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By Henry Howe

W. E. RUDER, Schenectady, N. Y.-In 1913 I presented a paper before this society on Grain Growth, and at that time it seemed to me that the only explanation for grain growth was that of critical strain. I do not think I published the photographs at the time, but I made some experiments on the effect of stretching sheets of metal. This allowed for fairly accurate determinations of the amount of cold deformation, At the time I worked-with silicon steel because one could see the change in grain growth with the naked eye. I stretched about 10-samples from 0.5 per cent. to 10 per cent., and, after heating to 1,050° C., I found that the maximum grain growth occurred at about 2 ½ per cent. cold deformation. This I designated "the critical strain" for maximum grain growth. About a year ago I talked with Prof. Jeffries, who explained to me his ideas of grain growth. It occurred to me that it would be a very easy thing to check the strain hypothesis against the strain and temperature hypothesis, if we took a certain number of these strips, strained exactly alike and heated to different temperatures; in that case the maximum grain growth ought to appear at a different percentage of deformation for each temperature. These experiments showed that there was, as Mr. Jeffries shows in his present paper, a decrease in germinative temperature with increased cold deformation. The samples were stretched from ½ to 8 per cent. and heated for 10 hr. in hydrogen. Samples were introduced into a furnace previously heated to temperature. A maximum grain growth was obtained at 5 per cent. deformation, when heated to 750° C.; at 2 ½ per cent. when heated to 800' C.; at 1 1/4 per cent., if heated at 950°C.; and at 5/8 per cent.. when heated at 1,100° C. This shows very clearly that the germinative temperature decreases with the increase in cold deformation. The growth was very much more marked, however, at the high temperature, i.e., the grain grew more rapidly and attained a much larger size than at lower temperature. In considering the photographs (Fig. A) those along the lateral edges should be ignored because.

Jan 4, 1917

By S. Skowronski

OvErpolEd copper, as commonly defined,- is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such coppcr is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in 'crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, which enablcs copper to be cast free from blowholes. It seems that when oxygen is present, other gases are less soluble in molten copper; when oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, while an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen,' and the effect of this action on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulfur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 1, 1919

By L. J. Murphy

The production of crude oil in the United States is exceeding consumption by one-quarter million barrels per day and, with the possibilities of West Texas, this condition of overproduction, unless controlled, is likely to continue for some time. The resulting low price of oil has caused the operator to observe closely his lease operating costs. The installation of more efficient and reliable machinery has followed and it can well be said that the art of producing oil is on the threshold of a new era. In this advancement electricity has played a leading part. This paper covers only the problem of electricity as applied to lease operation and does not consider other phases of the industry, such as drilling and pipe-line pumping, in which electric power has been utilized economically. In considering electrification of pumping wells, the first question the operator asks is whether or not his costs will be reduced and the second question is whether or not the production will be increased. The third question, although in effect it is closely allied to the first, is the cost of power. The last question can be answered only after a thorough analysis of operating conditions and a study of the power rates prevailing in the particular field under consideration. Within the past few years, the power companies have realized the desirability of a steady 24-hr, pumping load, have made their rates for oil-field service particularly attractive, and in general have shown splendid cooperation in assisting the oil companies in the satisfactory application of electric power to their leases. When everything is taken into consideration, the first cost is practically the same for electric drive as for gas engines when pumping on the beam with individual motors. This cost, at prevailing prices, should aver-age approximately $2200 to $2400 per installation when using 15 to 35-hp., two-speed pumping equipment, including motor and control, countershaft, motor house, belt, installation charges, and a prorated portion of the cost of transmission lines and transformers for serving a number of wells. Since there is practically no difference in the cost of the two installations, it is evident that electricity, to justify its consideration, must have a lower operating cost or produce more oil.

Jan 1, 1928

By F. R. Hutto Jr., F. L. Kady Jr., L. E. Weymouth

The behavior of particulate non-metallic materials in moving contact with smooth surfaces is of interest and concern to manufacturers and users of abrasives, of fillers, and of pigments alike. The theoretical aspects of the subject have been treated to considerable extent in the literature, and correlatic,ns are available that attempt to relate various methods of hardness determination." 2 The particle size and friability are characteristics of the abrasive that are not related to the smooth surface. The hardness, on the other hand, may be visualized as relative to that of the smooth surface. In a study of abrasive action, the role that hardness, per se, plays is a complicated one. For it is necessary to compare the "hardness" of the abrasive, usually a non-metallic, with that of the smooth surface, generally a metal. Hardness of non-metallics is defined as resistance to scratch and is almost universally described with respect to the Mohs scale.3 Minerals have been rated by Mohs numerically from the softest (talc = 1) to the hardest (diamond = 10). By definition, a mineral has a designated hardness when it is scratched by the standard that is numerically just above it on the scale; and conversely, when it scratches the standard that is just below it. Hardness of metals. however.. implies resistance to indentation, a property that has been measured by a number of methods. In fact, the indentation hardnesses of the standard minerals on the hlohs scale have been determined by the Rockwell tester. Reproduced below are two versions of this correlation. 'A conversion chart, prepared by Wilson Mechanical Instruments Division of American Chain and Cable Co., merely gives the conversion from Rockwell to Knoop hardness. The relation between Knoop indentation hardness and Mohs scale has been reported by G. S. Smith — A New Scale of Hardness, The Engineer, Aug. 26. 1949. G. F. Kinney in Engineerin Properties and Aplications of Plastics reports the Rockwell hardness of the minerals directly in the Mohs scale. The question immediately arises as to whether this relation is valid when applied in reverse; namely,

Jan 1, 1961

By F. J. Lecznar

An investigation of the problem of separating two minerals by a moving inclined plane has revealed that only minerals with considerable difference in sliding friction coefficients separate readily; that it is possible to separate two minerals when only one of them has a rolling friction coefficient; that difference in geometrical shape of the minerals is important to separation which improves as grain size increases; and that the thickness of the stream falling on the belt influences the grade of separation - the thinner the stream, the smaller the interference between the grains of the minerals to be separated and the higher the degree of separation. The problem of separating two minerals with different friction coefficients and shapes by a moving inclined plane has been investigated. Friction separators can be used to separate two materials that differ in shape and in friction coefficient. 1,3 Gladkov has presented some theoretical aspects of using a moving plane to clean corn and podded seeds; this method, however, did not result in practical application. When considering the separation of minerals, only those with considerable difference in sliding friction coefficients can be taken into account. Furthermore, it is possible to separate two minerals when only one of them has a rolling friction coefficient. The difference in geometrical shape of two minerals is also important to separation. It has been found that the separation of two minerals improves as the grain size increases. For example, coal and slate over 2 in. in grain size separate much better than materials of smaller grain size. As Table I indicates, the slate grains smaller than 25 mm gradually lose their flat shape with decreases in size and are more rounded than larger grains, which are almost flat. The smallest grains of slate in first and second fractions slide down the belt since their friction coefficients decrease and approach the value of the rolling coefficient. The percentage of separation of the first fraction is, therefore, low. Thickness of the coal stream falling on the belt also influences the grade of separation; the thinner the stream, the smaller the interference between the grains of the two minerals to be separated and the higher the degree of separation.

Jan 1, 1963

By T. Egleston

The manufacture of charcoal in kilns was declared many years ago, after a series of experiments made in poorly constructed furnaces, to be unprofitable, and the subject is dismissed by most writers with the remark that in order to use the method economically the products of distillation, both liquid and gaseous, must be collected. It is asserted with truth that the number of kilns required for a large production of iron would be so great that it is doubtful whether any works would be justified in making the necessary outlay for their constructiou, but it can also be asserted with equal truth that for any such production in a given locality the use of charcoal as fuel would be eqnally unjustifiable. It appears to have been forgotten that there were other manufactures besides iron in which large amounts of charcoal were used, but these consumers seen] to have been guided entirely by the results of the experiments of the iron men, who necessarily made the largest qnantity of it. Some authors speak in a doubtful way of the quality of the charcoal produced, and a few concede that with great care good charcoal can he made in kilns, but that most of the workmen do not like kiln 'charcoal. This is the real secret of the opposition to this method of manufacture. Most of these objections were written when charcoal was the most important fuel used by the iron manufacturer, and when what was a largeproduction of iron for several furnaces was less than that produced by a single modern one, in localities where other fuels can be had. Almost all that has been written on the subject related to the use of the fuel for the manufacture of iron in the blast furnace, where very peculiar properties are required, and where the qnantity produced is limited by the height of the furnace, and this in turn by the crushing resistance of the charcoal. A large production was, therefore, only possible when the best and hardest woods were used. Of all these objections there is not a single one which is not eqnally applicable to any method of charcoal manufacture, whether it be meilers, pits, or furnaces. Until recently, therefore, the manufacturers of charcoal iron

Jan 1, 1880

By J. E. Johnson

THE production of metal-working tools has been revolutionized within the last 18 years, since the invention by Taylor and White of a process of heat-treating steel tools, which resulted in increasing their cutting capacity several fold over what it had been before. This was an exceedingly important invention, although it consisted principally, in establishing this fact overheating when it accidentally, occurred in the ordinary:-process of forging, spoiled the steel, but if carried very much farther or to-a point that would have been considered absolutely ruinous to the steel under the old ideas, it resulted in imparting a cutting power several times as: high as had ever been obtainable before. The quality that gives the steel this power eventually received the name of "red hardness." This name originated in the fact that tools possessing this property retain their resistance to deformation even when subjected to, such severe cutting stresses that the metal just back of the point is heated, under certain conditions, to a visible red. It is interesting in this connection to note that the edge of the tool itself does not become red because it is continually cooled by the fresh metal into which it is forced. The result of Taylor and White's invention was an intensive study, of tool steels all over the world and, although there was-great diversity of analysis in the high-speed steels of the early days, these steels today generally have an approximately similar composition, the principal constituents being froth 15 to 20 per cent. of tungsten, from 4 to 6 percent. of chromium, from 1 to 2 per cent. of vanadium, and from 0.50 to 1 per cent. of carbon. It is probably safe to say that standard brands of such high-speed steels will do from five to ten times as much work in a given time as the carbon steels, and even the Musket steels, which were the sole dependence up to the beginning of this century, when the Taylor-White process was discovered. With the increasing cost of labor, it is not surprising that these steels have driven froth the market, for all but limited purposes, the older types of steel.

Jan 2, 1919

By T. D. Lynch, N. B. Pilling

The development of a proper treatment for shells in conncction with war contracts has brought to our attention the fact that the temperature of the liquid bath in which steel is quenched has a decided influence on the speed of cooling in the case of some liquids and very little in the case of others. Widely different physical results have been obtained by the use of water spray, water immersion, and oil immersion and further experiment has shown that the quenching effect of water used as a spray or an immersion varies greatly with the temperature of the water. The present experiments were undertaken with the idea of obtaining information of a quantitative nature regarding the quenching properties of a number of liquids used commercially in hardening steel. The general features of such cooling media are common knowledge and in the literature may be found records of numerous attempts to evaluate the cooling power of a liquid when used as a quenching bath. Much, if not most, of the data given on this subject is in the form of a simple statement of the time required for a certain heated mass to cool between two arbitrary temperatures when immersed in the liquid, quite regardless of the path of the temperature change. Our own purpose has been somewhat different. We have attempted to isolate that property of these liquids having to do with their ability to absorb heat rapidly, as distinct from the behavior of a considerable mass when exposed to different thermal environments. More specifically, from the data obtained through autographically recorded cooling curves of a small standard mass quenched under various conditions, we have tried to analyze the mechanism of heat absorption by the several liquids, measure the changes in its rate as a function of the temperature of the surface of transference, and ascertain the influence of the temperature of the liquid itself upon both. Without attempting an exhaustive citation of the literature, mention may be made of some of the more important contributions, notably the pioneer work of Le Chatelier,' followed by the extensive investigations

Jan 1, 1920

By T. Egleston

The necessity of using a refractory material capable of much greater resistance to chemical action and having a far higher melting-point than those which contain silica, which melt and sweat off in the furnace even when not exposed to bases forming with silica more or less fusible compounds, has led to a careful practical study of all those materials which contain very refractory bases. The results of these researches, extending over several years, and made on a very large scale in many of the largest works in Europe, are of the highest interest, not only considered as a step in the progress of the study of the materials themselves, but in the application of refractory materials to metallurgical uses in general. The result of the experience of the last seven years with these basic materials, as in general with all such substanccs, is that natural products cannot be used as such. They are either too uncertain in their quality, contain substances which may in certain cases be very injurious, or, when in a condition in which they might be used, are so rare as to become practically unavailable for employment on a large scale. The materials that may he used are therefore not only limited in number. but they must be prepared artificially. When the use of basic artificial material is further extended, no doubt the number of these substances will not only be greatly increased, but the methods of preparation will be both perfected and cheapened to such an extent as to permit their application in processes for which they have hitherto proved too expensive. The quantity of refractory materials required for making ingots will he from 130 to 150 Ibs. per ton, or between 6 and 8 per cent. of the metal produced. In an establishment producing 2000 to 3000 tons of steel per week, considerable space is required to handle the basic materials properly. It is proposed in this paper to briefly discuss these basic materials and their application in the only two metallurgical processes where they have as yet been applied. These are the basic Bessemer and the basic open-hearth process, known as the Thomas-Gilchrist processes.

Jan 1, 1886

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

INTRODUCTION IT is 10. years this summer since the first of the contributions which it has been my privilege to make to the working tools of the hydrometallurgist was set at work, but a full description of what has come to be known as "Dorr Machinery" has never been published in the Transactions of the Institute, and it has been suggested to me that an account of the same would prove of interest to members, although most of those engaged in cyaniding and concentration are probably familiar with it. The account which I shall give of the development of the machines must be recognized as being written from the viewpoint mainly of my own local experience and not from that of one who was familiar with the general metallurgical practice throughout the world. Most advances in any art are conceived before the time is ripe for their development and any .invention which comes into general use will usually be found to have been tried out in a crude way and abandoned more than once. If the early experimenter went as far as the Patent Office, his work may serve no other purpose than to prevent the issuance of the broadest patent to those who later may develop a commercial process. The cyanide process in the United States early in 1904 was mainly confined to the leaching of dry crushed ores, both coarse and fine, and sand treatment of tailings from concentration and amalgamation. In the Black' hills some plants were crushing in cyanide solution, leaching sands and handling the slime by the well-known decantation process. Filter pressing, in use for some years in Australia,had been tried in several places in this country and the Moors process had been abandoned at Mercur after' a short run, but was doing good work at the mill of Lindbergh, Dorr & Wilson, at Terry, and being installed at Bodie and the Liberty Bell. A general feeling, however, still existed that, slimes were to be avoided when possible, on account of the losses in treatment and the difficulty of making a good leaching product when they were present in large amounts, especially when the crushing was done in cyanide solution.

Jan 8, 1914

By H. Shaw

Gravitational measurements made by means of the Eotvos torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth's crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eotvos torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The. task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor. When the subterranean effects have been obtained, they are subjected to a critical examination, and an effort is made to recognize and

Jan 1, 1932

By Arthur G. Levy, Henry M. Howe

$1. Introduction.—Any given piece of metal is made up of a very great number of grains, usually microscopic, each of which is a perfect crystal save only in outward form, with cleavage planes of low cohesion, geometrically arranged quite as in fie familiar non-metallic crystals. The plastic deformation of such a mass occurs chiefly through the slipping of the crystalline blocks of which each grain is composed along these cleavage planes, causing steps called slip bands to form on a previously polished surface. In this slip, the metal immediately adjoining each of the cleavage planes along which the slip takes place is thought to pass extremely rapidly through a very mobile state into the amorphous state, in which it is harder than the remaining still crystalline metal between the amorphous layers thus formed along the slip planes. Whether the slip planes below the surface in ferrite can be detected by cutting, polishing, and etching sections is in dispute; but if this detection is possible at all, it is usually made impossible by heating the metal even gently. In short, the change along the slip planes does not persist through heating, and it is thought not to persist through time even at the room temperature, nearly all the amorphous metal recrystallizing. The network in Fig. 22 and the parallel N.-70-E. lines in Fig. 21 are slip bands in copper. When plastically deformed metal is heated, certain parts of certain grains may twin, that is, their component crystalline units may rotate into a position, or more exactly into an orientation, symmetrical with the initial orientation and hence with that of the remainder of that grain. As seen in a microsection of a metal the twinned areas usually have parallel sides. The existence of twinning is recognized in metallic sections either by the presence of such parallel-sided areas differing in brightness from the adjoining metal, especially when seen under oblique light after etching, or more surely by the zigzagging of the slip bands which form when twinned metal is itself deformed again. Hence the usual procedure in developing twins is to deform plastically so as to cause the twinning tendency; to heat so as to allow the tendency to assert

Jan 1, 1915

By Stanislaus Skowronski

OVERPOLED copper, as commonly defined, is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such copper is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a Well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, Which enables copper to be cast free from blowholes. It seems that When oxygen is present, other gases are less soluble in molten copper; When oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, Which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of Wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, While an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen, and the effect of this action. on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulphur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 3, 1918

Samuel Thomas Wellman, of Cleveland, Ohio, prominent in the iron industry on the Great Lakes, died suddenly of heart disease at Kennebago, Me., July 11. He was on his way to the camps of the Megantic Fish and Game Association .of which he was a member, when stricken. He was one of the founders and directors of the Wellman-Seaver-Morgan Co., of Cleveland.

Jan 9, 1919

By Walter E. Heinrichs

The following is a condensed version of an open letter addressed to Bil Gilbert of Sports Illustrated: Your article, "When a Law Fights a Law, Sports Illustrated. April 26, 1971, betrays considerable unfamiliarity with the subjects of ecology, social science, mining law and history. In a magazine as widely circulated as Sports Illustrated, an article of such a slanted nature misleads the general public.

Jan 1, 1971

By S. C. Sun, D. R. Mitchell

Experiments show that ores such as tungsten and tin, which slime excessively, can be deslimed and upgraded by ultrasonics. The method proposed depends primarily upon the stratifying and peptizing action caused when high frequency sound waves are propagated upward through ore pulp in a cylinder tube. Stratifying and peptizing are somewhat hindered by the accumulating action, which embodies additional effects of reflection and refraction.

Jun 1, 1956

By David Phillips, George Jura

WHEN Bridgman1 determined the volume-pressure relationships of bismuth to 100 kg Cm-2, he found two small volume discontinuities at 45 and 64 kg em-2. Probably every investigator in high pressures has determined the electrical resistivity of bismuth in this pressure range. Until Zeitlin and Brayman2 reported discontinuities in the resistance of bismuth at these pressures, no one had found resistance discontinuities

Jan 1, 1968

By W. L. Saunders

When work was begun in September, 1910, on the rock excavation for the foundation of the gigantic dam at Valhalla, N. Y., which is to convert Kensico lake into an important storage reservoir of the Catskill Aqueduct system, one of the first steps taken by the contractor, H. S. Kerbaugh, Inc., was the development of a quarry to supply the stone needed in the

Jan 1, 1915

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954