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By Royal Jackman

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investiga-tions. The development of X-ray examination of minerals and improve-ment in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investi-gators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation.

Jan 1, 1933

By Herbert Clark Hoover, Lou Henry Hoover

DIFFERENT methods of parting gold from silver, and, on the other hand, silver from gold, were discussed in the last book; also the separation of copper from the latter and further, of lead from gold as well as from silver ; and, lastly, the methods for refining the two precious metals. Now I will speak of the methods by which silver must be separated from copper, and likewise from iron.1 The officina, or the building necessary for the purposes and use of those who separate silver from copper, is constructed in this manner. First, four long walls are built, of which the first, which is parallel with the bank of a stream, and the second, are both two hundred and sixty-four feet long. The second, however, stops at one hundred and fifty-one feet, and after, as it were, a break for a length of twenty-four feet, it continues again until it is of a length equal to the first wall. The third wall is one hundred and twenty feet long, starting at a point opposite the sixty-seventh foot of the other walls, and reaching to their one hundred and eighty-sixth foot.

Jan 1, 1950

By R. M. Brick

THE etched microstructures of cold-worked alpha brasses, after reduc-tions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonomously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {111}, in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson5 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into sym-metry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By T. E. Davidson, C. G. Homan

This report deals with a study of the effects of extreme hydrostatic pressure on a polycrystalline material which exhibits a high degree of elastic anisotropy. Metallographically prepared polycrystalline bismuth samples were subjected to pressure levels up to 20,000 atm in a piston type gas-liquid system. The observed structural changes consisted of deformation localized along the grain boundaries, which appears to be a boundary migration phenomena, and widespread slip and cross slip. Subsequent deformation is progressive with increased pressure, and is substantially different in type from the deformation characteristic of uniaxial compression. A large amount of interest has been shown in recent years in the effects of extreme pressure on metals. In this connection, many investigations into the effects of pressure on physical and mechanical properties and reactions have been undertaken. Due primarily to the experimental difficulties involved, there has not been a great deal of study of the structural changes resulting from exposure of metals to extreme pressure. It has been difficult, for instance, to produce a true hydrostatic stress state in many of the extreme pressure devices used, and also to directly examine specimens metallographically before and after pressurization. The results of a preliminary investigation into one of the effects of extreme pressure, and its associated true hydrostatic stress state, on the structure of metals are discussed herein. Metals exhibit varied degrees of anisotropy in their physical and mechanical properties. Significant among the anisotropic properties is the modulus of elasticity, which varies by a factor of as much as three in some of the fcc metals, and by much larger factors in some of the less symmetrical elements. As a result of the variation of the modulus of elasticity with crystallographic direction, shear stresses will be induced in polycrystalline samples under true hydrostatic compression. Depending on several factors, these shear stresses could become of suffi- cient magnitude to cause localized plastic deformation. Presented herein are some of the structural changes observed in polycrystalline bismuth as a result of exposure to hydrostatic pressures of up to 20,000 atm. Although several other materials in both bicrystal and polycrystalline form are also currently under investigation, bismuth was chosen initially, due to its low symmetry and moderately high degree of anisotropy in the elastic properties. The fact that extreme hydrostatic pressure can induce structural changes in some elements in the polycrystalline state is of importance in itself. However, it may also be a factor in many of the other extreme pressure effects. For instance, this localized plastic deformation could substantially lower the recrystallization temperature, thus altering the effects of extreme pressure on this phenomenon. Also, as commented on by ridgman,' the hysteresis in the polymorphic transition of polycrystalline bismuth under extreme pressures could possibly be attributed to structural changes brought about by unequal compressibility. Therefore, to accurately determine the true effects of extreme pressure on metallic substances, one first must determine if any structural changes due to hydrostatic compression are also simultaneously occurring. The purpose of this work has been to determine whether the shear stresses induced by hydrostatic pressure in an anisotropic polycrystalline material, such as bismuth, could reach a magnitude great enough to cause plastic deformation and to study the resultant structural changes and effects. THEORY In a metallic crystal, the elastic properties are dependent upon the crystallographic direction and plane. Depending upon the degree of anisotropy of the elastic properties and other factors, internal shear stresses of sufficient magnitude to cause localized plastic deformation may be induced in polycrystalline material by true hydrostatic compression. The following highly simplified two-dimensional model of two adjacent grains in a polycrystalline aggregate under hydrostatic pressure serves to schematically demonstrate how these shear stresses arise in an anisotropic material.

Jan 1, 1963

By Norman Braly

THE following is not offered as an extended paper on the subject of shaft sinking, but more as a description of the present practice of shaft sinking in the Butte district. The Anaconda company is sinking at present the following shafts: Badger State, Moose, Mountain Consolidated, Mountain View, Pennsyl-ania and Tropic. At the High Ore and Leonard mines the shafts are being deepened by sinking two compartments and will subsequently be enlarged to the full working size by raising alongside the compartments which are now being sunk. The following other companies are also sinking shafts: Butte-Alex Scott, Butte and Zenith City, Boston and Corbin, North Butte Mining Co. (at the Granite Mountain shaft), East Butte Co. (at the Pittsmont shaft), and the Rainbow Lode Development Co. Shaft Timbering. The shafts of the Butte district, generally speaking, are of three compartments arranged in a straight line, and the pump compartment is usually arranged for the use of an auxiliary hoisting cage, as well as for carrying pipe lines and electric wires. The Rainbow shaft is practically square, and of three compartments. The length of the shafts outside of timber will vary from 17 to 22 ft., and the width from 6 ft. 6 in. to 7 ft. Fir timber is used in all shaft work. This may be obtained from the Coast, when it is known as Coast fir, or from Idaho or Montana, when it is known as native fir. The native fir seems to be the tougher wood, but it is hard to obtain clear lumber in the lengths and sizes necessary for shaft work. Some of the shaft timber of the Anaconda company has been treated with creosote as a preservative, but this practice has not come into general use, as the ground of the camp is so heavy that the timbers usually crush before they rot. The size of timber most .used for shaft work is 12 by 12 in., while 10 by 12 in., 10 by 14 in. and 12 by 14 in. are used for some of the special pieces around the shaft. The new Leonard shaft is timbered with 14 by 14 in. wall plates throughout.

Jan 8, 1913

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem'ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam'ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961

By J. Ruzicka

IN creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently bear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addi-tion to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabri-cated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment.

Jan 1, 1937

By Paul M. Tyler

Mineral raw materials, because they are essential to our industrial prosperity and military strength, must be made available in substantial quantities. regardless of cost. Variations in the cost of procuring minerals, as compared with the cost of obtaining other commodities, and changes in the cost of production of different minerals relative to one another, will naturally influence the quantities of a given mineral item that can be marketed readily. However, in the last analysis, the cost of winning minerals from the ground usually constitutes only a small fraction of the value of the end-use products and services derived from them. The miner's share of the cost of a typewriter, telephone circuit, or even a modem office building, is almost insignificant. Far more important to the ultimate consumer, therefore, than any minor saving in cost is the assurance of ample supplies of the minerals needed to aliment our expanding economy. To create a successful metal mining operation involves ( 1 ) the discovery and systematic development of a mineral deposit, (2) extraction of the ore, (3) the mechanical and metallurgical processing to eliminate worth- less or harmful impurities, and (4) the profitable disposal of the product. The first step of the technological process belongs chiefly in the realm of the geologist, the second is a mining engineer's job, the third is mainly up to the millmen and extractive metallurgists; whereas the fourth and equally important step poses a commercial problem that has aspects in common with the marketing of other products. Ore finding is far from being an exact science. There is no mathematical criterion for evaluating the efficiency of prospecting and exploration. Lady Luck shares the honors or assumes part of the blame along with the prospector and geologist. Marketing like- wise involves factors that seemingly defy engineering analysis. Although the other steps can be measured with some degree of mathematical accuracy, even they tend to vary so widely in basic principle, as well as in

Jan 1, 1959

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.' Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959

By A. W. McReynolds

One characteristic of plastic deformation which distinguishes it from elastic strain is the essential inhomo-geneity of plastic strains. Elastic strain varies continuously through a material, and average relative displacements of initially adjacent atoms are only small fractions of their initial spacing, (strains of the order of 0.01 or less). On the other hand, plastic flow corresponds to the appearance of discontinuities in strain of the lattice, such as dislocations or slip bands, where local strain, on an atomic scale, is several orders of magnitude higher. These discontinuities are visible on a microscopic scale as the familiar slip lines (Fig 1). In spite of this obvious microscopic inhomogeneity, however, macroscopic measurements almost invariably show a smooth curve of stress vs. strain (Fig 2b) even if measurements of linear strains be made to an accuracy of one part in 107. This macroscopic homogeneity of strain indicates that the discontinuities in strain on slip planes occur in increments too small or too slow to be recorded individually, and further that they occur sufficiently independent of one another so that the small increments add at random to a smooth stress-strain curve. The present paper describes observations of plastic strain in aluminum of commercial purity and in high purity Al-Cu alloys, where there exists a strong coupling between slip in various regions of the specimen such that once initiated it spreads rapidly through a large volume. The total effect is that of relatively large, rapid, and regularly spaced steps of strain followed by periods of only elastic strain. Fig 2a illustrates the type of "stair-step" stress-strain curve which results. The properties of this cooperative slip phenomenon will be described further in the section on results: in par- ticular it will be shown that each step corresponds to the propagation of a wave of plastic deformation through the specimen. Some interpretations of the mechanism by which it occurs will be made in the following section. Although the type of plastic wave phenomena to be described has not previously been reported, there are numerous cases of related effects in the plastic yielding of metals: YIELD POINT PHENOMENA The most familiar of such effects is the "yield point" observed in low carbon steels, brass, duralurninum, and the like. It consists in the sudden termination of the elastic portion of the stress-strain curve by a large plastic strain. Since the usual tensile machine is such that yielding of the specimen relieves the load, the resulting curve is as shown in Fig 3. As the strain continues, deformation occurs at a lower stress for some time, then follows a rising curve, but with no further sudden yielding. This effect has been observed in brass by Sachs and Shojil and later by many others. Edwards, Phillips and Jones2 made extensive studies of the effect in steel, and of the role of various alloying elements. Although there seems to be fairly clear evidence that the yield point is caused by a hardening of the material by precipitation of impurities, no satisfactory explanation for the sudden yielding has been given. Winlock and Leiter3 have shown that the strain. level of the upper yield point depends strongly on the rate of loading, the yield point increasing by almost a fac- tor of two as the strain rate goes from 0.002 in. per in. per min. to 4.4 in. per in. per min. This effect would seem to imply an incubation period before yielding is initiated at a certain stress. On the other hand, by going to very slow loading rates, Edwards, Phillips and Jones2 showed that the yield point does not become lower and eventually disappear as might be expected, but, on the contrary, begins to rise at loading rates below about 25 Ib per in. per min. becoming much higher than at rapid loading rates. STRAIN AGING If, instead of continuing straining of a specimen after occurrence of a yield point, the load is removed and the specimen aged, resumption of the test results in occurrence of another yield point as shown by the dotted curve of Fig 3. The new yield stress is generally higher than the previous maximum applied stress. This hardening of the material by straining and subsequent aging is undoubtedly related to quench age-hardening resulting from the aging of a specimen quenched from high temperature. Since neither effect is observed in pure metals, it is generally accepted that quench-aging in all cases is the result of hardening by precipitation of a supersaturated alloying element, and that strain-aging is probably a similar precipitation, accelerated by disruptions of the lattice by previous strain. Pfeil4 has shown that strain-aging does not occur in iron from which all of the carbon has been removed, but that only a very small carbon content, around 0.003 pct, is necessary to cause strain-aging. In accord with this observation is recent work by Dijkstra5 in this laboratory showing that the solubility limit of carbon in iron is extremely low, less than 0.001 pct at 400°C. Edwards, Phillips and Jones2 have shown that the strain-aging effect is also removed by the addition of small quantities of elements such as Mo, Mn, Ti, and the like, which readily form carbides. Their results demonstrate the

Jan 1, 1950

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By Henry Fay

The erosion of guns is a complex problem which can be solved only by a detailed study of all the factors involved. In the present paper it is proposed to submit the results of observations and experiments which have extended over several years. Certain facts have been established and preliminary reports have been published.' Conclusions have been reached since then which, it is believed, are worth presenting for the purpose of promoting discussion, and with the hope that ultimately the whole truth will be known. The particular phase of the problem which will be presented here is the hardening of the inner surface of the gun tube. It has been known for a long time that after firing a large caliber gun for some time, the surface of the metal becomes hard and brittle, cracks, and wears away.2 The character of this phenomenon may be learned by an examination of some results which are typical, obtained from a detailed study of a 12-in. gun. The gun was trepanned and rings representing various sections of the gun were cut out for examination. The first ring represented the metal at the muzzle end, and the other rings were removed at approximately 120, 240, 325 and 337 in., respectively, toward the breech end. The appearance of the surface of the metal in the different sections is shown in Fig. 1. The greatest amount of wear and maximum amount of hard surface layer was found in section marked E, which is nearest the powder chamber and at the beginning of the rifing; the maximum amount of cracking in D; the maximum amount of copper deposition in C. Section B showed heat cracks on both lands and grooves, and section A showed heat cracks on the driving edge of the lands only. There was much flow of metal in both sections E and D, and there was progressively less effect noticeable toward the muzzle end. The polished cross-section of these same pieces is shown in Fig. 2. The extent of the erosion is greatest nearest the powder chamber, and diminishes toward the muzzle end.

Jan 1, 1917

By T. L. Joseph, G. Bitsianes

The gaseous reduction of dense iron ore is a topochemical process in which reduction takes place at distinct interfaces between solid phases or layers. Under normal conditions, these interfaces remain parallel to the exterior surface of the ore body as they move inward. Certain conditions, such as cracking, high porosity, impurities, entrapped residual oxides, may cause departures from normal topochemical behavior. THE gaseous reduction of dense iron ore proceeds at interfaces between several solid phases or layers.',' Under normal conditions, these interfaces progress inward and remain parallel to the exterior surface of the ore body. This topochemical behavior is clearly illustrated in Fig. 1 which shows partially reduced specimens of natural and synthetic hematite. Using a coordinated sequence of macro, micro, and X-ray examinations, the authors1-'2 found that the number of interfaces and participating phases was in agreement with the Fe-0 system. Above 570°C, reduction of the ore involved a maximum of three common boundaries between four solid phases: iron, wiistite (Fe,O), magnetite (Fe,O,), and hematite (Fe,O,). Below 570°C, reduction proceeded through two interfaces between three phases: iron, magnetite (Fe,O,), and hematite (Fe,O,). The decrease in the number of phases below 570°C was due to the instability of wiistite below this temperature. The sequence of phases was also consistent with the equilibrium requirements. For example, the layers of iron oxides that were formed in topochemical fashion were always orientated in the order of increasing oxygen content. Thus, in Fig. 1 an outer layer of metallic iron is followed in turn by a thick intermediate band of black wiistite, by a thin layer of light magnetite, and finally by a relatively large core of hematite. This arrangement of the oxide layers was due to restrictions in reducing conditions which were imposed by the physical structure of the solid. The highly reducing gas on the outside of the particle gradually lost its reducing power as it penetrated into the specimen. On a macro scale, the layers of the various oxides appeared to be sharply defined and uniform in composition. Microexamination of the sections, however, revealed that the interfaces did possess measurable widths which varied with the porosity and chemical activity of the oxide phase undergoing reduction. For example, Fig. 2 shows three interfaces in a dense hematitic ore which was partially reduced at 850°C. At the iron-wiistite interface where the greatest porosity developed, the reaction proceeded over a zone 25 to 30 microns in width. Toward the interior, the interfaces became progressively narrower until at the magnetite-hematite boundary the reaction zone was about 1 micron wide. In this region the structure was exceedingly dense; the hematite possessing a porosity on the order of 3 pct. A careful micro study across polished layers of the various oxides revealed generally homogenous and single-phase structures. As reported in a previous paper,' the wiistite layer was characterized by an increase in oxygen content with depth of penetration. The topochemical behavior of reduction was studied in six types of ore of different origin, composition, and physical structure. In most cases, reduction proceeded at the boundaries of well defined layers or phases, and this behavior may be regarded as normal for most dense fine grained ores. Deviations from Ideal Topochemical Behavior A number of deviations from the normal topochemical behavior were noted. In these cases, the continuity of the reduction interfaces was disrupted in one of four ways: 1—Cracking of the specimen interrupted the geometric configuration, and the interfacial advance was no longer parallel to the exterior surface. 2—As a result of high porosity, the interfaces were spread over an appreciable distance and all but obliterated. 3—Impurities in the ore promoted a variety of deviations, including cracking. 4—A residual oxide phase was entrapped in the reaction product and left behind the advancing macro interface. Results from Cracking: A crack leading into the interior of an ore specimen presents a path of least resistance for the counter-flow of reducing gases and gaseous reduction products. Higher reducing conditions can be maintained along such cracks and reduction accordingly will propagate well ahead of the normally advancing reduction interfaces. Cracking was caused by a number of factors, one of which was the thermal spalling of impurities in the massive form. A more general type of cracking was due to reduction and was found in all dense varieties of natural and synthetic hematite, particularly in the temperature range of 500" to 700°C. The effect is shown clearly in Fig. 3. In this case, a dense sphere of pure hematite was partially reduced at 650°C for 100 min. The macrosection shows that one large reduction crack had penetrated the specimen and disrupted the normal topochemical advance of the interfaces. The outer layer of iron was only slightly affected but the thin dark layer of wiistite, adjacent to the ferrite, had widened perceptibly as it progressed along the crack. Farther inward, the magnetite layer was greatly disrupted and had penetrated irregularly to form islands of unaltered white hematite. A great deal of internal cracking is evident in the magnetite phase. From a practical point of view, the cracking of dense ores in the blast furnace could lead to desirable as well as undesirable effects. The general result

Jan 1, 1956