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By W. Mostowitsch, H. O. Hofman

In our investigation of the Behavior of Calcium Sulphate at Elevated Temperatures with Some Fluxes,' we incidentally studied the decomposition of ferric oxide when heated in a current of dry air. We found that at 1,500° C., with 15-min. periods of heating, Fe²,O³, hardly changed in weight, the greatest loss being 0.23 per cent., and we therefore concluded that the compound remained unchanged at 1,500° C. in a current of dry air. In a more recent experiment we heated Fe²,O³, in a current of dry air and found that there was a decided loss in weight. A new investigation upon the behavior of Fe², O³, using a larger amount of substance and heating for a longer period of time, revealed the fact that a measurable dissocia-

Jan 1, 1910

By HENRY JULLUM

THE ARGONAUT' mill stands at the crest and spreads down the western slope' of a hill, which incidentally covers the' outcrop of the Argonaut vein' at this point. The collar of the main shaft of the mine is situated on the eastern slope of the same hill 120 ft. below the highest ?point. The present mill, built in 1916, was designed to treat 250 tons per 24-hr. day. This capacity has not been attained recently owing to the inability of the mine to produce enough ore while extensive development and underground construction were under way. At present, however, the mine is more than able to take care of the mill requirements.

Jan 1, 1932

By A. Patton, F. N. Speller

The use of roll scale in the Bessemer process dates back, to the best of our knowledge, at least 20 years. It was first used by the Ohio Steel Go., Youngstown, Ohio (now the Ohio Works of the Carnegie Steel Co.) under the direction of Sam McDonald, Superintendent of the Bessemer Department at these works. Two 10-ton vessels and one blowing engine capable of blowing one heat at a time were employed. The object of using the scale was to shorten the length of the blow, or in other words, to increase the production with the same equipment. Various means were tried out for introducing the roll scale into the bath of molten iron: It was shoveled into the vessel before the heat was charged, so that the metal would flow over the scale; it was shoveled into the bath after the vessel was turned up; it was dumped into the empty iron ladle by the wheelbarrow-load, and at times was dumped on top of the molten metal in the iron ladle. But the practice of introducing the scale into the iron ladle had to be abandoned on account of danger from explosions and of skulling the ladles. It was soon learned that the proper place to charge the scale was in the empty vessel, so that when the molten iron was poured into the vessel it flowed over the scale, causing a considerabIe reaction to take place before the heat was turned up. Eventually, cylindrical chutes similar to those now in use were installed. Into these chutes the scale is dumped and carried into the empty vessel. Before this convenient means of introducing the scale was adopted, the Ohio Works had satisfactorily demonstrated that roll scale would increase production, by blowing 107 heats in one 12-hr. turn (1,087 tons) with one blowing engine, blowing one heat at a time; whereas, prior to the use of scale, the best practice at these works was about 80 heats under the same conditions. In using roll scale and other oxides of iron to facilitate and control the refining of pig iron in the converter, the Bessemer plant has borrowed one of the most active agencies used in the open-hearth process with, as would be expected, much the same results. The effect of such additions to the Bessemer charge may be discussed as to the influence of this practice on quality, production and cost.

Jan 1, 1917

By E. Posnjak

IT is rather the general belief that acidified solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no. oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by, passing air for 3 hr. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will be proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2. His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 1, 1927

By P. W. Davies, B. Wilshire

PREVIOUS investigations on the effect of stress changes on the high-temperature creep and fracture behavior of metals have been confined mainly to the testing of complex alloys.172 Most of these alloys are structurally unstable during creep because of such effects as recrystallization, overaging, and so forth, so that the results are of limited application. The only pure metals on which observations have been made appear to be lead3,4 and aluminum5 tested under conditions which allow rapid recovery to take place. The present work describes the effect of a single stress change on the creep and fracture properties of a metal in which recovery is very slow. A Ni 0.1 at. pct Pd alloy was used so that grain growth and recrystallization did not occur during creep testing. Specimens of this material were heat-treated to give a uniform grain size of 10 grains per mm. Creep tests were carried out at 500°C using Denison T.47 machines; details of the creep-testing procedure have been given elsewhere.' All specimens were tested at a constant initial stress of 5 tpsi which gives, in an uninterrupted test, a minimum creep rate of ~10-3 pct per rnin and a life of -7000 min. Specimens were loaded under these standard conditions and after 1500 min, when secondary creep was well-established, the stress was changed to either 8, 7, 6, 4, 2, or 0 tpsi for a period of 180 min. After this time the original load was reapplied and the tests continued to fracture. The results are shown in Fig. 1. No detectable creep occurred during the period of reduced load, even at 4 tpsi, and on reverting to 5 tpsi the creep rate returned to its original value immediately. Increasing the stress to 8, 7, or 6 tpsi resulted in an instantaneous extension followed by a period of transient creep leading to a new steady creep rate. On returning from these higher stresses, the resulting creep rate at 5 tpsi was very low compared with the original value. Furthermore, the higher the stress during the stress change, the lower was the final creep rate. It is significant that the rupture life is comparatively unaffected by any of these stress changes.

Jan 1, 1965

By R. D. Vaughn

The limiting cases of non- Newtonian fluids flowing inside a concentric annular duct are developed without using a model of the fluid behavior. The solutions provide limits with which to test the various models of fluid behavior such as the power law and Bingham plastic models. The results of previous theoretical work are discussed in terms of limiting cases. This limiting case study also shows that experimental work on flow of non-Newtonian fluids in annular ducts should be confined to ducts for which the ratio of the radius of the inner wall to that of the outer wall is less than 0.3 and preferably less than 0.2. INTRODUCTION During the last 10 years the problem of laminar flow of non-Newtonian fluids in concentric annuli has received much attention large1y because of its application to the hydrodynamics of the wellbore. Recently solutions utilizing the power law1,2 and Bingham plasticl,3,4 models have been published. In this paper the method of limiting cases, which has been successfully applied to laminar-flow heat transfer516 will be applied to the problem of flow of non-time dependent, non-Newtonian fluids through annuli. This method permits solutions for the limiting cases to be made without using a model of unknown validity. The solutions, therefore, provide limits with which to test the various models which have been or will be proposed. A pertinent conclusion concerning the region of experimental work is also provided. DEVELOPMENT OF LIMITING CASES The limiting cases for the axial flow of fluids in concentric annuli may be defined with reference to Fig. 1. It is possible to define two limiting cases which pertain to the physical dimensions of the annulus. First, the annulus must degenerate to a circular pipe as the radius of the inner wall decreases or, as k = (k R/R) ? 0. Second, the annulus must approach the limit of parallel plates of infinite extent as the spacing between the inner and outer tubes becomes small in comparison with the radius R of the annulus, or as k?1. It is also possible to ascertain three limiting cases which pertain to fluid behavior. With reference to Fig. 2, as a fluid becomes progressively more pseudoplastic, the shear stress-shear rate relationship progressively approaches the indicated horizontal line more closely. At this limit the shear stress becomes independent of the shear rate. At the other extreme of increasingly dilatant behavior, the vertical asymptote is approached. Intermediate between these two limiting cases lies the case of the Newtonian fluid. Fluids which exhibit a yield shear stress also approach the limiting case of "infinite" pseudoplastic behavior. The remainder of the theoretical development is concerned with the description of and the solutions

By CHARLES R. KETES

I. INTRODUCTORY. Lake Valley, New Mexico, has long been one of the most widely known mining districts of southwestern United States. For many years its silver-mines have been among the most famous of the country, visited by many mining men and geologists; yet little information regarding the origin of the ore-deposits and the influencing geologic conditions has found its way into print. With the recent revival of public attention, after a decade and a half of utter stagnation, to the mining of silver in the Southwest, special interest attaches to the genesis and geologic disposition of the ore-bodies which are so finely open to inspection in the Lake Valley district. Moreover, the local features here described are typical of the conditions existing over a much larger field. The fact that the ores are chiefly the chloride and the chloro-bromide of silver adds further interest. Data bearing upon the genesis of haloid ore-deposits are, at the present time, very much sought. Arid regions offer particularly favorable conditions for the formation of such ores. This New Mexican district appears to supply solutions to many problems concerning this class of ores, which have long vexed the student of ore-deposits. II. LOCATION AND HISTORY. The town of Lake Valley is situated in Sierra county, in the southwestern part of New Mexico, and 100 miles northwest of El Paso, as the crow flies.From a mining standpoint, the location of the place is itself suggestive, as it lies on the southeastern slope of the great quaquaversal arch of the Colorado plateau. The center of this vast dome is in north-central Arizona, and radii about 150 miles in length reach its foot in all directions. Around its basal margins runs the broad mineralized belt containing most of the great mines of the Southwest, which extends from south-central Colorado southward and southwestward through New Mexico, thence westward through Arizona, northwestward and northward through southeastern California and western Nevada, and, finally, eastward through Nevada and Utah into Colorado again. This great mineralized belt is important as geographically limiting profitable mining over the greater part of five States.

Jan 1, 1908

By E. M. Norris

In the summer of 1917 it was decided to fireproof the main Tramway hoisting shaft of the Anaconda Copper Mining Co. at Butte, Mont. The shaft has three hoisting compartments and one pump compartment; it is timbered with 12 by 12-in. (30.5 by 30.5-cm.) fir timber, and is 2475 ft. (754 m.) deep. Subsidence and displacement of the surrounding country rock had produced exceedingly heavy ground, and had carried the shaft out of line, in several places, by as much as 2 ft. (0.6 m.) displacement. Constant repairing and realigning of the timbers had been necessary in order to maintain clearance for the cages. The most feasible method of fireproofing, therefore, seemed to be to cover the timbers with a coat of concrete applied with the cement gun. The cement gun, which is operated by compressed air at ordinary mine pressures, feeds a mixture of sand and cement through a hose to a nozzle having a water connection. The mortar in fluid form is thus sprayed upon the prepared surface in thin layers, which can be built up to any desired thickness. The cement gun can be set up at any convenient point; satisfactory results have been obtained with the nozzle a distance of 500 ft. (152 m.) from the gun. The shaft was thoroughly overhauled and the timbers put in the best possible state of repair. Between the 1000 and the 1400 levels, much loose ground lay against the shaft timbers on the north side; this was breast-boarded back and a 30-in. (76-cm.) reinforced-concrete retaining wall was erected, leaving a space of 12 in. (30.5 cm.) outside the shaft timbers to allow for future movements of the ground. For convenience in handling men and materials, it was arranged to concrete the auxiliary hoisting-cage compartment and the pump compartment first, using the cages of the main hoist to serve the cementing crews. The auxiliary cage was then available while the remainder of the shaft was being concreted. A tight partition of 2-in. (5.08-cm.) plank was erected between the auxiliary and the adjoining hoisting compartments, for better protection of men riding on the cages. The application of concrete made this

Jan 1, 1920

By John Ryan

SIR HUMPHREY DAVY'S epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demon¬strated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the work-men's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines has demonstrated some dan¬gers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but 1-potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Conse-quently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Dangerous coal mine gases may be placed in two groups: (1) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CHI) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture.

Jan 2, 1927

By Glenn A. Marsh, George Bernard

It is often assumed that aerated oil field brines which are to be injected underground contain dissolved oxygen in amounts which will cause appreciable corrosion. Through the use of a new portable dissolved oxygen meter, accurate determinations were made at three brine conditioning plants. At two older plants, dissolved oxygen concentration in the final treated brine was found to he almost zero In spite of aeration during the conditioning process. At a new plant, dissolved oxygen was initially present but disappeared soon after the brine was "inoculated" with oxygen-free brine from one of the other plants. Corrosion tests at the two older plants have substantiated predictions that the brines would lint be corrosive. These results show that mechanical deaeration may not always be required in brine treating plants. INTRODUCTION The present work was undertaken to add to our knowledge of aeration and deaeration of oil field brines in brine conditioning plants. It is commonly assumed that brines which are exposed to the air soon become more or less saturated with dissolved oxygen. Since oxygen-containing brines are known to be corrosive, precautions are often taken to keep air out of brine through the use of closed systems or mechanical deaeration. The study of oxygen in brine has been seriously hampered in the past because of the lack of a suitable analytical tool. The standard Winkler method for the determination of dis-solved oxygen is satisfactory for use in fresh water, but not in many oil field brines. Corrections have to be made for a number of reducing substances such as ferrous iron and hydrogen sulfide which are commonly present in natural brines. Very often the correction factors are much greater in magnitude than the amounts of oxygen which are to be determined, and consequently erroneous results are obtained. Also. erratic Winkler data are obtained when appreciable concentrations of calcium and magnesium salts are present. The first step in carrying out a systematic study involved designing a portable dissolved oxygen apparatus which would operate in natural brines. Subsequently, this apparatus was used in three brine conditioning plants. Dissolved oxygen data obtained here, and certain corrosion rate data, illustrate the interesting behavior of oxygen in these oil field brines. APPARATUS A portable dissolved oxygen meter described in detail elsewhere,' was developed specifically for use with oil field brines. It is a polarographic apparatus employing a small rotating platinum electrode (cathode) and calomel reference electrode (anode). A potential of 0.7 volts is applied across the electrodes while they are immersed in the brine to be tested. 4References given at end of paper.

Jan 1, 1952

By A. J. Lyon

THE stability and permanence of any structural material used in aircraft are of paramount importance. The spontaneous hardening, or age-hardening; which takes place in some of the aluminum alloys under ordinary conditions of temperature and atmosphere, is accompanied by an increase in tensile strength and proportional limit and a decrease in elongation or ductility. Within the last few years the introduction of a number of strong and ductile casting alloys led to a study by the Materiel Division, Air Corps, of the permanence of the physical properties in several of these alloys. It has been found that even though some alloys have good properties directly after casting or heat treatment, they are not satisfactory for stressed parts that require a combination of strength and ductility. It has also led to the conclusion that all alloys that can be hardened by artificial aging-heating in a temperature range below 170° C. (340° F.)-will harden spontaneously if allowed to stand for a sufficient length of time. It follows that, in aircraft work where the factors of safety are limited on account of the necessity of keeping the weight of the structures as low as possible consistent with their safe operation, the properties of the alloys in the stable or final condition should be used as a basis for design rather than the properties obtained on the material directly after casting. The work of Wilm in Germany, Hanson and Gayler at the National Physical Laboratory in England, and Merica, Jeffries, and others in the United States, has shown that the spontaneous hardening is characteristic to a greater or less extent in all aluminum-base alloys in which the solubility in the solid state of the alloying constituents decreases with the temperature. It has been shown that, by heating to a temperature as near as possible to the melting point of the material and soaking at that temperature for a sufficient length of time and then quenching or cooling rapidly, a maximum amount of the soluble constituents can be retained in solution and the condition of maximum hardening effect upon aging can be obtained. Also, in ordinary sand and chill castings, without heat treatment, a sufficient amount of the alloying constituents is held in solution to cause important changes in the final physical properties.

Jan 1, 1928

By G. Donald Emigh

WESTERN phosphate resources which lie in Ida- ho, Montana, Utah, and Wyoming, have seen great expansion of activity in recent years. Growth has been two-pronged: expansion in fertilizer use, and since 1949, into the elemental phosphorous industry. Elemental phosphorous, produced in the electric furnace, goes largely into chemical making. Phosphate ore was first recognized in the West about 1889. Production started in 1906, and for many years consisted of underground operations by small companies operating sporadically. In 1920 Anaconda Copper Mining Co. opened the underground Conda mine near Soda Springs in southeastern Idaho, and has maintained and increased its operations since then. About 1930 Montana Phosphate Products Co. began underground mining in Montana and has remained a steady producer. In 1945 San Francisco Chemical Co., one of the oldest companies in the western field, initiated strip mining at the Waterloo mine near Montpelier, Idaho, and later at Leefe mine near Sage Junction, Wyo. In1946 J. R. Simplot Co. began open pit mining at Gay mine near Fort Hall, Idaho. In 1950 Victor Chemical Works began underground development work in the area of Maiden Rock, south of Butte, Mont.: and has since mined there. Monsanto Chemical Co. began open pit mining near Soda Springs, Idaho, in 1951.

Jan 11, 1954

By A. B. Kinzel

ALTHOUGH calcium carbide and other compounds of calcium, as well as a number of calcium alloys, are well known and are the basis of important industries in the of United States, calcium metal has been thought of as something of a rarity and has received comparatively little attention from industrial metallurgists. The metal may he made in a number of ways, but the electrolytic deposition of calcium from a molten calcium chloride bath was the first process to be used for its commercial production and is still the standard procedure. Calcium metal has elicited little interest among nonferrous metal producers, as the demand has been relatively small and its production restricted to only a few plants, exclusively in France and Germany.

Jan 1, 1941

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty's theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By J. H. Scaff, H. C. Theuerer

Germanium may be reversibly converted from n to p type by heat treatment. Data for the conversion and the associated changes in resistreatment.tivity are given and the results are interpreted in terms of changes in the donor-acceptor balance. MEANS for controlling the electrical properties of germanium in a predictable manner are of interest because of the increasing utilization of this element as the semiconducting material in electrical devices. Since both the mechanism and the magnitude of the electrical conductivity depend upon the kind and quantity of impurities present, the conductivity usually is adjusted by first carefully purifying the germanium, and then, by standard alloying procedures, adding the elements desired. The elements usually added are from the third or fifth periodic groups depending upon whether p- or n-type germanium is desired. However, in the development of germanium rectifiers during the war, it was found that it was possible also to modify reversibly the conductivity of germanium and even to produce conversion from n to p type by heat treatment.1,5 Since then a detailed study of this effect has been made. The data are presented in this paper and an explanation is offered for the effects observed. Preparation and Experimental Procedure The method used in preparing the germanium ingots for this investigation has been previously described.' The method consists essentially of (1) reduction of GeO2* and (2) preparation of a 50-g ingot from the reduced material. Graphite containers are used in both steps. In the first step the GeO2 is reduced in hydrogen at 650 °C to form a sponge germanium which, to assure complete reduction and to obtain massive materials, is fused subsequently in the reduction furnace by gradually raising the temperature to 1000°C. The button of germanium thus obtained corresponds to a yield of 99.8 pct. The final ingot is prepared by fusion of the germanium button in a helium atmosphere. A cylindrical crucible in a vertical silica tube furnace is employed and the crucible is heated by an external induction coil. The ingot is solidified from the bottom upward by raising the induction coil at a constant rate with power to the coil kept at a fixed value. In such ingots, segregation is normal and most of the impurities are concentrated in the last region of the ingot to freeze. It follows then that the major portion of the ingot is purer than it would have been if freezing had occurred in a random fashion. Moreover the orderly advance of the freezing surface during solidification establishes in the ingot a succession of surfaces of constant composition, if it is assumed that the liquid is homogeneous and that diffusion in the solid is negligible. Therefore, some information on the distribution of impurities in the ingot may be acquired by determining the shape of the solid-liquid interface at different stages of solidification. This is of importance because the concentration of impurities will be seen to affect the response of germanium to heat treatment. Such information is difficult to acquire by direct means, for the impurities responsible for the electrical properties of germanium prepared in this way are present

Jan 1, 1952

THE first session of the production engineering group on Wednesday, morning, with J. B. Umpleby as chairman, recorded the principal developments since the Fort Worth meeting. Added to this was a lively discussion of pressure maintenance. Recent advances in the air-gas lift have resulted from the need of applying the method to smaller wells at lower costs. In many places intermittent flow has given excellent results, and numerous mechanical de-vices for its automatic control have been, developed. Papers by C. V. Millikan on the Mid-Continent field and by A. H. Bell on California, fields formed the basis for discussion. The maintenance of initial sand pressures was ably discussed for two Texas fields by t. V. Foran in a paper that not only outlined the technic of operation and the results obtained but also contained noteworthy cost data in terms of increased ultimate production. Mr. Foran recommends the use of air in the first stages of pressure maintenance as a means of determining sand conditions and directions of flow, later turning to gas, if available, because of its greater solubility on oil. A round table discussion on petroleum engineering educational problems, with H. G. George as chairman, brought out much interesting discussion that is difficult to summarize. The other Wednesday morning session was a refinery engineering symposium with T. G. Del-bridge as chairman and the economical application of heat for the general topic. A paper on the modern pipe -still, by H. S. Bell, and another by C. W. Stratford on the modernization of the cylindrical still elicited a lively discussion.

Jan 3, 1928

By A. J. Lyon

The stability and permanence of any structural material used in aircraft are of paramount importance. The spontaneous hardening, or age-hardening, which takes place in some of the aluminum alloys under ordinary conditions of temperature and atmosphere, is accompanied by an increase in tensile strength and proportional limit and a decrease in elongation or ductility. Within the last few years the introduction of a number of strong and ductile casting alloys led to a study by the Materiel Division, Air Corps, of the permanence of the physical properties in several of these alloys. It has been found that even though some alloys have good properties directly after casting or heat treatment, they are not satisfactory for stressed parts that require a combination of strength and ductility. It has also led to the conclusion that all alloys that can be hardened by artificial aging—heating in a temperature range below 170" C. (340" F.)—will harden spontaneously if allowed to stand for a sufficient length of time. It follows that, in aircraft work where the factors of safety are limited on account of the necessity of keeping the weight of the structures as low as possible consistent with their safe operation, the properties of the alloys in the stable or final condition should be used as a basis for design rather than the properties obtained on the material directly after casting. The work of Wilm in Germany, Hanson and Gayler at the National Physical Laboratory in England, and Merica, Jeffries, and others in the United States, has shown that the spontaneous hardening is characteristic to a greater or less extent in all aluminum-base alloys in which the solubility in the solid state of the alloying constituents decreases with the temperature. It has been shown that, by heating to a temperature as near as possible to the melting point of the material and soaking at that temperature for a sufficient length of time and then quenching or cooling rapidly, a maximum amount of the soluble constituents can be retained in solution and the condition of maximum hardening effect upon aging can be obtained. Also, in ordinary sand and chill castings, without heat treatment, a sufficient amount of the alloying constituents is held in solution to cause important changes in the final physical properties.

Jan 1, 1929

By A. J. Lyon

The stability and permanence of any structural material used in aircraft are of paramount importance. The spontaneous hardening, or age-hardening, which takes place in some of the aluminum alloys under ordinary conditions of temperature and atmosphere, is accompanied by an increase in tensile strength and proportional limit and a decrease in elongation or ductility. Within the last few years the introduction of a number of strong and ductile casting alloys led to a study by the Materiel Division, Air Corps, of the permanence of the physical properties in several of these alloys. It has been found that even though some alloys have good properties directly after casting or heat treatment, they are not satisfactory for stressed parts that require a combination of strength and ductility. It has also led to the conclusion that all alloys that can be hardened by artificial aging—heating in a temperature range below 170" C. (340" F.)—will harden spontaneously if allowed to stand for a sufficient length of time. It follows that, in aircraft work where the factors of safety are limited on account of the necessity of keeping the weight of the structures as low as possible consistent with their safe operation, the properties of the alloys in the stable or final condition should be used as a basis for design rather than the properties obtained on the material directly after casting. The work of Wilm in Germany, Hanson and Gayler at the National Physical Laboratory in England, and Merica, Jeffries, and others in the United States, has shown that the spontaneous hardening is characteristic to a greater or less extent in all aluminum-base alloys in which the solubility in the solid state of the alloying constituents decreases with the temperature. It has been shown that, by heating to a temperature as near as possible to the melting point of the material and soaking at that temperature for a sufficient length of time and then quenching or cooling rapidly, a maximum amount of the soluble constituents can be retained in solution and the condition of maximum hardening effect upon aging can be obtained. Also, in ordinary sand and chill castings, without heat treatment, a sufficient amount of the alloying constituents is held in solution to cause important changes in the final physical properties.

Jan 1, 1929