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By F. N. Rhines

DESPITE the large amount of study which has been devoted to the subject our present knowledge of the copper-oxygen system remains incomplete and unsatisfactory in many respects. This applies particu-larly to those regions in which solid metallic copper exists. The primary object of the present paper is the contribution of new information relative to the solid solubility of oxygen (or cuprous oxide) in copper at atmospheric pressure, together with certain observations in the low-pressure regions of the system. It seems appropriate also to present a brief summary of the outstanding previous work on the constitution of mixtures of copper with its lowest oxide in order to show the relation between the new facts and the system as a whole. The earliest recorded investigations of the copper-oxygen system are those of M. S. Lucas (1) § and of M. Chevillot(2) in 1819 and 1820. Lucas believed that liquid copper is capable of dissolving its oxide, but neither he nor Chevillot was able to furnish convincing proof of this property. It was not until 1866 that T. Graham° definitely established the existence of such a solubility. Nine years later W. Hampe(4) measured its extent and roughly outlined the copper-rich portion of the system. The first really precise examination of the constitutional relationship between copper and cuprous oxide, however, was that of E. Heyn(5) who in 1900 published a temperature-concentration diagram covering the range from 0 to 10 per cent of cuprous oxide at atmospheric pressure. Within these limits of composition cuprous oxide was found to dissolve in liquid copper, forming at 3.4 to 3.5 per cent a eutectic which melted at 1065° C. R. E. Slade and F. D. Farrow(6) extended these studies to mixtures of higher

Jan 1, 1934

By Persifor Frazer

CONTENTS. PAGE 1. Committee House of Commons Report (1843).......521 2. Clark (1880).............521 3. Schröder and Schertel (1884).... . 521 4. Committee House of Lords Report (1887).......523 5. Vita (1890).............524 6. Irvine (1890-1)............524 i. Cramer (1891)............525 8. Bailey. Cohen. Tatham and Hartog (1891))......525 9. Morrison (1891)............525 10. Brunner (1891)............525 11. Bell (1892).............585 12. Oades (1892).............526 12a. Purcell (1892)............526 13. Sennett (1892)............526 14. Bulier (1892).............526 1.7. Wiesner (1892))...........526 16. Thomson (1892)............530 17. Fletcher (1892)............530 18. Committee Engineers' Club Report (1892).......530 19. Cohen and Hefford (1892)..........531 20. Discussion Soc. Chem. Ind. (1893). ..532 21. Reuss (1893).............532 22. Thomson (1894—5) ...........535 23. Clowes and Feilmann (1895). ...536 24. Callan (1895)...........536 2.5. Wright (1895)............536 25A. Mabery (1895)............536 26. Re- (1896). ..........536 27. Herman (1896)............ 537 28. Cohen and Russell (1896).......... 537 29. Dennstedt and A hrens (1896). ..537 30. Cohen (1897). ...........537 31. Drehschmidt (1897)........... 538 32. Pfeiffer (1898). .........538 33. Fritzche (1898)............ 540 34. Ost and Wehmer (1899)........... 540 35. Donkin (1899). .........541 36. Beilby (1899)............. 643 37. Berthelot (1900)............ 544

Jan 1, 1908

By R. C. Schmidt, B. E. Kennedy

The Mont Klahoyo magnetite deposit is located about 600 km (373 miles) northwest of Abidjan, Ivory Coast. During an exploration period ending in 1977 an international joint venture group investigated the deposit and proved reserves of 670 Mt (739 million short tons) grading 36% iron. The deposit occurs at the northeast end of the Baoubly-Kiriao chain of Precambrian iron formations with associated amphibolites, pyroxenites, and gneisses of the Liberian Shield. The ore body is represented by a highly metamorphosed banded quartz-magnetite iron formation with alternating beds of iron silicates and quartz-magnetite. Amphibolite-pyroxenites and sillimanite-cordierite-garnet gneisses form hanging and footwall rocks. The iron formation has been folded into an elongated, overturned 2-shaped major drag fold with axes trending and plunging approximately northeast. Beds are vertical or dip steeply to the southeast. The ore zone has an average thickness of 130 m (427 ft) and outcrops intermittently over a distance of approximately 5.5 km (3.4 miles). Based upon detailed studies of drill cores and the results of ore dressing test work, eight stratigraphic units, identified as K- 1 to K-8, are recognizable in the iron formation. Four interbedded units are low grade silicate zones (silicate facies) while the remaining quartz-magnetite units are oxide facies, representing the important Mont Klahoyo deposit ores. Ore-bearing "K" units are subdivided further into 11 ore types, based upon their specific lithologies, iron content, and concentration characteristics. Identification of these ore types proved particularly useful to mine planning and flowsheet design. A cap of oxidized material overlies the primary quartz- magnetite iron formation, but no enrichment has occurred. It is thought that the Mont Klahoyo iron formations were deposited chemically in a volcanic environment as a siliceous iron formation with volcanism the primary source of iron and silica. Metamorphism converted the siliceous iron formation to a coarse-grained, quartz-magnetite-silicate iron formation.

Jan 1, 1983

By Yingchang Tsenshan Wang

UUIN L&SS 1» Paqb I. Introduction........................................................658 1. Subject and Scope...............................................658 2. Acknowledgments...............................................659 3. Review of Previous Work........................................659 Field Data...................................................659 Experiment.a1 Data............................................662 4. Plan of Present Investigation.....................................662 Method of General Procedure...................................663 I1. Experimental Work..................................................663 A. The Solution of Sphalerite..............................:........663 1. The Solvent Effect of Iron Sulphates upon Sphalerite...........663 2. The Solubility of Sphalerite in Salt Solutions of Silver, Copper and Lead...............................................668 B. Formation of Zinc Carbonates....................................674 3. The Reactions of Carbonates and Bicarbonates With Solutions of Zinc Salts............................................674 4. The Reaction of Zinc.Sulphate Solution With Limestones.......684 C. Peculiar Conditions Affectitig the Formation of Zinc Silicate (calamine) and Zinc Carbonate (smithsonite)..........................686 5a. The Effect of Carbon Dioxide Upon the Basic Silicate and the Carbonates of Zinc in Water, and Its Bearing Upon the Conditions of Theii Precipitation..............................686 5b. The Reactions of Solutions of Soluble Silicate With calamine and Smithsonite in Solution in Presence of Carbon Dioxide..689 6. The Reactions of a Mixture of Hydroxide and Silicate of Sodium with a Dilute Solution of Zinc Sulphate...................691 D. High-Temperature Methods.....................................692 7a. The Influence of Temperature on the Formation of Calamine..692 7b. Possible Effect of Heat on Calamine and Srnithsonite.........697 E. Summary of the Experimental Work..............................698 III. Petrographic Work....................................................700 1. The Occurrence of Sphalerite in Limestones or in Cherts............701 Summary of the Blende in Limestones and in Cherts.............7432 2. The Partially Altered Sphalerite and the Oxidation Products........702 a. Smithsonite with Blende....................................702 b. Calamine with Blende......................................703 c. Smithsonite and Calamine..................................703 d. Summary on the Partially Altered Sphalerite and Its Oxidation Products..............................................704 IV. Concl~~siom ........................................................-705 V. Microphotographs and Photographs with Their Explanations.............705

Jan 1, 1916

By E. L. Affleck, W. G. Stevenson

In both Canada and the United States, a company making a public offering of securities must comply with regulations which have been passed by Federal, State and/or Provincial Legislatures. These regulations usually require the distribution of an acceptable prospectus which provides essential background information about the issuer, the project and the share offering. when the public offering has been accepted, the unlisted company may then seek a listing of its shares for trading on a Stock Exchange. Once listed, the company will be subject to rules of the Stock Exchange. This paper will deal with the specific information required for inclusion into a prospectus being submitted for a resource company and particularly those parts of concern to mining engineers and geologists.

Jan 1, 1985

By Sooi P. Chong

Expansion of concentrator capacity at Iron Ore Company of Canada's Carol Lake plant resulted in a dramatic increase in the production of fines. With iron recovery from the fines running only 18%, Carol Lake engineers initiated an extensive test program which resulted in the installation in July 1977, of a full-scale plant utilizing Reichert cone concentrators. Results to date have indicated a 100% increase in iron recovery from the concentrator's fines product. Carol Lake is located near the western boundary of Labrador, Newfoundland, some 960 km (600 mi) northeast of Montreal. Concentrator operations began in 1962 with a design capacity of 7 million t/y (7.7 million stpy). The bulk of the concentrate was pelletized at a 6 million t/y (6.6 million stpy) pelletizing plant completed in 1963. The remaining concentrate was sold in the international market. The concentrator was first expanded in 1966 to 10 million t/y (11 million stpy) capacity. In 1967, the pellet plant was expanded to match the increase in concentrate production. Sales increases led to a further expansion in 1973. By 1977, more than 40 million tons (44 million st) of crude ore were processed to recover in excess of 17.42 million tons (19 million st) of concentrate and 10.4 million tons (11.5 million st) of pellets.

Jan 12, 1978

By P. Chaudhari, Michael B. Bever

The heat of solution at infinite dilution of selenium in bismuth, the heat of mixing of selenium and bismuth, and the limit of solubility of selenium in bis~rzuth have been determined at 573, 623; and 663°K by metal solution calorimetry. The heat of forrrzation of the compound Bi2Se at these temperatures has been determined from the heat effects associated with the precipitation of the compound from a saturated solution oj selenium and bismuth. The published information on the thermodynamic properties of the system Bi-Se is limited. The heat of solution at infinite dilution of selenium in bismuth at 623°K has been measured.' The heat of formation at 273 K1 and room temperature2 and the heat capacity at 80 K3 of the compound Bi2Se3 have been reported. An estimate of the heat of formation of the compound BiSe at room temperature has been published.2 Information on the phase relations in the system Bi-Se is available.' In the investigation reported here the following quantities have been determined at 573", 623", and 663°K: 1) the heat of solution at infinite dilution of selenium in bismuth, 2) the heat of mixing of selenium and bismuth in bismuth-rich solutions, 3) the limit of solubility of selenium in bismuth, and 4) the heat of formation of the compound BizSe. These quantities were determined by the addition of selenium to bismuth-rich solutions in a metal solution calorimeter. The determination of the heat of formation at the tem- perature of the calorimeter bath involved the precipitation of the compound from a saturated solution in the calorimeter. 5,6 This method differs from that commonly used which requires the addition of the compound and of a mechanical mixture of its components and yields the heat of formation at the temperature from which the additions are made (273 K EXPERIMENTAL PROCEDURE AND CALCULATIONS The solution calorimeter has been described in detail.' Pure bismuth (99.999+ pct) was used as the bath at the start of a run. The calorimeter was calibrated with small amounts of bismuth added from 273°K; the differences of the heat contents of bismuth at 273°K and the temperatures of the baths are listed in Table I. After the calibration, additions of hexagonal selenium (99.999+ pct) were made. Loss of selenium by evaporation was negligible. No unusual experimental difficulties were encountered.9 The differences in the heat contents10 of selenium at 273°K and the temperature of the bath, listed in Table I, were subtracted from the measured heat effects to give the "adjusted heat effects". The methods by which the heat of solution at infinite dilution, the

Jan 1, 1968

By Frederick T. Williams

THE purpose of this paper is to discuss the relative merits of the large 31/8 in. machine and the small 21/4-in. tappett machine in driving development-headings ; and although the . data here presented were obtained from cross-cut headings alone, experience has shown that the results are equally true in drifting, raising and winning. Recently we drove two parallel cross-cuts through the same formation, using a 3k-in. machine at the breast of one cross-cut., and a 2k-in. machine of the same make at the breast of the other. The results of this work afforded an ideal comparison, since in both cases the headings were advanced through rock practically of the same hardness and breaking-properties ; the amount of sludging was equal, and there was no difference in the condition of the steel or the machines, in the air-pressure or in the experience of the operating-crews. Some operators in the Cripple Creek district contend that there is ground which cannot be handled with the small machine, the holes being too small to contain enough powder to pull the ground, etc. The results obtained in working the property of the Portland Gold Mining Co., however, show that the ground worked by them does not fall in this class. During a period of two years there have been driven, with the small machine, 4 miles and 308 ft. of development-headings, through a diversity of ground, including Pike's Peak granite (a coarsely porphyritic type of granite), highly indurated, andesitic or phonolytic breccia, true massive andesite, trachytic phonolyte, tuffas, and along dikes of decomposed basalt and hard phonolyte; in every instance a satisfactory record was made. The headings here described were driven through highly indurated, andesitic breccia, having a hardness of from 5.2 to 7.2

Mar 1, 1906

By William J. Coulter

WITHIN the United States the problem of meeting maximum production by our metal mines has been solved by: (1) Conservation of man power by mechanization. (2) Increasing man-power efficiency as expressed in tons per man-shift by the adoption of new and more efficient methods. (3) Production from submarginal properties made possible by some form of government subsidy. (4) Selective mining of high-grade areas. (5) Drawing on broken ore reserves and reducing advanced development work to a minimum. (6) Making maximum use of available equipment. (7) Repairing equipment that normally would be replaced. (8) Working a seven-day week on a three-shift basis to get maximum use of equipment and man power. (9) Adoption of incentive plans to increase maximum efficiency and unit production. (10) Important advancement in metallurgy, resulting in larger recoveries. (11) Improvements in safety, health, and general working and living condi-

Jan 1, 1945

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By Oliver Smalley

EXCEPT for the work of Guillet, who conducted a systematic investigation on the zinc-replacing value of nickel in brass, and extended his investigation with a view to developing commercial high zinc content nickel brasses, the author does not know of any systematic research on the subject. The most promising commercial alloys and their physical properties obtained by Guillet are given below: Maximum Elonga- Reduction Copper Zinc Nickel Stress, tion, of Area, Brinell Tons Per Per Cent. Per Cent. Sq. In. 55.0 41.0 5.0 24.4 46.5 94 Sand cast. 22.6 27.0 90 Chill cast. 56.7 39.74 3.35 30.0 43.0 51.7 97 Casting annealed 2 hr. at 750° C. 33.9 33.0 50.7 144 Cold-drawn bar. 55.15 42.3 2.24 29.8 33.0 116 Casting annealed 2 hr. at 750° C. 32.3 29.0 151 Cold-drawn bar. These test results scarcely justify the use of such quantities of so expensive a metal, and could have been obtained from ordinary commercial brass. For purposes of comparison, the physical properties of ordinary brasses, ranging from 70 per cent. to 50.1 per cent. Cu in both the cast and normalized1 conditions are included in Table 1. These incidentally furnish a useful standard of the properties of castings and of rolled, extruded and forged brass when correctly annealed. A close study of some of the well-known special brasses containing nickel reveals a series of alloys which bewilder by their complexity, and one can only hazard a guess at the function and commercial value of each of the many elements used.

Jan 10, 1925

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By Richard F. Miller

The investigations of large-grained specimens carried out by Polanyi and Schmid,l Sykes,2 Goucher,3 Yamaguchi,4 Gough, Cox, and Sopwith,5 Carpenter and Elam,6 Aston,7 and others have shown qualitatively that grain boundaries restrain the deformation of adjacent crystals. But whether or not the influence of the grain boundary is confined to the glide planes intersected by the boundary has not been demonstrated in any of these investigations, nor has there been carried out any quantitative analysis of the influence of a boundary on the deformation of a crystal. Indeed, the specimens employed in the previous work contained so many complicating factors that it would have been difficult to observe any variation of the extent of the influence of the grain boundaries in relation to their sizc. The specimens were small, the grain boundaries irregular and at no particular angle to the specimen axis or the

Jan 1, 1934

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By Rollin E. Hook, Attwell M. Adair

The response of CrzO3 and C~304 to various heat treatments was studied in are-melted iodide chromizim over the temperature range 1000" to 1750°C. These oxides, which are present as impurity phases in this material, were identified by X-ray diffraction teclzniques which were supplemented by optical metallop-aphy. As a function of increasing temperature, Crs04 is first observable in samples annealed at 1300°C and coexists with Cr2O3 (the low-temperature oxide) over a temperature range exceeding 200°C. As the temperature decreases, Cr3O4 dissolves with the concomitant precipttation of Cr2Y2. Both oxides precipitate predominantly at pain boundaries. The reactions which occur are involved with at least ternary equilibria, possibly due to iron which is present as an impurity in arc-melted iodide chromium. HILTY, Forgeng, and Folkman' reported in their investigation of the Fe-Cr-0 system that Cr3O4 (with about 8 pct Fe substituted for chromium) is a primary phase found in alloys with 9 or more pct Cr. They reported that this phase is stable only at high temperatures and that below the liquidus Cr3O4 is disproportionated into Cr2O3 and chromium-rich metal for both Fe-Cr-O alloys and in oxygen saturated pure chromium. Further, they proposed that CrsO4 forms by a peritectic reaction between Cr2O3 and the liquid. On the other hand, Hook, Garrett, and Adair2 found in their investigation of impurity phases formed in "pure" chromium (material consolidated from iodide chromium crystals) that Cr3O4 forms intergranularly and is stable as low as 1500°C which is 375OC below the melting point of chromium. The purpose of the research described herein is to determine the temperature range of stability of Cr3O4, and to show the nature of its decomposition. This further investigation indicates that Cr3O4 undoubtedly occurs in this material as low as 1300°C. The chromium studied was consolidated and fabricated from iodide chromium crystals (ICr-5) and contained Fe r 135 ppm, Si = 20 to 100 ppm, and 0 = 35 to 137 ppm. A complete chemical analysis is given elsewhere.' Annealing was conducted in 1 atm of purified helium and all samples were rapidly cooled (-200°C per sec) by withdrawing them from the furnace hot zone under a high flow rate of helium. The details of the electrolytic-etching technique and electrolytic-digestion techniques for preparation of insoluble residues for X-ray examination are given elsewhere also.' EXPERIMENTAL RESULTS The Starting Material. The as-swaged rod (final swaging done at 900°C) had a wrought grain structure and contained a dispersion of CrzO3 inclusions of maximum particle size of about 2 or 3 p, Fig. 1. The microstructure also contained a dispersed

Jan 1, 1964

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

NEW MEMBERS The following list comprises the names of those persons who became members during the month of December, 1913: Members ADAMS, CHARLES W., JR., Smelting, American Smelting & Refining Co., Murray, Utah. ARMSTRONG, FRANK H., Mechanical Engineer Vulcan, Mich. ARNOLD, JOHN B., Attorney-at-Law Room 840,200 5th Ave., New York, N. Y. BOYS, HARRY R., Mining Paso Robles, Cal. CAVANAGH, JOHN L., Min. Engr., Nova Scotia Steel & Coal Co.; Wabana, Newfoundland. CHOW, KAI CHI, Student 1120 Amsterdam Ave., New York, N. Y. CLARK, ARTHUR B., Mining Engineer 72 Harbour Bldg., Butte, Mont. CURLEY, JOHN R., State Mine Inspector P. 0. Box 633, Leadville, Colo. DAVIS, ANGUS W., Mining Engineer, Consolidated Mining & Smelting Company of Canada, Trail, B. C., Canada.

Jan 1, 1914

By A. K. Jena, M. O. Bever

The thermodynamic behavior of dilute solutions of copper, silver, and gold in liquid tin is not explained by current solution theories.1-3 The relative partial gram-atomic enthalpies, or heats of solution, of silver, gold, and platinum in liquid lead at 623°K have been measured in the investigation reported here. Their interpretation requires a modification of the regular-solution theory although lead-rich solutions may be expected to be simpler than tin-rich solutions. The liquid metal solution calorimeter used has been described.4 At the start of a run the bath consisted of 621 g of reagent-grade lead. Several calibrating additions of lead were made during a run; a value of 3.48 kcal per g-atom5 was taken for H623°K - H273°K Two runs were made with each of the solutes silver, gold, and platinum. Annealed wire samples of 99.999+ pct purity were used. Four to six samples each weighing 0.5 to 1,0 g were added from 273°K to the bath at 623°K and the associated heat effects were measured. The samples dissolved in approximately 3 min. No serious experimental difficulties were encountered. The heat effects of the additions in a run plotted against the average atom fraction of solute before and after each addition314 were linear functions of the concentration in lead of silver, gold, and platinum, respectively. By subtracting the difference between the heat contents of a solute element at 623° and. 273°K5 from the measuredheat effects, the partial gram-atomic enthalpy relative to the solid solute was obtained. The relativ: partial gram-atomic enthalpy at infinite dilution and the concentration dependence of the partial gram-atomic enthalpies obtained from the plots of vs atomic fraction x are listed in Table I. The relative partial gram-atomic enthalpy at infinite dilution of silver in lead of 5.46 kcal per g-atom at 623°K compares with values at 723°K of 5.74' and 5.765 kcal per g-atom. These data yield a temperature coefficient of 3.0 cal per g-atom-OK. The partial gram-atomic enthalpy at infinite dilution of gold in lead at 623°K is 0.89 kcal per g-atom compared with 0.85 kcal per g-atoms (obtained by extrapolation) and 0.95 kcal per g-atom.5 By combining these values for 623°K with those for several other temperatures5" the temperature coefficient of was found to be 3.2 cal per g-atom-OK. No thermodynamic data are

Jan 1, 1968

Jan 1, 1969