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By J. B. Goddard

The discovery of rhenium on the ion exchange resin used at the uraniun in-situ leach operations at Palangana, TX, led to a laborabory study of possible recovery methods. Rhenium was present in small amounts in the ammonium carbonate leach liquors as the perrhenate anion, ReO4-. It concentrated on the anion exchange resin, which was a factor of 10 more selective for rhenium than for uranium. Various elution systems were investigated for stripping the rhenium from the columns after the uranium had been eluted with chloride or nitrate solutions. Although the per-chlorate ion was most efficient on a molar basis, nitrate ion combined the benefits of efficiency and low cost. A 3N or stronger concentration of nitrate containing up to 0. 5N H + was found to be the system of choice. A rhenium sulfide concentrate containing up to 14010 Re was obtained from these effluents by hydrogen sulfide precipitation. Preliminary experiments were run to produce rhenium metal powder by oxidation of the concentrate to NH4ReO4 followed by hydrogen reduction at elevated temperature.

Jan 1, 1984

By Kendall E. Born

Production of crude oil in Tennessee during 1943 was approximately 8200 bbl., slightly less than the 1942 production, Counties. Some half dozen wells in Clay, Fentress, and Pickett Counties, pumped intermittently, produced about 1000 barrels. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas, respectively. The Morgan County production was about I0,000,000 cu. ft. and approximately 8,000,000 cu. ft. was produced from the Jamestown gas field from six wells. The production of oil by counties is shown in Table I. Thirteen wells were spudded during the year; three were drilling on Dec. I, 1943. Of the nine completions, representing 10,488 ft. of hole, three were gas' wells of commercial size although only one of them has been placed on the line. The completions are listed in Table 2. The distribution of tests according to physiographic divisions is given in Table 3. Cumberland Pluteuz.-There were three completions in the northern part of

Jan 1, 1944

By Kendall E. Born

Production of crude oil in Tennessee during 1943 was approximately 8200 bbl., slightly less than the 1942 production, Counties. Some half dozen wells in Clay, Fentress, and Pickett Counties, pumped intermittently, produced about 1000 barrels. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas, respectively. The Morgan County production was about I0,000,000 cu. ft. and approximately 8,000,000 cu. ft. was produced from the Jamestown gas field from six wells. The production of oil by counties is shown in Table I. Thirteen wells were spudded during the year; three were drilling on Dec. I, 1943. Of the nine completions, representing 10,488 ft. of hole, three were gas' wells of commercial size although only one of them has been placed on the line. The completions are listed in Table 2. The distribution of tests according to physiographic divisions is given in Table 3. Cumberland Pluteuz.-There were three completions in the northern part of

Jan 1, 1944

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process.

Jul 1, 1956

By W. Joseph Schlitt

The characteristics of successful heap and dump leach operations are first reviewed in a general sense. Then attention is focussed on solution management as the key operating parameter in leaching. The first part of this study includes a detailed conceptual analysis of fluid flow. This identifies the relationships between the flow parameters and the chemical and physical properties of the rock. Then these relationships are extended to practical systems in order to establish optimum application rates and solution distribution methods for heaps and dumps. The study shows that there is a maximum effective application rate, qmax, that can be used without causing solution short circuiting. This rate is a function of the minimum permeability in the heap or dump. The expression for qmax is qmax (gal/ft2/hr)[~]0.9 k (darcies). Here k is the appropriate permeability coefficient. Using this equation, qmax is found to be on the order of 1 gal/ft2/hr (4 cm/hr) for a typical heap or dump leach operation.

Jan 1, 1984

By R. P. Steijn

IT has been observed by a number of investigators that under certain conditions metals freeze into an aggregate of small hexagonal strands, parallel to one another and with their axes approximately in the direction of growth.'" This structure has been termed "cellular structure" and is explained in various ways by different workers, notably by Rutter and Chalmers." These investigators attribute the phenomenon to the presence of minute quantities of solute atoms which induce constitutional supercooling. However, if this is true, observations of the cellular structure in extremely pure substances, like frozen distilled water' and germanium of less than 0.0001 atomic pct metallic solute,' are difficult to comprehend. The purpose of this communication is to describe several observations made of the prismatic structure in zinc of 99.99 pct purity. Zinc single and bicrystals grown in a constant gradient electrical resistance furnace exhibit the cellular structure after etching in 15 pct HC1. (See Figs. 1 and 2.) It is noticed that the hexagonal substructure sometimes continues unbroken across the bicrystalline grain boundary.

Jan 1, 1956

By C. O. Brawner

Simple, specific rules for achieving slope stability in open-pit mines are impossible to devise. Each pit has a different mining program and a different set of environmental conditions, and its final slope design must be based on an individual evaluation of the actual site. The overall philosophy of pit stability, however, is tending towards a limit design concept. Since slope angle has a great influence on the economics of most open-pit mines, efforts are being made to reduce the theoretical factor of safety for slope stability to very near 1.0. (Factor of safety is here defined as shear strength/shear stress on the most probable plane of failure.) Actually, where detailed, statistically significant testing has been done and a comprehensive ground control program is being instituted to warn of movement at an early stage, safety factors as low as 1.1 or 1.2 may be justified. The cost of the necessary procedures, however, is high. There are many factors that influence stability, but this article will be confined to three-rock structure, groundwater, and blasting.

Jan 8, 1969

By John Dasher, M. C. Chang

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to beneficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly -24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant.

Jan 3, 1959

U.S. Steel Uncovers Massive Iron Ore Deposits in Nevada United States Steel Corporation has confirmed that mineral investigation in Lyon County, Nevada. has been under way since 1960. Confirmation followed press reports of a statement attributed to a Nevada State inspector of mines to the effect that the Corporation has found a major iron ore deposit that may also contain copper ill West Central Nevada. Drillings over the years in a number of locations have indicated extensive iron ore bodie containing a possible quarter of a billion tons of ore of a basically magnetite composition. analyzing less than 40% iron, which would require beneficiation for commercial use. Some of these deposits are deep- lying while others would permit open pit mining. These bodies contain copper in quantities of approxiimately 0.3%. More recent drilling in another area has disclosed evidence of additional deeply-lying deposits of a lower fe content but with more promising indications of copper. A realistic estimate of fe and cu ore reserves cannot be made until more drilling is completed.

Jan 1, 1970

Executive Committee, Board of Directors Howard C Pyle, Chairman, J L Gillson, Vice¬Chairman, A W Thornton, Elmer A Jones, Augustus B Kinzel Finance Committee, Board of Directors J S Vanick, Chairman, John P Hammond, J W Woomer Investments Gail F Moulton, '60, Chairman, Andrew Fletcher, '62, John M Lovejoy, '61, C R Dodson, ex off as AIME Treasurer, J S Vanick, ex off as Chairman of Finance Committee Endowment Andrew Fletcher, Chairman, N G Alford, W J Coulter, Harold Decker, J V N Dorr, R B Gilmore, J B Haffner, Kenneth Hill, 0 H Johnson, J D MacKenzie, D H McLaughlin, J R McMillan, W S Morris, L F Reinartz, H DeWitt Smith, Wilfred Sykes, J R Suman, C E Weed Honorary Memberships C E Reistle, Jr, '60, Chairman, Grover J Holt, '61, Augustus B Kmzel, '62, (ex off as Past Presidents of AIME) M L Haider, '60, D H McLaughlin, '61, John M Lovejoy, '62, L F Reinartz, '63, Howard C Pyle, ex off as President of AIME

Jan 1, 1959

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, 'however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel ' 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650' C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931

By John Birkinbine

This piece of Carpenter crucible steel has exhibited a tensile strength of 116,000 pounds per square inch, an elastic limit of 89,170 pounds, an elongation of 25 per cent., and a reduction in area of 42 per cent. The test-specimen had a length of 2 inches between fillets, and was an inch bar reduced to an area of 0.504 square inch. This unusual tensile strength was determined before the bar had been hardened so as to show the remarkably velvety fracture here exhibited; but a piece of the same, tested after hardening, is reported to have stood a stress of 214,000 pounds per square inch. Another test-piece is said to have shown 136,000 pounds tensile strength, 97,300 pounds elastic limit, 20 per cent. elongation in 2 inches, and 40 per cent. reduction of area. Mr. Carpenter claims that this steel, containing 2.27 per cent. chromium and 1.04 per cent. carbon, can be welded like iron, and has proved most desirable,for the highest class of die-steel.

Jan 1, 1895

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10' v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

By J. E. Steiner, J. M. Hodge, M. A. Orehoski

Ingots of four steels (1045, 1080, Ni-Mo-V, and Ni-Cr-Mo-V) were cast at pressures varying from about 1 to 760 mm of mercury, so as to obtain a range of hydrogen contents in each steel. The susceptibility of these steels to flaking was evaluated by cooling hot-rolled blooms at a range of cooling rates, varying from water quenching to slag cooling, and studying the occurrence of flaking as a function of cooling rate. The steels exhibited differences in susceptibility to flaking, and a tlzreshold value for hydrogen content for each steel was found, below which the susceptibility was very low and above which the susceptibility increased markedly with increasing hydrogen content. Mechanical property evaluations, metallogvaplzic exantinations, and X-my diffraction determinations o,t retained austenite were made on samples from the blooms. A mechanism of flaking which is consistent with the observed behaviors, the effects of hvdrogen content, and the differences in susceptibility among the steels investigated is postulated, based on the results of mechanical property evaluations and metallographic and X-ray diffraction studies. ThE important role of hydrogen as a factor in the occurrence of "flakes" or "hair-line cracks" in steel has now been established by many investigations. These have included investigations by steel producers and forging manufacturers, to whom the prevention of flaking is a very real and serious problem, and many research studies aimed primarily at establishing the mechanism of this behavior Several investigators3 have reported that steels cast at reduced pressures (absolute pressures of about 1 mm) not only are low in hydrogen content but are essentially insensitive to the formation of flakes. These investigations have shown that a general relationship exists between hydrogen content and susceptibility to flaking. The difficulty of obtaining suitable samples of steels of a given composition with the desired range of hydrogen contents, particularly in the relatively large sections in which flaking most commonly occurs, has been the principal obstacle to quantitative evaluations of these relationships. Steels with intermediate hydrogen contents between 1 ppm, and the 4ppm or higher of air-cast steels are generally not available in commercially produced steels. Laboratory procedures, in which the hydrogen is introduced into solid steel samples by heating in a hydrogen atmosphere under pressure, generally involve a limitation in the size of the sample which can be treated, and thus are not representative of the behaviors in large sections. The availability of a facility at the South Chicago Works of U.S. Steel, in which several ingots could be cast from a single heat of steel at total air pressures ranging from 0.25 to 760 mm of Hg, has made it possible to overcome this obstacle and to obtain ingots of a given steel covering the intermediate range of hydrogen contents desired. These ingots, furthermore, are of a size suitable for the production of product with section sizes large enough to be representative of the products in which flaking most commonly occurs in commercial production. In these experiments, this facility was used to study the relationships between hydrogen content and the susceptibility to flaking of four steels, two plain carbon steels at 0.45 and 0.80 pct C and two low-carbon alloy steels representing a medium and a rather high hardenability level. These flaking studies were supplemented by evaluations of mechanical properties and by metallographic studies on samples from the blooms, in order to obtain pertinent information on the factors other than hydrogen content which influence the susceptibilities of these steels to flaking. Based on the results of these tests, a mechanism for the initiation and propagation of the flaking cracks, which is consistent with the observed behaviors, is postulated. MATERIALS AND EXPERIMENTAL WORK Steelmaking and Conversion. To provide material for the investigation, five 29- by 35-in., hot-topped, big-end-up ingots were cast from each of four 80-ton, basic electric-furnace heats of four different steels (a 1045 steel, a 1080 steel, a Ni-Mo-V steel, and a Ni-Cr-Mo-V steel). A double-slag practice was used on all steels and the two plain carbon steels were Si-A1 deoxidized with an addition of 2 lb of A1 per ton, while the Ni-Mo-V and Ni-Cr-Mo-V steels were deoxidized only with silicon and

Jan 1, 1964

By George E. Beavers

It is well to understand at once that converter gas is always mixed with copper blast-furnace gas at Copperhill before entering the Glover tower, and, at times, roaster gas is also added along with the converter and blast-furnace gas. Fig. 1 is introduced to show the variations in the sulfur dioxide content of the gas and the ability of the acid-plant operator to control the variations, resulting in a very even grade at the Gay-Lussac tower entrance. The sulfur dioxide content of the gas entering the Gay-Lussac tower must be low and regular to assure low niter consumption. The blast-furnace gas alone is rather uniform as regards sulfur dioxide content and the variations, as shown in Fig. 1, are chiefly caused by converter changes—out for charging, slag pouring, copper pouring, and, of course, the "finish." The combined gas during the converter finish is, at times, almost free of oxygen and the sulfur dioxide content reaches 13.0 per cent. At such times air is added at the Glover tower.

Jan 1, 1934

By N. Plint, E. T. Pinkney

Copper segregation developments within the Anglo American Group are described with particular reference to the work of the TORCO Project Team. Some radical differences have been adopted in the mechan-ical approach as compared with methods used by previous workers. Most important among these are the following: (1) The heating unit is a fluidized-bed roaster. (2) A moving bed segregation chamber is used in which a packed bed of heated ore, to which reagents have been added, moves slowly downwards under gravity and is discharged at a controlled rate by means of a suitable valve mechanism. (3) The quantities of reagents used (sodium chloride and some form of carbon) are only a small fraction of those recommended by other investigators. (4) Retention times of only 2 min have been satisfactory for the complete segregation of many types of ore. Project TORCO is the code name given by Anglo American Corp. of South Africa, Ltd., to the investigation undertaken in Zambia to develop a plant capable of treating large tonnages of refractory copper-bearing ores by the segregation process. The process has now been under investigation for six years (1960-66) and during that period work has progressed from bench-scale laboratory tests through small-scale pilot-plant work to a 500-tpd commercial pilot unit. Test work has been carried out mainly on the ores of the Zambian Copperbelt and results have been encouraging. Recoveries on the order of 90% have been obtained on all Copperbelt ores tested with high concentrate grades. PRELIMINARY INVESTIGATION Laboratory scale segregation test work on Nchanga banded sandstone ore and oxidized ore from Kansan-shi was originally conducted by Professor Maurice Rey. SociCtC Miniere et Mktallurgique de Pefiarroya, in 1957. Both ores responded favorably to the process. In November, 1960, the consulting engineers of Anglo American Corp. of South Africa, Ltd., initiated preliminary investigations on the application of the segregation process to Copperbelt ores. In early laboratory work, samples were heated in a closed, externally heated tube furnace for one hour at temperatures ranging from 800 to 830°C. The free moisture content of the ore feed was 4% and reagent additions were 0.5% salt and 1.0% coal. Both salt and coal were pre-crushed to -48 mesh Tyler.* All samples except an ore from the Bancroft mine responded well to the process and recoveries of over 90% were obtained. The presence of dolomite was responsible for the relatively poor recoveries from the Bancroft ore, as tests on one of the other ores with additions of calcite or dolomite confirmed. Recoveries dropped from 94 to 45% Grades of all the rougher flotation concentrates produced were low at 10-15% copper. The laboratory investigation was then followed up on a pilot-plant scale. An attempt was made to carry out the segregation process in a coal-fired 5-ft-diam fluidized-bed roaster. The feed consisted of a banded sandstone from Nchanga to which 0.5% sodium chloride had been added. Reducing conditions were maintained in the roaster by the addition of coal in excess of that required for heating the feed. The excess coal and added salt constituted the segregation reagents and the temperature of the bed was held at approximately 750°C. Recoveries of copper and grades of concentrates were low. The reasons for lack of success were: (1) The reaction is a gaseous one and a fluidized-bed roaster is therefore unsuitable as a segregation unit. (2) Coal in excess of that required for heating was introduced into the fluidized bed and under these conditions some of the copper would be reduced in situ. The term "reduced in situ" is used here to describe any copper mineral reduced to the metallic state in its original site within the ore particles. If this copper is to be recovered by subsequent froth flotation it must first be liberated from the gangue by grinding or some other method which, in practice, is usually not feasible on ores of this type.

Jan 1, 1969

By W. R. Hibbard Jr., R. W. Guard, N. G. Ainslie

Evidence is presented that copper-base solid solutions of different solutes having equal grain sizes, no preferred crystal-lographic orientation, equal electron-atom ratios, and, within experimental scatter, identical initial yield strengths, need not have identical stress-strain curves at strains larger than about 0.04. The stress-strain behavior is rationalized in terms of the proposed Suzuki chemical interaction between solute atoms and extended dislocations using what is thought to be a somewhat different means of representing stress-strain data. ALTHOUGH the effect: of alloying element upon the strength characteristics of sold solutions is a subject which has received considerable attention in the past, the exact relationships between the common deformation parameters and certain common variables are not really known in some cases. As a result some of the experiments reported in the literature in which these variables are inadequately controlled lose some of their persuasion regarding underlying principles. Nonetheless, facts are known which bear pointing up: When the true stress, a, and true plastic strain, E, of tensile deformatic~n are plotted on a double logarithmic coordinate system, one may observe a straight-line relationship at strains greater than 0.02. The form of the curve in the linear region is given by a = Ken! where a represents true stress, E, true strain, and K and tn, constants. If the relationship holds, K and m define the flow characteristics of the material being tested. m and K, however, may vary with other parameters. Hollomon found that in a-brass, m is influenced by grain size. French and HibbardZ found in alloys of copper that inverse relationships existed between m and 1) the solute concentration for a given solute, 2) the 0.01 yield strength, and 3) the constantK. Lacy and Gensamer3 observed (du/d~) (= U/Em) to increase with increasing values of K in systems of alloyed ferrites (although with considerable scatter of data which may be attributed to uncontrolled grain size). Brick, Martin, and Angier* deduced in copper-base alloys a straight-line relationship (with some scatter) between the change in the Dph number due to solid-solution strengthening and the change in the Dph number due to work hardening which suggested that copper-base alloys having equal yield strengths might have identical stress-strain curves in the plastic flow regions. French and HibbardZ concluded that the yield strength of copper-base solid solutions is the proper basis for comparing the effects of solute elements. Also, Allen, Schofield, and ate' showed that, within their experimental variation, copper-base alloys of zinc, gallium, germanium, and arsenic having the same electron-atom ratios have the same true-stress true-plastic strain curves. Dorn, Pietrokowsky, and ~ietz' also found that with aluminum-base alloys the stress-strain curves in the flow regions are approximately the same if "equivalent" concentrations of alloying elements are used. Solute valence and lattice parameter distortion were the parameters used to determine equivalency. The present report describes an investigation in which an attempt was made to obtain copper-base solid-solution alloys of four solute elements having within close tolerances equal grain sizes and yield strengths, and to see if the level of yield strength does indeed define the flow curve regardless of solute type. During analysis of the data certain unexpected features of the stress-strain curves became apparent which gave rise to some speculation and are discussed at length in the paragraphs that follow. EXPERIMENTAL PROCEDURES Alloy Preparation—Using the data of French and HibbardZ as a first approximation, four different binary copper-base alioys were designed so as to have the same yield strength. In addition, other alloys were prepared in which the solute aoncentrations varied slightly from those calculated above so as to span a range of yield strengths, see Table L The yield strengths of all alloys prepared except the copper-tin alloys were subsequently found to Lie fairly close to one another. The copper used in the alloys was produced by the American Smelting and Refining Co. and was of very high purity (99.999 pct). The alloy additions and their initial purities are as follows:

Jan 1, 1960

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.' Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner's treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1'2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965