instrument is meant one that will run continuously with little attention and with a consistent degree of accuracy. That is, if it is in error by 5 per cent. one day, it must be in error by a like amount on any other clay, and not by 2 per cent. or 10 per cent. The earlier forms of recorders were complex and delicate, or mechanically unsatisfactory and inaccurate, and required considerable attention to keep them in operation. Within the past few years, however, the development in the manufacture of temperature recording devices has been highly satisfactory and many excellent instruments are now available. .

Jan 9, 1919

Jan 1, 1881

By Irving Fatt, R. M. Weinbrandt

Efforts have been made for many years to observe pore structure of sedimentary rocks on a microscopic scale. A better description of the pore structure in reservoir rock would aid in the development of relations between flow through tube network models and flow in consolidated reservoir rock. The unique qualities of the scanning electron miscroscope (SEM) make it the ideal tool to use in a study of pore structure. Previous methods of studying pore structure included plastic casts of pore space and optical microscopy.l-7 There is now available a new method to observe three-dimensional flow channels in reservoir rock: a scanning electron microscope having variable magnification from X20 to X20,000 and approximately 1000 times the depth of focus of the conventional light microscopes. This microscope also can obtain stereoscopic images and can measure and diagram flow channels so that it is possible to construct a network of tubes that will model consolidated reservoir rock. THEORY OF THE SCANNING ELECTRON MICROSCOPE The scanning electron microscope (SEM) functions by projecting a beam of electrons through magnetic focusing lenses at a specimen and recording secondary electrons excited by the primary beam. The amount of secondary electron emission portrays the topography of the specimen because more secondary electrons are emitted from high points than from low points. A schematic of the SEM is shown in Fig. 1. The property of the SEM that is of most importance in this study is its great depth of focus. The depth of focus results from using electrons

Jan 1, 1970

By Robert H. Hafner, Irvin R. Kramer, Stewart L. Toleman

IN his paper on the calculation of hardenability from chemical composition, Grossmann1 discussed the effect of most of the alloying elements used commercially. The purpose of the work reported in this paper was to determine the effect of several other elements on hardenability-arsenic, antimony, beryllium, cobalt, columbium, germanium, tellurium, tin, aluminum, and titanium-and to extend the range of composition of some of the elements studied by , Grossmann-chromium, copper, manganese, molybdenum, nickel and silicon. EXPERIMENTAL METHODS To determine the effect on hardenability, suitable amounts of the alloying elements were added to experimental heats and the hardenability determined by means of end-quenched hardenability specimens. The steels were melted in a high-frequency induction furnace with a basic crucible, using ingot iron as a base for some of the heats and S.A.E. 1015 for others. The alloying additions were made as ferroalloys or as metal, depending on the ' alloying element. Hundred-pound heats were split and poured into square, tapered, cast-iron ingot molds with hot tops. Aluminum was not used as a deoxidizer in most of the heats. The ingots were homogenized for 12 hr. at 1260°C. (2300°F.) , and forged into rounds of 1 ½ in. diameter. These bars were normalized twice from 840°C. (1550°F.) before machining into Jominy bars. The composition of the steels was deter- [ ] mined in most cases by samples taken from the end-quench hardenability specimen. As suggested by crafts,2acid-soluble

Jan 1, 1943

By D. A. Farmen

INTRODUCTION In early 1978, engineering personnel at The Carter Mining Company began using photogrammetry coupled with a computer modeling technique to aid in mine planning efforts. The decision to develop this approach was based on the following needs: 1. A method to accurately capture excavated quantities for reporting purposes, 2. A method to produce accurate up-to-date maps for planning purposes, and 3. A computer-based mine-planning technique that would be compatible with techniques used in the past. The system developed utilizes a photogrammetric contractor to provide thousands of aerially-surveyed data points for input into the computer system. Each month the Rawhide and Caballo mines are flown by the photogrammetric contractor. The terrain of the active pit area is digitized and punched out on computer cards. This information is read into The Carter Mining Company's computer facilities, and an updated two-dimensional topographic grid model of the pit is generated. This surface is used to generate quantities moved during the month, to update isopachs, and to update quantities contained in fixed block progression polygons used for forecasting purposes. The system has greatly reduced the amount of manhours spent in field surveying and provides a useful tool for expeditiously evaluating many different forecast cases. It also provides the

Jan 1, 1983

By George S. Koch

Since 1882, world zinc production has increased. In contrast, US zinc production rose until about 1915, but since then has remained nearly constant, with a slight tendency to decrease. Production from the Tri-State district, the largest early source of zinc in the US, has gone down steadily; this decline has been balanced by a growth in the rate of other districts. These changes in US production are due to economic, not geological, factors. Recent exploration has located large minable ore bodies: additional deposits will undoubtedly be found in the stratabound carbonate rock and volcanogenic environments. A statistical analysis of the exploration effort in the Middle Tennessee district indicates that new discoveries can be expected there. Thus, the US is in an early stage of the production cycle for zinc. Of major mining districts in the US, only the Tri-State is exhausted under current economic conditions; large zinc resources of low-grade material, which would repay mining at higher prices or improved technology, are known to exist in that district .

Jan 1, 1982

By William Fink

MANY investigators have attempted to determine the true nature of the internal changes taking place during aging. Merica, Waltenberg and Scott1 were the first to propose a theory of age-hardening. They attributed the age-hardening of duralumin to the precipitation of minute particles of the compound CuA12. Later Zay Jeffries and R. S. Archer2 augmented the above theory by suggesting that the small CuA12 particles acted as "keys" causing "slip interference." Many other investi-gators3 have devoted much time to the mechanism of age-hardening, some corroborating the "precipitation" and "slip interference" theory, others coming to different conclusions because of effects that to them seemed unexplainable by the early theories; e.g., the increase of electrical resistance upon aging, the fact that no change in lattice parameter could be detected during the early stages of aging even at elevated tempera-tures, and the fact that the density did not change as would be predicted. In 1932, Merica revised4 his earlier precipitation theory to take care of these presumably anomalous effects. This revised theory, the "knot" theory, assumes that substantial age-hardening occurs before actual precipitation of solute as discrete particles. The assumed mechanism is one of diffusion of solute atones into groups forming distorted regions which act as "hard" spots and cause slip interference. These "knots" are assumed to have approximately the same lattice arrangement as the solvent.

Jan 1, 1936

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all week-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The-Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend .a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining reports maps privately issued, and similar material, which will he classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and. assurance is given that most careful service will be rendered to them.

Jan 6, 1915

By F. S. Crawford

IRON and copper are mined in the Lake Superior district. The iron mines of the district have the best safety record for that industry in the country as a whole, while the copper mines of the district rank second in two of the four years recorded (Table 1). In Utah copper comes mainly from open-pit mines, which enables that state to lead easily in safety. All of the Michigan production comes from deep underground workings. About 60 per cent of the iron miners in St. Louis County, Minnesota, are employed at open-pit mines; this favorably affects the combined open-pit and underground accident-frequency rate, as this county provides most of the Minnesota-mined iron ore. In Michigan, however, there are few open-pit mines, the bulk of the production coming from underground mines, while all of the Wisconsin production, just across the state line from Michigan, is from underground mines. In spite of the fact that fewer mines in Michigan use the safer open-pit method, the iron-mining industry of that state maintained a consistently low record from 1931 to 1934; however, it was many points behind its nearest competitor, Minnesota, with its much greater production from open-pit mines.

Jan 1, 1939

By Robert Isaac Williams

The Questa mine is located in northern New Mexico on the western flank of the Sangre de Cristo Mountains about 75 miles north of Santa Fe and ranges in elevation from 6,800 to 10,000 ft. GEOLOGY The rocks of the area are Precambrian metamorphic rocks covered by Tertiary extrusive andesites and rhyolites and intruded by Tertiary granitic rocks. These Tertiary intrusives are localized in an east-west belt about 20 miles long and 2 miles wide, extending from Questa to Red River. The Questa orebody is associated with a north-trending aplite intrusive about 3/4 mile wide and 1 3/4 miles long. In the area of mineralization, the metasomatism of aplite has produced a mottled porphyritic rock. This hybrid rock has caused much of the controversy about the Questa mine intrusive. The orebody is essentially monomineralic and consists of numerous closely spaced molybdenite veins varying in thickness from ' 'paint" to 3 in. and occurring in both the andesites and the intrusive. In the intrusive the veins are often siliceous. Common alteration minerals associated with the molybdenite ore vary with the original composition of the rock. The alteration of the aplite has produced phenocrysts of orthoclase, albite, oligoclase and biotite; veins of quartz, orthoclase, and biotite; and graphic myrmekitic intergrowths of feldspars and quartz. In many places near the contact, the andesite is indistinguishable from the metasomatized aplite. The dominant alteration in andesite, however, is the development of fine-grained biotite with apatite, rutile, and sphene.

Jan 1, 1969

By C. S. Simons

Manufacturers of filtering, thickening or clarifying equipment, have been active in developing machines to meet increasingly rigid operator requirements, and the innovations resulting from this effort are moving into commercial applications. In general, the results of these applications are reported to be good. Little has been reported on progress in theory. The growing insistence on the part of pollution control agencies that waste water discharged into streams contain less and less suspended solids is being felt by a broad cross section of industry. A new clarifier, based on the often rediscovered fact that suspended solids settle more rapidly in inclined channels, is being marketed by Neptune MicroFLOC of Corvallis, Ore. This unit employs modules of inclined tubes, mounted in the upper zone of the clarifier, which carry the water flow. These were developed for light solids, such as those encountered in domestic water treatment and in paper mill waste water. In these applications, flow rates up to about three times those permissible in conventional clarifiers are reported to give comparable overflow turbidity. By combining these units with mixed media filters, high clarity may be obtained with minimum capital. Use of such units in the metallurgical industry, particularly where water reuse or effluent quality is important, should grow.

Jan 1, 1970

By John T. Dickman, Ralph E. O’Dette

Chemical Abstracts Service (CAS) is in the process of evolving a computer-based information system which will process all of the material selected for abstracting in the area of chemistry and chemical engineering and its related fields such as the earth sciences and technologies. This system is already operational to some extent and is expected to be fully utilized by 1971. The objective of CAS is to make chemical and related information more readily available, more usable and more used. Chemical Abstracts handle some 5000 abstracts weekly from 13, 000 journals and patents from 25 nations. These cover all of the 80 CA subject sections which relate to chemistry and also extend into areas of interest to geologists, mineralogists, and mining engineers. In this way, CAS fulfills its objective of complete coverage of its major fields, informative abstracting, and indexing to maximum specificity. The concept of a computer-based information system is that of a single machine-language data base into which the results of intellectual analysis of the literature are entered and from which computer programs produce a variety of publications and services applicable to the needs of a wide range of users.

Jan 1, 1969

By R. U. Jackson

Belt conveying is a method of transportation that requires proper servicing and maintenance if completely economical results are to be obtained from the system. With a trucking system, it is common practice to deliver the trucks to a servicing station each day or at the end of each shift. With railroad transportation there is a similar procedure. Sufficient credit is seldom given to this periodic inspection and maintenance procedure, yet it is the key to the successful operation of trucking and rail haulage systems. How about the belt conveyor transportation system? Here is a system that requires no operator for each individual unit. It requires only a main switch and an adequate sequence interlocking system, and the system is so simple to operate that maintenance is considered as only a casual requirement-nothing is done about it until after trouble has developed.

Jan 1, 1956

By H. L. Stone, A. O. Garder

A numerical method of solving the partial differential equations which describe the one-dimensional displacement of oil by gas has been presented. Possible extension of the method to treat multidimensional flow is discussed, and the limitations of this extension are indicated. Using this method, it is possible to allow for the existence of a gas cap, the presence of any number of gas-injection or oil-production wells and the evolution of dissolved gas from the oil. It is also possible to allow for variation in the cross-sectional area, elevation, porosity and permeability of the reservoir. The influence of relative permeability and the force of gravity in the direction of flow upon the displacement is considered. The influence of capillary pressure upon the flow and the effect of gravity in the direction perpendicular to flow are neglected. The physical properties 01 the fluids are considered to be Junctions of pressure only, and equilibrium between contiguous phases is assumed. The numerical calculations can be readily carried out by the use of a digital computer. Several example analyses have been performed using the IBM 704 computer, and about one-third of an hour of computing time was required per case. Reservoir behavior predicted by use of this numerical method was compared to data obtained by other methods for three cases — complete pressure maintenance, dissolved-gas drive and gas-cap drive. The independent solutions to these problems were obtained by analytical solution, laboratory experiment and field data, respectively. Agreement of the numerical solution with data from these sources was good; this agreement establishes the convergence and accuracy of the numerical method. INTRODUCTION Most petroleum reservoirs can be produced by any one of several alternative programs. When a reservoir is produced by primary methods, production economics can be influenced by controlling the number and location of wells and the flow rate of each well. An even greater influence may be achieved by augmenting the recovery of oil obtainable by primary methods. This can be accomplished by injection of fluids such as water, natural or enriched gas or a bank of light liquid hydrocarbons. Selection of the most desirable operation requires a means of predicting the reservoir behavior which will result from each of the several alternative programs. The purpose of this paper is to present a mathematical method for predicting the behavior of reservoirs produced by gas-cap drive, dissolved-gas drive or pressure maintenance by gas injection. The method described herein takes cognizance of phase changes caused by a decline or an increase (due to gas injection) in reservoir pressure, of the presence of a gas cap and of the effect of gravity on the flow of gas and oil. Relative permeability relationships are used to define the flow properties of the rock. Allowance is made for variation in cross-sectional area, elevation, permeability and porosity of the reservoir. Both the influence of capillary pressure upon the flow and pressure gradients in the gas cap are neglected. Whenever a liquid phase and a gas phase are in contact, they are assumed to be in equilibrium. The physical properties of the fluids are considered to be functions of pressure only. Therefore, if the method is to be used to predict the effects of a gas-injection program, mixtures of the injected gas and formation crude should-have the same physical properties as mixtures of formation gas and crude. The equations to be presented in this paper apply only to a one-dimensional case; therefore, they neglect the influence of gravity in the direction transverse to the flow. As is well known, this gravitational influence may lead to overriding of oil by gas. Consequently, this procedure as presented is most applicable to long, thin reservoirs for which gravity overriding is not important. On the other hand, the equations presented can be generalized to treat multidimensional flow and, hence, to consider gravity overriding, if desired. A word of caution on two points is advisable here, however. First, the authors have not demonstrated the accuracy of the numerical technique for multidimensional flow. Second, and more important, capillary pressure will often be of importance in multidimensional problems. Obviously, in such cases a generalization of the

By D. J. Carney, C. W. Boquist, E. C. Rudolphy

Effect of variations in sinter feed composition on sinter strength, bulk density, re-ducibility, chemical composition, and microstructure were determined by sintering experimental samples on a production sintering machine. Increasing amounts of roll scale, ore fines, return fines, and blast furnace slag were most beneficial to feed permeability, sinter bulk density, and strength. Burnt lime additions improved feed permeability but were not beneficial to sinter strength or bulk density. Sinter reducibility was adversely affected by all additives. DEVELOPMENT of methods for evaluating sinter quality, which would in some way predict the behavior of the sinter during charging and smelting in the blast furnace, has been given considerable attention in recent years. In a previous investigation at South Works of the United States Steel Corp., standard sinter sampling and testing procedures were developed.1,2 By modifying the sinter sampling device, a method of sintering experimental mix sinter samples upon a production Dwight-Lloyd sintering machine was also developed. This technique afforded a rapid and controlled method of investigating the effects of the various raw materials and additives on sinter quality and was used in this present investigation. Since the beginning of the present study in 1953, the results of numerous sinter investigations have been published, most of which were concerned with production tests of iron ore sinter, both here and abroad. Three groups of investigators reported results of experimental sinter studies that were related to this investigation. Voice et al.3 studied the effects of controlled variables on sinter quality by producing and testing experimental Northants iron ore sinter using an experimental sintering unit. Mor-rissey and Powers' determined the relationship between iron ore sinter quality and the moisture and coke content using a small laboratory sintering system. Burlingame et al.5 studied the effects of "additives" upon iron ore sinter using a laboratory sintering apparatus and laboratory grade raw materials. At South Works, it was considered desirable to study the effects of sinter mix composition and additives upon the quality of a flue dust-base sinter produced on a production sintering unit. Extrapolation of controlled laboratory test data to sintering plant operation lacking such precise control is not altogether satisfactory. Therefore, the present study was conducted in a manner which approximated production conditions as closely as possible. The raw materials used were those commonly encoun- tered in the production of flue dust and flue dust ore-type sinters and these were varied within extremes encountered in this type of sinter production. Experimental Procedure The experimental sinters were produced from 100 lb mixtures of sinter feed. The principal raw materials and additives used, their particle size, and approximate chemical composition are listed in Table I. The mixing of the raw materials was accomplished by means of a miniature single shaft pug mill shown in Fig, 1. The use of the pug mill as a mixer was decidea upon after encountering difficulty in reproducing the mixing and chopping effect of the sinter plant pug mill with other types of available small mixers. The miniature pug mill was constructed, consisting of 31/2x2x1/4 in, blades spaced 3 in. apart along a 3 ft shaft. Preliminary tests were run with this small mixer to establish the proper rotation speed and the required number of passes through the pug mill to thoroughly mix and distribute all the raw materials in a manner approximating the production Pug mill- Although the effects of varying the mosture content were determined in one particular series of tests, the amount of moisture added was changed as the composition of the experimental mix was varied. The aim in making water additions was to achieve a permeability as high as possible for each particular

Jan 1, 1956

By W. H. Brandt

THERE has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidence. Particularly noteworthy among the empirical work is that of Grossmann,12 who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.1-5 They have shown that formation of pearlite proceeds by a process of nucleation and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to fill in a small part of the gap. A method was presented recently14 for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eutectoid steel was calculated, using linear extrapolations of the ferrite and cementite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and V, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1945

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

THE book covers principally the assaying of silver and gold and the determination of these values in ores, sweepings, and base metal. It seems to have been written more for the goldsmith and jeweler than for the primary producer of metals. There were approximately sixty different substances needed in the operations described and not over a dozen different types of raw material (ore, matte, crude or alloyed metal) are mentioned. The methods of separation used were essentially simple and reasonably reliable, though the processes were not sufficiently understood to permit the selection of the simplest effective ingredients, and there was a great tendency to employ complicated fluxes, with unnecessary repetition of long-continued heatings indicative of a leisurely pace of life. Practically all the processes described are based on a few chemical facts: the inability of gold to combine with sulphur, while silver and the base metals form easily fusible sulphides; the ready oxidation of base metals; and the ii- solubility of gold in nitric acid. Fluxes serve to make earthy impurities fusible, and to carry oxidizing or sulphurizing ingredients. Many of the processes of assaying had changed little up to the beginning of the present century. Even as late as 1924, when the writer took a University course in fire assaying, the crucibles, cupels, scorifiers, molds, and tongs were identical with those of the sixteenth century, though the wind furnace had a stack on it and the muffle for cupelling was gas-fired.* The fluxes were purer, but of the same essential composition. That this branch- or twig-of metallurgy had not advanced in any funda-

Jan 1, 1949

By H. N. Wolcott

AMONG the many cases of replacement of one mineral by another, that of quartz or silicates by pyrite, or even other sulphides, is not uncommon, but the reverse of this process does not appear to have been recorded, even if it has been observed. It, therefore, seemed to the writer that the case described below was worthy of record. FIG. I.-GROUND MASS OF CHALCOPYRITE (C) CONTAINING ROUNDED GRAINS OF PYRITE (P) SHOWING DIFFERENT DEGREES OF REPLACEMENT BY QUARTZ (Q), AND ALSO QUARTZ VEINLETS CUTTING THROUGH THE PYRITE. (PHOTOGRAPHED BY REFLECTED LIGHT.) The specimens described in this paper were obtained by R. B. Morton of Idaho Springs, Colo., from the Old Town Mine, in Russell Gulch, and are in the collection of Cornell University, where the writer studied them. In the rough, the specimens appeared to consist largely of chalcopy- rite, with some grains of tetrahedrite. The polished surface of some of

Jan 6, 1917