Search Documents

Jan 1, 1958

By T. R. Wright

IN few mining regions in the world are the ores so varied and complex as in the Andes of central Peru. Consequently, in few localities is one company engaged in so many and such diverse metallurgical operations as the Cerro de Pasco Copper Corp. Concurrent with the mining of complex lead-zinc ores in Peru, and the consequent expansion of the Corporation's metallurgical activities, a department of metallurgical research was established in 1927 at La Orova. Facilities were provided for research in ore dressing, hydronivtallurgy pyrometallurgy, electrometallurgy, and analytical chemistry. In addition to laboratories. various pilot plants were built, including a concentrator, leaching plant, "by-product" smelter, and electrolytic refineries. These pilot plants are not diminutive units; they are designed and equipped as semicommercial plants for operation on a continuous 24-hour basis thus assuring the duplication of pilot plant results in actual practice. In general, the sequence in the development of metallurgical operations hasbeen as follows: (1) investigations in the laboratory to determine the most effective and economical method of treatment; (2) continuation of the research project on a pilot-plant scale when the evaluation of the laboratory

Jan 1, 1945

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes.

Jan 1, 1950

By C. E. Jackson, E. C. Nelson, A. L. Christenson

Much information regarding the transfornlatio~lal characteristics of a steel as it cools in a known manner from the austenitic state can be obtained from dilatometric studies. This method has received more arid more attention because of its great flexibility, accuracy, and ease of interpretation. 'The method is entirely applicable to any rate of heating and cooling although the experumental procrdures for high rates of cooling have offered some difficulties. This paper presents a description of equipment employing cooling rates up to 500 °C. per secorld and the results of dilatometric observations on six commercial steels are included. French and Klopsch1 studied the cooling transformations of a serirs OF carbon steel, using the thermal arrest method. This was followed by the systematic investigatiol1 of Esser and co-workers on the effect of carhon2 and other alloying additions. in which the transforlnation temperature\ were determined by magnetic induction measurements indicated by a string galranoineter. Emphasis was placed on determining Ar' trailsformations and the critical cooling rates for these steels. The maglietic measurements wrere used in an effort to obtain more accurate data at higher cooling rates. Measurements of thermal arrest were made also to check the validity of the magnetic indications, and good correlation was found between the two, although Esser's,Ar' temperature measurements on iron-carbon alloys were about 200°F. lower than the measurements made by Fresnch and Klopsch. A notable contril~ution by Esser was the introduction gas quenching. wever and Rose4 used a moving-coil galranometcr in the study of the .Ar and Ar" of iron-carbon alloys by the thermal arrest method and obtained somewhat lover Ar" temperatures than those observed by Esser below I per cent carbon and considerably higher ahove. They concluded that the cooling rate had little influcncc on the Ar" temperatures above 0.4 per cent carbon, although Esser had observed a decrease in the -4r" temperature with increasing cooling rate with similar steels. Digges determined the .Ar" temperature4 for a scries of high-purity iron-carbon alloys, and close agreement with his results was obtained by Greninger. The thermal arrest method. together with metallographic observation used in both these studies, represents the latest investigations of this type. Any investigation by thermal analyses is dependent on the heat of reaction and the specific heat of the

Jan 1, 1945

By George A. Moore

A recent survey of existing analytical results, and an attempt to correlate them with each other and with the known history and behavior of the samples, indicated that none of the commonly applied methods could be considered established as intrinsically reliable. It was. therefore, desired to attempt to establish the reliahility of some one method by external evidence. If this were to be accomplished, other methods could then be evaluated in terms of the method establibhed. The correct method was accordingly to be chosen without regard for cost, speed, or convenience; with the requirements for routine application to be reserved for 1ater consideration. The method of total combustion was chosen and submitted to a limited number of tests against primary standard samples. Considerable experimental difficulty was encountered, indicating that additional work on the experimental arrangements is desirable. While the work to (late by no means represents a completed investigation, it is helieved that the combustion method is basically sound and that its development should be continued. Choice of Method Of the several available methods, mechanical disintegration. electrochemical methods'2'3 modifications of the Sieverts experiment,% and vacuum fusion, were all judged to contain one or more factors of un- certainty not at present completely cvaluated or suhject to complete control. These methods, therefore, were considered currently unsuitable for referee purposes. Solid evolution was considered to be of doubtful significance when conducted in the alpha range. A reasonable chance for a true analysis was found for evolution in the gamma range. Preliminary tests have indicated a very slow rate for evolutioll from gamma iron. indicating a running time of possibly 100 hr. for a one-centimeter sample. Difliculty in distinguishing such slow. evolution from blank gas was anticipated, hence the method was not consitlerctl the most suitable for the present purpose. The combustion method was evaluated as being most sound on fundamental principles. The only important unknown would be to determine that the iron oxide formed did not occlude water at the tcmperaturv of the combustion.with the odvious precautions of using a sound and clean specimen, providing a system sufficiently tight to give acceptable blanks in longtime runs, and providing a suficicntly sensitive measuring system, reasonable, precise, and truthful analytical results could be logically expected. Apparatus The equipment as originally operated is shown in Fig. I, and the glassw-are in its latest modification in Fig. 2. The sulphuric acid drier and small safety tube in the upper right of Fig. I were replaced by a KOH drier and combined manometer safety tube, to permit operation at reduced

Jan 1, 1945

By Harold F. Yde

Hydraulic tailing fill in the Butte deep-level mines resulted from studies made in 1958 by The Anaconda Co. Mining Research Department. At the time of the study, dry mine tailing was hauled via rail cars from the Anaconda tailing ponds, 25 miles distant, to the tailing fill plants of the underground mines at the Leonard, Anselmo and Mt. Con mines. Presently, tailing from the Weed concentrator in Butte is delivered to the Kelley shaft via pipeline and stope filling has become automated. Tailing at 30% solids is pumped 8000 ft horizontally and upward from the concentrator to the Kelley fill plant, where it is dewatered and deslimed by three Krebs cyclones. These discharge the material into the cased and grouted mine delivery boreholes at desired densities of up to 70% solids. The vertical boreholes and 4-in. rubber-lined Victaulic pipe carry the material downward to horizontal distribution lines, which in turn tap into the 3-in. stope-filling, unlined Victaulic pipelines.

Jan 1, 1970

By N. E. Rogen, N. J. Grant

AGE-hardening in nickel-chromium-titanium-aluminum alloys in the composition range characterized by the Nimonic alloys, is dependent upon the precipitation of the Ni3(AI,Ti) (y') phase.1 This phase is found to precipitate at about 700°C.1 Ni,Al is a face-centered-cubic ordered structure with a lattice parameter of 3.560 A. The atomic configuration is such that the aluminum atoms occupy the cube corners and nickel occupies the cube faces with titanium substituting for the aluminum preferentially. A maximum of three out of every five aluminum atoms can be replaced by titanium atoms in the -y 'phase.' When the solubility of the y'-phase is exceeded for titanium the T(Ni,Ti) phase is formed. The T-phase is an ordered close-packed hexagonal intermetallic structure which shows little solubility for the other elements in these alloys. The lattice parameter for T-phase is a - 2.5454 kr and c = 8.2900 kx units."

Jan 1, 1959

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.'-' One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors' determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

PRESIDENT WILLIAM KELLY, District 5 IRON MOUNTAIN, MICh PAST PRESIDENTS E P MATHEWSON, District 0 NEW YORK, N Y ARTHUR S DWIGHT, District 0 NEW YORK, N Y FIRST VICE-PRESIDENT J V W REYNDERS, NEW YORK, N Y TREASURER CHARLES F RAND, NEW YORK, N Y

Jan 1, 1923

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

GEORGE F. COMSTOCK (author's reply to discussion*).-Mr. Thum's description of the effects of butt welding and spot welding on the micro-structure of steel are interesting and timely. The speed with which the changes noted by Mr. Thum must take place is indeed remarkable, but the writer has noted a similar very rapid diffusion of carbide in annealing a t a rather high temperature certain samples of soft sheet steel containing massive cementite segregated on a small scale. The massive cementite in such steel can be dissolved and distributed very quickly if the proper temperature is attained. Mr. Thum's explanation of the structure he found in the spot welds seems entirely reasonable, but the mystery of the decarburized material in the butt weld is one that might well be the subject of further research. The possibility of decarburization by air ,might perhaps be worthy of a little more consideration than he gives it, for the oxides formed would be gaseous on account of the presence of carbon, and hence not visible in the microscope, and the effect of the pressure might be to squeeze the carbon oxides, which would normally form blow-holes, out of the metal or possibly into such small volumes as not to be noticed The removal of carbon by liquation and squeezing into the fin would be an effect similar to the "bleeding" of a steel ingot that is rolled while the center is still liquid, giving a soft low-carbon interior in the finished section while the segregate was removed in cropping the pipe. This effect in Mr. Thum's butt welds could, however, only be obtained if the weld was heated to near the melting point of the steel, and if the carbon was considerably segregated in the bars at the start, for the first effect of the high temperature would be to promote diffusion rather than the contrary segregation and Equation. It is gratifying to learn from Dr. Ruder's remarks that his researches have resulted in no disagreement with the few points brought out by the writer's experiments. In addition to the three forms in which nitrogen may occur in iron that he mentions, it would seem that a fourth form is often found; This is apparently a eutectoid, like pearlite, and sometimes almost as coarse as the massive cementite seen in soft steel sheets that have been annealed for a long time. One of the things needed in the metallographic study of steel is an etching reagent that will distinguish definitely between nitride in this form and the more common pearlite or cementite.

Jan 6, 1919

DAVID COLE, El Paso, Tex. (communication to the Secretary*).-I notice that Mr. Callow takes issue with me on certain points I have previously contributed to the Transactions, to which I would reply," follows: Regarding Inspiration: Mr. Callow's refinements of gravity methods made just prior to the advent of flotation in the Southwest were intended to be "down to the minute," and the gravity flow sheet for Inspiration ores which he brought out at that time as the result of his long campaign of experimentation was regarded by many as the last word in wet gravity work. It was not my intention to discredit this good work when I said "he threw small light on slime treatment." "Minus 200 mesh," however, is not-synonymous with "real slime." Repeated treatments by gravity methods will result in the separation of a very large percentage of the fine granular sulphides in sizes much finer than 200 mesh, and I gave him due credit for that. The unavoidable losses were made in the "real" slime which I mentioned in the paragraph which Mr. Callow refers to as my "statements on page 1871," and his refinements were not a solution to the real slime problem. Mr. Callow has called attention to the fact that his best results at. Inspiration in gravity work were obtained on Joe Bush ore and he presents a table, viz., Tests Nos. 68, 71, and 72; and asks us to consider and compare these results, made by his refined gravity methods, with the results obtained by 'flotation methods in the new mill "during the second half of 1915 and in August, 1916." Of course, the ore treated in the mill was what happened to come. It was not Joe Bush ore, and therefore comparisons of detail figures are of no value. In regard to Mr. Callow's statements under the caption "Callow Cells Adopted by Arizona Copper Company," I would say that those who have been sufficiently interested to read my paper and' his remarks will notice what amounts to contradictory statements on several points which I cannot allow to go unchallenged. I was on the ground constantly and got my information at first hand. The tables published were the official ones. Mr. Callow was not present during the period and has been laboring under that disadvantage.

Jan 5, 1917

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10'3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey' to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N's are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen's computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.' The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By T. B. Counselman

PROBABLY the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of being high in phosphorus because of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetite area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake Superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mines, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened up the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium, and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi, and it is these big open-pit deposits that constitute our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers, and tables, which later were replaced by classifiers. Ore particles finer than 100 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes. The latest and most important process that has been

Jan 1, 1943

This discussion of the paper of Chester W. Washburne should have been printed following the remarks of H. A. Wheeler, in Bulletin No. 100, April, 1915, pp. 835 and 836, but was inadvertently omitted. ROSWELL H. JOHNSON:-There is one reason why the hydrostatic interpretation of gas pressure is not wholly acceptable. As we go clown in the sands we seem to get excesses of gas. Particularly in this field it becomes excessive in quantity relative to the amount of water in the sand. If this holds in other fields as well it must mean that there has been an ascension of water, because these sedimentaries when laid down, were filled with connate water. If we do get an ascension of connate water, produced by some such phenomena as its expansion by heat or by the formation of new gas by pressure upon organic materials at great depth, we can hardly expect the pressure to be controlled merely hydrostatically. * In reply to Mr. Wheeler's inquiry as to gas wells with pressure higher than hydrostatic pressure, I would cite the original wells given by Orton on which he based the hydrostatic theory. He used in his calculation a head of 600 ft. above tide, assuming the outcrop of the Manitoulin Islands to be in Lake Superior, whereas the Trenton does not outcrop at Lake Superior. The Manitoulin Islands are in Lake Huron, the level of which is 580 ft. above tide. No allowance is made for the lower density of the fresher water near the outcrop, the weight taken for the whole column being the water of high density found at the wells.

Jan 5, 1915

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965