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By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

[Queensland :-(Continued.) petrography of the Mount Morgan mine, LV, 263. Queensland tin mine and mill, Santa Barbara, Guanajuato, Mex., XXXVI, 227. Quenner disintegrator, XLI, 801; XLII, 15011. Quenstedt, F.: petroleum deposits, Suabia, XLVIII, 14881. Queretaro, Mex., silver mines, XXXIX, 360. Quicksilver: mining and reduction, LI, 110. Oceanic mine, Cambria, Cal., LI, 110. Quicksilver and iron decompose silver sulphide, XL, 872. Quicksilver deposits: China, -XL111, 49. Pacific slope, XXXVI, 1311.. Siberia, Vhdivostok district, XLIV, 16001.]

Jan 1, 1918

By F. R. Hensel

PURE silver and silver-lead alloys have been studied as to their suitability for bearings.1-8 A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materials.† The silver-rich end of the diagram as reported in the literature9-11 was found to be sketchy and it was necessary to carry out considerable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. TEST MATERIALS In the beginning of the work, only fused alloys were investigated. Later, research [TABLE I. Composition of Fused Silver thallium Alloys Tested for Antifriction Properties PERCENTAGE ALLOY No.OF THALLIUM 15330.48 153406 231 HT2.04 2312.10 232 HT3.83Balance 2324.07Silver 233 HT5.86 2336.38 2349.84 234 HT10.07] was carried out on electroplating methods and diffusion processes. In preparing the fused alloys, care was taken to exhaust the toxic fumes caused by the thallium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in. diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr2O7, 8 c.c. H2SO4, and 100 c.c. H2O. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C. show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475°C. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not result in complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1945

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reasonable expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In-a bulk tonnage such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: l (1) by screening or sizing, (2) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing, while it is possible to produce a very acceptable product from mediocre cleaning if the coal is well screened and mixed.

Jan 1, 1950

By M. T. McDonough

THE data relative to the effect of metal depth on slag volume was obtained from the operation on two acid electric furnaces in which heats of various sizes were produced. The furnaces used were of 3 and 5-ton rated capacity; the heats investigated ranged from 6 to 8 tons. Heats of 7 and 8 tons were made in the larger furnace; heats of 6 tons in the smaller one. Bath depths and diameters were measured on the furnaces when cold and each is accurate to one inch. Both the metal charge and the slag were weighed on a track scale accurate to ± 25 lb. All other components added to the furnace were weighed on a wheelbarrow scale accurate to ±5 lb.

Jan 1, 1947

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1932

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By W. P. Lass

The purpose of this article is not only to describe the plant and method of cyaniding the Treadwell concentrates, but to present some of the results of the experimental work obtained in the past three years for the Alaska-Treadwell Qold Mining Co., at Douglas Island, Alaska, under the direction of F. W. Bradley, Consulting Engineer, and Robert A. Kinzie, General Superintendent, of the affiliated companies. At the time the experimental work was undertaken the concentrates were being shipped to the smeltery at Tacoma, Wash., and the cost for treatment of 3-oz. (gold) concentrates was $11.95 per ton, divided as follows : Smelting-charges,......... $4.00 Loading, freight, insurance, etc., . 2.89 Interest due to time loat in transit and in settlement,... 0.05 Loss due to settlement for 95 per cent. of the gold at $20 per ounce, 6.01 Total,...$11.95 From the experimental work described later, it was estimated that 96 per cent. extraction could be made by treatment on the ground, and that the cost, when treating 80 tons per day, would be $3.25 per ton, divided as follows : Per Day. Per Ton. Labor,. $86.16 $@.827 Chemicals,.76.60 0.960 Power and steam-heat,... 67.60 0.845 Marketing-, refining- and other charges, . 49.36 0.617 Totals,.. $2.59.72 $3.250 Adding to this total the 4 per cent. treatment-loss, which on 3-02. concentrates amounts to $2.48, gives a total cost of $5.13 per ton. Comparing this with $11.95, the cost when shipping to the smelter, leaves a net gain of $6.22 per ton by the local

Jan 1, 1912

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By R. W. Raymond

THE absence of a convenient glossary of terms connected with mining and metallurgy has long been felt by the general public. It is to meet this want, not to furnish a technical manual for experts, that the following glossary has been prepared. It originated in an attempt on my part to revise for publication the manuscript of a compilation prepared from the appendix of Yale's work on Mining Titles and one or two other sources, to serve as an appendix to a new work on mining law, about to be published by Mr. H. N. Copp, of Washington, D. C. This revision soon assumed, contrary to my original intention, the proportions of a reconstruction; and with the consent of Mr. Copp, and for the purpose of receiving from my fellow-members valuable aid, I presented my still incomplete work as a paper at the Lake Superior meeting of the Institute, inviting from any quarter suggestions of new terms or better definitions to be incorporated in the glossary before its final publication. This invitation was so widely and generously responded to, that I cannot undertake to make in this place individual acknowledgments to those members of the Institute, and professional colleagues outside of it, who have favored me with assistance and advice. The labor bestowed upon this paper since its presentation at the Lake Superior meeting has considerably exceeded that of its first preparation, as may be inferred from its great increase in length, as well as the numerous alterations which it has undergone. It could certainly be still further enlarged and improved; but I think a comparison of it with any of the glossaries of the same class now in print will show, at least, that it is an advance upon what has hitherto been accomplished. 1 shall be grateful, however, for further criticisms and suggestions; and I purpose at some future time to incorporate in a supplementary paper the results of such additional collections or corrections as I may obtain. To avoid too great prolixity, I adopted at the outset the following general principles: 1. To include the most important technical words and phrases used by American miners and metallurgists, or occurring in English books and periodicals.

Jan 1, 1881

By J. Spotts McDowell

INTRODUCTION The magnitude of the thermal expansion of silica brick, and its inability to withstand rapid temperature changes, present problems of considerable importance in the manufacture of siliceous refractories. In the study represented by the experimental data herein described, these problems are considered from the point of view afforded by the results of recent investigators: Fenner and his associates of the "Geophysical Laboratory, Washington, D. C., who have established the stability relations of the silica minerals, and Endell and co-workers in Berlin, who have studied the changes brought about in the constitution of siliceous refractory materials upon the application of heat. In the process of manufacture, the quartzite from which the brick is made changes in part into cristobalite and tridymite. The attempt is herein made to determine by microscopic methods the degree of transformation in various specimens of test bricks manufactured at slightly varying temperatures of burning, with varying coarseness of grain, and to determine the effect of repeated burning. The effect of variations

Jan 10, 1916

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metallurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each temperature from room temperature to fusion temperature, and cooled at a rate that is not generally controllable but is predetermined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each temperature zone. The nature of the zones produced by other types of welding is the sane. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and disadvantages of the extent of the zone are of prime moment, and are discussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known. GENERAL METHOD The scheme of procedure in the work herein reported involved the testing of the metal of each temperature zone adjacent to the weld in so

Jan 1, 1935

By George C. Stone

AS most of you probably know, Australia has had many strikes. The two places that had the worst reputation were the Broken Hill mines and Port Pirie, where the smelter was located. About four or five years ago, the smelter changed hands. The new proprietors - immediately endeavored to get on better terms with the men and made such progress in that respect that, the men came to them and said, "There is no use giving us any more money. You have just raised our pay one- bob a day, but the store-keeper and the boarding-house keeper have raised their prices. The boarding housekeeper raised our board three bob a week and the storekeeper took the rest of it and we are no better off." Learning that what the men needed most was firewood wood the company bought the wood on a tract of ground across Spencer's Gulf and- sent men over to cut it. The wood was brought to the works and given to a man to cut up. He thought he had an easy job and loafed, but when the committee representing the men discovered that his loafing added to the cost of 'the wood, it promptly disciplined him and made -him work as he had never worked before. The next question that arose was the distribution of the wood. The committee got bids from several cartmen whose prices varied from about two to five shillings. It gave the work to the next to the lowest bidder. The fact that if delivering the wood cost more, the user would have to pay for it, was an entirely new idea to the men.

Jan 1, 1920

By E. R. Kaiser

ACTIVITY on long-range and on immediate wartime problems shared the attention of specialists in coal research during 1943. Programs of the principal coal laboratories were more adequately financed than in previous years, but all reported shortages of technical personnel. Expansion in coal research in the year to come will depend primarily on the availability of qualified research talent.

Jan 1, 1944

By Richard McCaffery

CONTENTS PAGE 1. Research on Blast-furnace Slags (A Progress Report). By Richard S. McCaffery 5 2. Determination of Viscosity of Iron Blast-furnace Slags. By Richard S. McCaffery, Clarence H. Lorig, Ira N. Goff, Joseph F. Oesterle and Oscar O. Fritsche 27 3. Effect of Magnesia on Slag Viscosity. By Richard S. McCaffery, Joseph F. Oesterle and Oscar O. Fritsche 55

Jan 1, 1931

By Alexandre Mitinsky

The theory of elasticity, the science of the strength of materials, and all our calculations regarding engineering structures are based on Hooke's law, that in loaded bodies the deformations are proportional to the load producing them. Without this law it would be impossible to design intelligently engineering structures such as bridges, frames, axles, etc. This being the case, the proportional limit,l that is, the point at which deformation ceases to be proportional to load, is the most important factor in engineering design. Further, the working fiber stress should be fixed in reference to the proportional limit instead of, as is usual, in reference to the ultimate strength. The incorrect use of the ultimate strength instead of the proportional limit in setting the working fiber stress is probably due to two reasons: (1) it is a more delicate operation to measure the proportional limit; (2) it is usually assumed, though incorrectly, that the proportional limit is determined by the ultimate strength. In Germany the poin't at which permanent set first appears is often taken instead of the proportional limit. The two points will coincide if Gerstner's law, that elastic deformations are proportional to the loads producing them both before and after permanent set, is true; and the limit of proportionality and the elastic limit or point of permanent set will both be represented on a stress-strain diagram, by the point at which the line ceases to be a straight line and becomes curved or changes its inclination. It is to be further noted that the difference in definition between proportional limit and elastic limit introduces a difference in methods of determination in the testing laboratory. The German method of determining the elastic limit by alternately loading and unloading the test specimen is a lengthy process and time has in itself a very considerable influence on the results of physical tests.

Jan 1, 1916

By W. C. Weslow

AN extended program devoted to the development of a matrix for holding diamonds of a size and. kind not heretofore generally used is being carried on by the Carboloy Company, and this paper describes the part of the development that affects mining and its allied industries. Labora-tory and field work so far has indicated the following: 1. Tungsten carbide and cobalt form the most desirable known matrix material for the holding of diamonds for drilling work. 2. Industrial bort diamonds in sizes and of a class not generally heretofore acceptable and therefore less expensive can be successfully held in this cemented carbide matrix. 3. In exploratory drilling, the combination of bort diamonds, impreg-nated throughout a matrix of tungsten carbide and cobalt, when fabri-cated onto drilling crowns, is an indicated economic substitute for drilling crowns in which the diamonds are set by hand, mechanically or by casting. 4. This impregnated type of drilling crown or bit has definite possi-bilites of revolutionizing the drilling of blast holes, particularly in the harder formations. This will be brought about by the development of high-speed light-weight rotary equipment using an impregnated diamond bit to replace the percussion drill now in general use. (The development of this rotary equipment is well past the laboratory stage at this time.) 5. That the use of a rotary bit is a preventive measure in the fight against silicosis. The development of this product was started by G. F. Taylor at the Research Laboratories of the General Electric Co. It was early recog-nized that it had possibilities in the drilling field and the present product is the result of considerable experimental work with other powdered metals as well as with tungsten carbide and cobalt.

Jan 1, 1940

[Furnaces (see also Blast jurnaces) :-(Continued.) McGill, Nev., LI, 765. roasting: XLIX, 184, 188. Anaconda, Mont., XXXVII, 462, XLIX, 676. concrete hearths for, XLVI, 419. Crouse, XLVI, 413. gas, XXXVIII, 163. Heberlein, XXXVII, 634.]

Jan 1, 1918

By Arthur G. Levy, Henry M. How

The purpose of the investigation on which this paper is based is to determine whether the structural change which occurs in the slow cooling of steel below the transformation range has an important effect on its engineering properties. We recognize two distinct things which occur in steel when it is brought from above to below the transformation range, first, the transformation proper, that is, the breaking up of the austenite or solid solution of the cementite in the remainder of the iron, and the liberation of its components as undissolved cementite and as ferrite or alpha iron; and second, a structural change consisting in the gradual coalescence of the ferrite and cementite respectively into larger and larger separate masses. Let us distinguish these from each other by speaking of them as " the transformation " and " the structural change " respectively. If the cooling is at all rapid the unevenness of contraction induces severe stress; so that in a sense a slow cooling has a third influence, the prevention of such stress. This transformation from austenite to ferrite plus cementite can complete itself only below the transformation range; and, because this structural change is a change in the structural arrangement of the products of that transformation, it too can complete itself only at temperatures below that range, say below 725°; and of these temperatures it is only those between 600° and 725° that give the metal sufficient mobility to permit this structural rearrangement to progress with ally rapidity. The transformation is now known to be rapid, but the structural change is relatively slow. The transformation, the liberation of the dissolved cementite from the state of solution in the austenite to a free state, leaves the steel structurally in the

Jan 1, 1913

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