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By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

C. Edward Stafford, Chester, Pa.:—Doring all my business life, I have been engaged in the manufacture of Bessemer and open-hearth steels, but, during my long connection with the Shoenberger Steel Co. of Pittsburg, I had some experience in the manufacture of high-grade puddled iron for horseshoes, and in making, by Dr. Otto Wuth's process, extremely pure, low-phosphorus puddled blooms (analyzing from 0.005 to 0.01 per cent. of phosphorus and sulphur), which were melted with low-phosphorus pig-iron in acid open-hearth furnaces, to make extra locomotive fire-box steel. I have also seen the Danks puddlers in operation at different times and places, notably where they were most successful, at the Otis Steel Works, Cleveland, Ohio; then under the management of our friend, Mr. S. T. Wellman. These Danks blooms were made solely for open-hearth melting-stock, to which they were well adapted. (The unavoidable presence of bits of ore-fix imbedded in the mass of the metal always prevents the profitable manufacture of merchant iron from Danks' blooms.) With the experience just described, I was to some degree in position to value fairly the means, methods and results of Mr. Roe's mechanical puddling from the metallurgical or technical and economic points of view, when given an opportunity by Mr. Roe to see his puddling-furnace or machine in operation in Pottstown, Pa. Briefly, the furnace, with water-cooled bottom, is rectangular in plan, about 20 by 8 ft. in the clear, suspended by trunnions at the middle of the long sides, at a height of 17 or 18 ft. above the general level. The oscillation (65" each way from the vertical) is accomplished by geared segments (attached to the downward-projecting side or trunnion-plates) with which engage pinions driven by a reversing engine. The whole section

Jan 1, 1906

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968

By G. B. Gibbs

Equations are developed which describe the growth of graphite nodules during a-phase graphi-tization under various limiting conditions. When carbon diffusion is rate controlling a modified Birchenall-Mead equation predicts an "apparent activation energy" of 31 keal mole-1 for the parabolic growth constant. If reaction at the graphite or cementite interface is the slowest process growth kinetics are linear and the activation energy must be >50 keal mole-1. A comparison with the experimental observations confirms that carbon diffusion determines the rate of reaction. Apart from minor approximations associated with Lou! carbon solubility in a iron the theory may also be applied to I-phase graphitization. It is well-known that cementite exists as a meta-stable phase in Fe-C alloys and that if a specimen is held at diffusion temperatures for a sufficiently long period the cementite decomposes and graphite is precipitated. Graphitization occurs by the nu-cleation and growth of carbon nodules and several impurity elements catalyze the reaction when present in minute amounts.1 The growth kinetics of nodules have been extensively investigated in the fee ? range2, 3 and recently in the bee a range.1, 4 Experimental growth curves (nodule radius vs time) have slopes which decrease with time, but the scatter of points is generally too great for the precise shape of the curves to be determined with certainty. Birchenall and Mead5 concluded that they are parabolic in ? iron, indicating diffusion control, and that the migration of carbon atoms determines the growth rate. Harris et al, 1 advanced similar ideas for a-phase graphitization. On the other hand, Burke3 chose to regard the initial growth region as a transient followed by a linear law indicating interface control (i.e., cementite decomposition or graphite crystallization as the slowest process). Jeminson and Higgins6 originally considered the initial steep portions of "parabolie" to represent a linear growth law also. In support of these ideas it has been noted that the apparent ac-

Jan 1, 1965

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,' a pure metal and its vapor,' and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By Edward Keller

GOLD MOVEMENT ON SURFACE OF AURIFEROUS COPPER WHEN LATTER IS SUBJECTED TO OXIDATION SOME years ago the writer's attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived. I So, later, he made a few simple experiments, which are described herewith. In: order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by I in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent. copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scorifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while

Jan 1, 1919

By G. L. Oldright

Nearly all of the present schemes for treating complex (i. e. lead-silver-zinc-copper) ores are based on the idea that lead holds, and will hold for some time, the strongest economic place from the viewpoint of supply and demand of all the non-ferrous metals. Copper, it is thought, will come back to its own when European affairs are stabilized, although at that time competition from Chile, Peru, and Katanga, in particular, will be more severe than in pre-war days. The future for silver and for zinc is uncertain. New uses are developing for zinc, and the market has remained better than many expected, but the stabilization of world markets will bring in foreign competition instead of relief. The cost of producing zinc from simple zinc ores, by the retort process, will, from the nature of the labor required and the increasing cost of fuel, increase steadily. As a result, the small producers of purely zinc ores around Joplin are shutting down their mines, even with a good market price for zinc; on the other hand, the producer of lead from complex ores, in the Rocky Mountain states, is confident of a profit from the sale of his lead, and is seeking means to make the zinc in his ore pay some part of the cost of treatment. However, the tonnage costs for mining and ore dressing are much higher in the Rocky Mountain states, as may be seen by comparing tax-return statements from the various states. Even before the recent drop in the price of silver, many mines were operating on a very slender margin of profit; labor and supplies cost more. Mining at greater depth has shown most orebodies to grow increasingly more complex, so that improvements in mining and ore-dressing practice have not been sufficient to compensate for the additional expense involved in beneficiating these ores. The smelters have bad to meet the same general economic situation, so they can only give

Jan 1, 1924

By G. L. Oldright

NEARLY all of the present schemes for treating complex (i. e. lead¬silver-zinc-copper) ores are based on the idea that lead holds, and will hold for some time, the strongest economic place from the viewpoint of supply and demand of all the non-ferrous metals. Copper, it is thought, will come back to its own when European affairs are stabilized, although at that time competition from Chile, Peru, and Katanga, in particular, will be more severe than in pre-war days. The future for silver and for zinc is uncertain. New uses are developing for zinc, and the market has remained better than many expected, but the stabilization of world markets will bring in foreign competition instead of relief. The cost of producing zinc from simple zinc ores, by the retort process, will, from the nature of the labor required and the increasing cost of fuel, increase steadily. As a result, the small producers of purely zinc ores around Joplin are shutting down their mines, even with a good market price for zinc; on the other hand, the producer of lead from complex ores, in the Rocky Mountain states, is confident of a profit from the sale of his lead, and is seeking means to make the zinc in his ore pay some part of the cost of treatment. However, the tonnage costs for mining and ore dressing are much higher in the Rocky Mountain states, as may be seen by comparing tax-return statements from the various states. Even before the recent drop in the price of silver, many mines were operating on a very slender margin of profit; labor and supplies cost more. Mining at greater depth has shown most orebodies to grow increasingly more complex, so that improvements in mining and ore-dressing practice have not been sufficient too compensate for the additional expense involved in beneficiating these ores. The smelters have had to meet the same general economic situation, so they can only give

Jan 3, 1924

By H. H. Power, C. H. Pishny

When an oil operator becomes a party to a proration agreement he may wonder, with good cause, whether production prorated .today is merely deferred until tomorrow or whether oil might be lost. Various types of evidence obtained from production records when studied quantitatively are of great assistance in arriving at definite conclusions. A study of individual examples cited in this paper leads towards some solution of the problem, particularly when they are considered in the aggregate. Many production curves on various pay horizons were studied. A disappointingly large number of these were of contributory value, but inconclusive. However, there were enough curves of similar type from the Wilcox sand at Earlsboro, Bowlegs, Seminole City, the Cromwell horizon at Little River, and the Simpson dolomite at Valley Center, Kansas, from which reasonably definite conclusions were drawn. Assuming that deferred production is later made up with no increase in ultimate recovery, a curve (Fig. 1) shows the normal flowing and pumping life of a composite well, contructed by the family curve method. The initial production of the well shown is 1700 bbl. daily and the allowed production is 25 per cent. On this basis the average daily allowed rate for the first month is 425 bb1., or the area BCDE, which is equivalent to the area AFDG under the normal decline curve. The potential production for the second month is 1500 bbl. and the allowed production 375 bbl. daily. By this procedure a potential curve for each succeeding month is obtained (points A, H, I, J and K). If the well is opened it should produce somewhere near its potential curve for a short period and then decline at a more rapid rate than the potential curve. This theoretical analysis is basic. Actual examples exhibiting all points raised by the ideal curve are rare. Proration in the Mid-Continent area has been effected mostly by leases rather than by individual wells; hence a well may produce any

Jan 1, 1931

By K. C. Carriere

INTRODUCTION The purpose of this section is to introduce the reader to the concepts of computer control of grinding circuits, and to flag some of the opportunities to be encountered, but without becoming overly involved in details of process, equipment or software. It is assumed that the reader has some familiarity with computer hardware and software, and in particular with the grinding process. The paper is organized into four parts: a general commentary of the need for computer control of grinding, a discussion of the process considerations involved, a more detailed elaboration on the current state of applicable computer technology, and a case study indicating one approach towards such a project. A brief installation survey and references for further reading are also given. This section will primarily deal with supervisory computer applications. Direct Digital Control and microprocessor systems are generally used as replacements for analog controls and thus are not considered in depth. Many configurations of grinding circuits exist, necessitating certain assumptions. Since many new concentrators use an open circuited SAG mill feeding a closed circuit ball mill, this configuration is used as a model although the principles stated can be extrapolated to any circuit. Motivation The use of computers for industrial control has been one of the dreams of control engineers and operators alike for many years. The concept of a plant running at optimal conditions with minimal operator involvement is very attractive from economic and technical standpoints. Accomplishment of this goal has been a long struggle, but today likelihood of success of such a project is very high, considering the reliability of modern hardware and the sophistication of available software. The primary motivation of any control system must be economic, i.e. it must pay for itself and make money for the owner, directly or indirectly. In grinding control the benefits which can be expected include: a) Higher through-put b) More uniform product in particle size, density and volumetric flog: c) Reduced operating costs including media consumption, power consumption and liner wear

Jan 1, 1982

By R. W. Raymond

CLARENCE King born January 6,1842, at Newport, R. I. His ancestors on both sides mere New Englanders, of English blood, and among them not a few distinguished themselves in art, science, politics or commerce. His grandfather, Samuel Vernon King (partner in 1803 in the house of Talbot, O1yphant & King, later known as King $ Co.), was a pioneer in the China trade, and four of his sons succeeded him in the business. Three of the four died in the far East; and one of

Jan 1, 1903

TO THE BOARD OF DIRECTORS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS Gentlemen: - I herewith present a report of some. of the more important activities of the Institute for the year of 1922. The outstanding feature of the year is the optimism felt by our members despite the continued depression in the mining industry. January 1, 1921, found many of our members out of employment or drifting into other industries to tide them over the depression, but almost universally the feeling has been that this was but a temporary condition and that sooner or later the necessary production of raw materials would enable these members to return to their former activities and renew their participation in Institute affairs. As the year passed conditions improved and, before it ended, many had found employment in their previous occupations. Bearing in mind that this depression has been very real, we have reason to be well satisfied with the work that the Institute has been able to do. The loss of members through inability to pay, dues has been large, and income has been correspondingly reduced, but it proved to be materially in excess of that anticipated early in the year, so that a substantial and unanticipated balance was carried forward toward the activities of 1923. PUBLICATIONS Following the example of other technical societies, and to conserve our resources, no Year Book was published in 1922. The lack of an up-to-date membership list for the use of our members was regrettable, but the saving of $5000 proved to be worth while. During the year, Volumes LXV, LXVI, and LXVII were printed and sent to members. These volumes were composed largely of the papers of 1920 and 1921, publication of which had been delayed partly through lack of funds and partly for the purpose of segregating into volumes those papers dealing with the same general subject. The segregation of papers had been suggested by a number of members who had advised that they were not primarily interested in all subjects

Jan 1, 1925

By R. P. Rothwell

AT this our first meeting I beg to call the attention of the members of our Institute to what is certainly a question of the greatest possible importance to the industries we represent; and more particularly to the welfare of the coal and iron trades : I refer to the enormous waste of coal in mining and in its preparation for market, as now practised in our anthracite coal-fields. It is a fact which many of you can certify to, that we are wasting fully one-ha f of all the coal in the veins we are now working, and there are cases, which might be mentioned where this proportion, immense as it is, has been greatly exceeded. The popular belief that our deposits of anthracite coal are "practically inexhaustible," is very far from being founded on facts. On the contrary, supposing the present rate of increase in the production to be maintained, it is probable that a maximum yield for our coal-fields would be attained in about fifteen years ; there are in fact some of our smaller basins where the principal veins are nearly exhausted and the production has already attained its maximum. There are others, again, where the depth attained-and it must be borne in mind that we commenced working at the surface outcrop-moderate though it is (scarcely ever reaching eight hundred feet), has so increased the cost of mining as to imperil the capital invested, and though it requires but little foresight to predict the time when the difficulties of mining will be very considerably increased by reason of the greater depth, greater quantity of water, fire-damp, and other fruitful sources of cost, yet, ignoring these recognized facts, we continue to waste more than one-half of the coal where it is obtained with the least danger, expense, and trouble, that is, near the surface-either above water-level or at a moderate depth below it. The inspection of almost any accurate mine map will satisfy you that, on an average, we leave fully one-third. of the coal in the ground as pillars to support the roof; in some places more than one-third thus remains, while it is very rare that less than one-quarter is left. In almost every case this coal is absolutely lost, for it will very rarely pay to reopen gangways and lay roads to it after that portion of the mine has been abandoned. Is it necessary in all cases to support the roof, and where it is, may not some artificial

Jan 1, 1873

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,' from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,' from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By R. H. Goodrich

Development in this district during the year 1929 was little different from that of any other year despite the somewhat depressed condition of the oil business in general. The year was marked by: (1) An intensive geophysical campaign in the search of deep-seated salt domes; (2) the rather successful exploration and development of lateral sand production on the flanks of some of the older domes. Geophysical Exploration Geophysical work is confined almost exclusively to the torsion balance and seismograph. At the beginning of the year there were approximately 185 individual instruments of all types engaged in the search of structures in the Gulf Coast of Texas and Louisiana. This total includes 3 magnetometers, 83 torsion balances and 100 seismographs. The number of parties operating the torsion balances was 47; seismographs, 20; magnetometers, 3. It is estimated that 4,800,000 lb. of dynamite or other explosives were used in seismic exploration. During the year the torsion balance and seismograph were credited with having discovered the following salt domes: Texas, Danbury dome, Brazoria County, H. & T. B. R. Co., and Clodine dome, Fort Bend County, John Fredricks and Wm. Stanley, Satowsky Survey; Louisiana, Iowa dome, Calcasieu and Jefferson Davis Parishes, T. 9 S., R. 6 and 7 W., and Cameron-Meadow dome, Cameron Parish, T. 14 S., R. 13 W. Because of the secrecy maintained in these developments, it is somewhat hazardous to venture opinion as to the number of salt domes found during one year. The discovery of gas at Mykawa district and at Genoa district, in Harris County, Texas, is considered of more than passing importance, because there is indication in the performance of these two districts that commercial accumulation of oil and gas may be found in the Gulf Coast on structures other than the wore or less definite salt dome type. While it is generally conceded that the accompanying structure in these instances are deeply buried salt domes, it is a fact that neither the seismograph nor the drill have indicated the presence of salt.

Jan 1, 1930