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By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By William Metcalf

One of the first questions that naturally occurs to one who handles steel is, " Why does steel harden?" To answer this question the chemist and physicist have devoted much thought and experiment, and while they have enriched our store of knowledge of the nature and composition of steel, it cannot be said that they have yet solved the problem involved in its hardening. In this communication I desire to direct attention to a line of investigation yet new, in the hope that it may receive the attention. of those who have the time and ability to pursue it. I refer to magnetism. There are so many parallels between the action of magnetism on iron and steel and their behavior under different processes of manipulation that it would seem. as if there must be some connection between tile forces at work in the different cases, if, indeed, there be not an identify of force in all of these cases. Magnetism, as me know it, may be merely the visible manifestation of forces, which may serve as a guide to lead us to an exact knowledge of the structure, tile strains, and the resistances with which me have to deal in iron and steel. If a magnet be brought close to a pile of iron filings, the little pieces of iron will fly to the maguet and attach themselves to it, with their longer axes lying in the direction of the force. If molten cast iron be poured into an iron mould,—a chill,—the iron upon crystallizing will form needlelike crystals, with their long axes normal to the surfaces of the mould. • If the iron is at the proper temperatare and the quantity small, compared to the mass of the mould, the whole of it, will be chilled, or set, in 'the hard needlelike crystals

Jan 1, 1881

By J. K. Furst

The reasons for manufacturing steel by the deplex process are, briefly…

Jan 1, 1915

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By F. F. Claussen

The method of making silver ingots in use at this Mint being radically different from that employed at any other Mint of the United States or, so far as known to me, any Mint in the world, there may be some interest in a description of the apparatus used and a brief history of its distinguishing feature, viz., the rotary ingotmould, which, though not a recent improvement, is comparatively unknown. The furnaces used for silver-ingot-melting are four in number and have a capacity of some seventy thousand standard ounces of silver per day of eight hours. This output is increased, when the exigencies of the service demand it, to one hundred thousand ounces. They are built of fire-brick and elevated 21/2 feet from the floor of the melting-room, in order to have space to place iron boxes and to work, in case a crucible breaks in the furnace and its contents run into the ash-pit. The furnaces are circular in horizontal section, 2 $ feet in diameter and 29 feet high inside in the clear, and rest on castiron plates, with top-plates of the same, and sides encased in boileriron. The furnace-covers are also of cast-iron, dome-shaped, and are handled by means of a small crane and lever. The furnaces stand in sets of two, and one crane and one ingot-machine serves two furnaces. The crucibles used are made specially for this purpose of a mixture of black-lead and fire-clay; the size known as No. 200 will contain and safely melt, without danger of slopping over, from 8600 to nearly 10,000 ounces of standard silver; and this is the usual weight of the ingot-melt at this Mint, as against 1800 ounces at the Carson City mint and 2600 to 3000 ounces at Philadelphia and San Francisco. Each crucible will endure, on the average, ten melts. The crucible stands in the center of the furnace, on the bottom of an old one, cut down to a height of about three inches. The fuel used is coke. Experience has shown that, notwithstanding the higher first cost, Connellsville coke is cheaper than Alabama coke and much more suitable to the work. A small triangular black-

Jan 1, 1888

By John H. Holloman

In recent papers, O'Neill,' Vivian, and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: where e is the strain and AO and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is .lotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept ii; very fruitful and should be kept in mind in any study of the deformation charactcristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite numbcr of specimens, each with a different strain history determined by the preceding part of the flow curve Each of these specimens can also be considered to have a fracture strength. Uniortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By K. R. Van Horn, L. W. Kempf

Plastic deformation of most commercia1 metals within a sufficiently low temperature range results in profound changes in structure and properties, of which the causes and effects are not completely understood. One of these effects is the presence of internal residual stresses and strains, which ordinarily do not appear to require specific consideration in most structural applications but which may be quite undesirable in particular instances. For example, in heavy sections that require considerable machining before assembly, residual stresses may be undesirable because of the distortion they cause when their balance is disturbed by machining or otherwise. In addition, the distribution of stresses may be such that it acts in the same direction as the applied load, thus bringing about premature failure or reducing the load-carrying capacity of the member. One source of residual stress in metal structures is the plastic deformation that may occur during rapid cooling from relatively elevated temperatures, as in the cooling of a casting in the mold or the quenching of a heavy section from elevated temperatures during heat-treatment. These residual stresses are usually undesirable because their direction of operation and magnitude cannot be controlled well enough to permit utilization of the changes in properties of the metal that they may bring about. The most convenient manner of controlling such residual stress is by proper selection of the cooling rate or by reheating to a temperature at which plastic flow can take place, resulting in relief of the residual stresses and strains. Both of these methods of control, however, may cause a reduction in the optimum properties obtainable from the previous operation. A compromise must be struck, and if it is to result in the best possible combinations of properties, specific information must be available regarding the magnitude of the stresses and the rate at which they are affected by variations in cooling rate or in reheating temperature. The complete quantitative estimation of residual stress in complicated metal shapes is exceedingly difficult, if not impossible. In simple sections, however, relatively quantitative analysis may be applied and useful cstimations of stress distribution may be made. This paper is concerned largely with the rate of relief, upon reheating, of internal residual stress in simple aluminum-alloy structures. Since even with simple structures quantitative estimation of residual stresses is laborious and costly, an attempt was made to find other means of collecting data upon which commercial heat-treatments might be based. Incidentally, a few data were collected bearing on the problem of relaxation of aluminum alloys. Determination of Residual Stresses The magnitude and distribution of residual stresses in simple aluminum-alloy shapes rapidly cooled from elevated temperatures has been discussed in a previous paper.' Fig. I reproduces some of the data

Jan 1, 1942

By L. W. Kempf, K. R. Van Horn

Plastic deformation of most commercia1 metals within a sufficiently low temperature range results in profound changes in structure and properties, of which the causes and effects are not completely understood. One of these effects is the presence of internal residual stresses and strains, which ordinarily do not appear to require specific consideration in most structural applications but which may be quite undesirable in particular instances. For example, in heavy sections that require considerable machining before assembly, residual stresses may be undesirable because of the distortion they cause when their balance is disturbed by machining or otherwise. In addition, the distribution of stresses may be such that it acts in the same direction as the applied load, thus bringing about premature failure or reducing the load-carrying capacity of the member. One source of residual stress in metal structures is the plastic deformation that may occur during rapid cooling from relatively elevated temperatures, as in the cooling of a casting in the mold or the quenching of a heavy section from elevated temperatures during heat-treatment. These residual stresses are usually undesirable because their direction of operation and magnitude cannot be controlled well enough to permit utilization of the changes in properties of the metal that they may bring about. The most convenient manner of controlling such residual stress is by proper selection of the cooling rate or by reheating to a temperature at which plastic flow can take place, resulting in relief of the residual stresses and strains. Both of these methods of control, however, may cause a reduction in the optimum properties obtainable from the previous operation. A compromise must be struck, and if it is to result in the best possible combinations of properties, specific information must be available regarding the magnitude of the stresses and the rate at which they are affected by variations in cooling rate or in reheating temperature. The complete quantitative estimation of residual stress in complicated metal shapes is exceedingly difficult, if not impossible. In simple sections, however, relatively quantitative analysis may be applied and useful cstimations of stress distribution may be made. This paper is concerned largely with the rate of relief, upon reheating, of internal residual stress in simple aluminum-alloy structures. Since even with simple structures quantitative estimation of residual stresses is laborious and costly, an attempt was made to find other means of collecting data upon which commercial heat-treatments might be based. Incidentally, a few data were collected bearing on the problem of relaxation of aluminum alloys. Determination of Residual Stresses The magnitude and distribution of residual stresses in simple aluminum-alloy shapes rapidly cooled from elevated temperatures has been discussed in a previous paper.' Fig. I reproduces some of the data

Jan 1, 1942

By J. E. Warren

To clarify the specific questions raised by J. E. Warren's discussion, the following remarks are offered. 1. It is correct that stratification is assumed in the application of the statistical zonation technique, but this does not constitute a limitation. If, in fact, the reservoir is not stratified the zonation technique will show it. The reservoir is then considered as one zone with a particular distribution of permeabilities. 2. The statistical zonation technique was intended as wells may not be an adequate measure of the lateral permeability changes; e.g., if the data presented in Table A-4 of the subject paper are evaluated on the basis of two crossed classifications with interaction, the variation between zones is significant with a probability greater than .99; however, the variation betwen wells is also significant with a probability greater than .87. It is apparent that the technique suggested by the author can be generalized to provide a powerful method for describing petroleum reservoirs. This generalization can be achieved by treating the core data as a two-way classification to determine the between-zones and the between-wells variations; then, the build-up permeabilities can be analyzed, perhaps on at least-squares basis, to establish the probable distribution of the permeabilities within the zones associated with the individual wells. an additional tool for the reservoir engineer to use together with other techniques and all available information. If pressure build-up permeabilities are available, they should certainly be included. Pressure build-up tests were not available for the reservoir considered in the paper. 3. The proposed correlation of zones between adjacent wells was the best of the techniques that I examined. It is not so much a "measure" as an indication of lateral permeability changes, regardless of whether they are seemingly random or form an obvious trend.

By John Lamont, Walter Crafts

The principle formulated by Grossmannl for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the increasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been! determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. Testing Procedure Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 29 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By John Lamont, Walter Crafts

The principle formulated by Grossmannl for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the increasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been! determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. Testing Procedure Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 29 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By Eric R. Jette

In order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned. Heterogeneous Reactions The thermodynamic side of metallurgical reactions has received much attention in the past; the mechanisms, relatively, very little. The main reason for our present lack of information on the mechanisms of these reactions lies in the fact that every one of importance is a heterogenkous reaction; i. e., the substances involved in the reaction exist in more than one phase, while, if we neglect the large amount of work which has been

Jan 1, 1931

By William E. Ford, Edward Salisbury Dana

THIS Appendix contains a series of tables, more or leas complete, of minerals arranged according to chemical composition or to certain prominent crystallograhic or physical characters. These, it is believed, will be of service not only to the student, but ago to the skilled mineralogist. The type used in the printing of the mineral names indicates their relative importance. Table I is a complete list of the species named in this book arranged fist according to the prominent basic elements which they contain and secondly according to their acid radicals. Table II is of Minerals arranged according to their System of Crystallization The other tablets make no claim to completeness, being limited often to common ah important species. For an exhaustive system of Determinative Tables based particularly upon blowpipe and chemical characters, the student is referred to the work of Professors Brush and Pen- field, mentioned on p. 330.

Jan 1, 1922

By W. H. Newhouse

During the past few years the writer has been impressed by the close relation of many epigenetic orebodies with anticlinal structures. In the literature on ore deposits there is occasional mention that an oreshoot or district is on an anticline, but in most of the descriptions no weight or significance is attached to the relation, and usually the fact is concealed in a mass of structural detail. A few writers have stressed the relationship in a few districts or on a certain type of deposit. Church, Spurr, Butler, Stahl and Schuette have called attention to certain features, but the general extent of such a correlation has not been made known in any publication that the author has seen. A recent article1 on the localization of ore deposits, by well-known geologists, does not consider this common association. The author has seen in the field a number of the structural features described, and in addition has made a fairly complete review of the literature. This paper presents enough of the examples found to show the frequency of the relation to anticlines, and since only a few deposits on synclines are known, all of these of any importance of which the writer knows are mentioned. With certain qualifications which are discussed later, epigenetic ore deposits of replacement or vein type are mostly found where local upwarps of the earth's crust have taken place. Where formations antedating the ore deposits are present in the proper attitude to demonstrate vertical warping (i. e., more or less horizontal beds) the structural feature on which a mineral district, or mineralized area is located is almost always anticlinal, or domelike in nature. Some or even most of the ore deposits in a given district may be on the flanks of the upwarp, but few major districts are located definitely on downwarped areas. Synclinal basins within certain limits of size appear to be unfavorable to the type of fracturing that admits ore-bearing solutions. Replacement orebodies frequently are localized in small anticlines or domes, the size of the anticline or roll often being more or less commensurate with that of the enclosed oreshoot. This feature certainly ranks

Jan 1, 1931

By Walter Weeks

LITTLE study has been made of the pressure changes and energy losses that take place when an air current is divided into splits which subse-quently unite. The discussion and the experiments that are described in this paper deal with the division of an air current into square splits of equal size, the area of each of the splits at the downstream junction being one-half the area of the main duct. APPARATUS AND SYMBOLS The duct system shown in Fig. 1 was built of Y4-in. redwood and made as smooth as possible.The section of the top over the splits and the zone of mixing was of plate glass to permit observation of the stream lines. FIG. 1-DUCT SYSTEM. Static pressures were measured by means of pinhole tubes and a precise inclined manometer. Measurements of rates of flow were .made by determining the drop in pressure through concentric square orifices in the splits. The air was supplied by a fan operated by a direct-current motor that received its current from a motor generator set. Delicate rheostats in the armature. of the motor. made possible the perfect control of the fan speed, which was indicated on an electrical tachometer. Vanes to straighten the. flow were placed at the head of the main duct.

Jan 1, 1933

By Irwin Remson

Some unique hydrogeologic issues are inherent in the problems of siting, designing and licensing a mined geologic high-level nuclear waste repository. The problems involve hydrogeologically unfamiliar rocks for which little proven technology has been developed, long containment periods, elevated temperatures, and externally-imposed management constraints. In evaluating the existing national program, it should be recognized that hydrogeology is only one aspect of the total nuclear waste disposal problem, that the use of multiple barriers requires that the hydrogeologic system be considered in its entirety as a total system, and that engineering modifications can improve the isolation capabilities of certain barriers. Important research questions involve the mechanics of transport through dense fractured and unfractured rocks, methods for measuring vertical hydraulic conductivity, and a variety of geochemical questions. Current expectations for "high quality data" from either in situ or laboratory testing are unrealistic, and a modified approach to repository hydrogeology is needed. The dilemma is that the hydrogeological characteristics that make a potential host rock more satisfactory for respository siting are the same characteristics that are difficult to characterize and make the particular site more difficult to license. Finally, evaluation of the containment potential of any candidate site will become meaningful only with detailed underground exploration, mapping and testing in the host rock formations at the repository levels.

Jan 1, 1984

By Henry M. Howe

The brilliant and very original matter in Professor Jeffries' discussion† should rank not only as an independent paper, but as a most important one. In particular, the explanation which it gives of the remarkable Sauveur phenomenon, over which so many of us have puzzled long and hard, is so clear, complete, and cogent as to go far toward establishing Professor Jeffries' hypothesis. The very leatures of Professor Sauveur's photographs which fit this hypothesis so exactly are reproduced in Chap-pell's photographs of steel coarsened under somewhat different conditions.' The ideas developed by these discoveries are so novel that convenicnce of language seems to call for new conventional terms for expressing them. In what follows here I propose certain terms for this end, for criticism and improvement, and I attempt to generalize from Professor Jeffries' hypotheses. Generally speaking, a given set of grains which undergo no growth in the cold will, when the temperature is raised progrcssively, start to grow on reaching a certain temperature, and will continue growing at all higher temperatures. The "germinative" temperature is that at which growth begins, quite as the conditions which cause a seed to grow are "germinative." We have then an inert temperature range below the germinative temperature, and a growth range above it, the germinative temperature being the limit between these two ranges. So, too, a germinant grain is one which is at its germinative temperature, and hence beginning to grow, while inert grains are those below their own germinative temperature, and the term "growing grains" includes those which are germinant and those which are above their germinative temperature. These last could be called " supergerminant" if the distinction should be needed. "Germinative temperature" seems better than "critical temperature

Jan 1, 1917