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By Oscar Lee

RESERVE Mining Co., owned jointly, by Armco Steel Corp. and Republic Steel Corp., controls 9% miles of magnetic taconite ore on the eastern end of the Mesabi Range lying between Mesaba and Birch Lake. The ore reserve which can be mined by open pit methods is conservatively estimated at 1.5 billion tons under a shallow, loose overburden requiring no rock stripping. Taconite now being mined is in the upper cherty horizon. It has been metamorphosed by the intrusion of gabbro and most of the iron oxide is altered to magnetite. The nonmagnetic portion of the iron is practically all in the form of silicate. The magnetic iron is finely disseminated through the rock and requires grinding -150 mesh for clean liberation of the iron oxide from the gangue.

Jan 5, 1954

By William R. Webster

This is a subject which our Institute has made peculiarly its own. In the first volume of its Transactions the analysis of steel received attention, and every subsequent volume has borne witness to the acuteness and industry of our members in the investigation of this subject. The keynote mas struck, in this as in so many other lines of progress, by A. L. Holley, in his paper on " Tests of Steel," read at the Easton meeting of October, 1873 (Trans., ii., 116)—an essay which may rank as a classic by reason of .its elegant form, logical force, and clear prevision of all the bearings of its theme, Taken together with the brief report of the discussion which followed it (in which Dr. Drown emphasized the effects of heat-treatment and mechanical handling, and Dr. Sterry Hunt the importance of minute variations in chemical composition, and of possible isomeric and allotropic conditions), it constitutes, after the lapse of twenty-five years, an admirable and adequate introduction to the long list of technical papers which have succeeded it. Three years later came the epoch-making papers of Dr. C. B. Dudley on the relation between the chemical composition and physical properties of steel rails, which, with the voluminous discussion they evoked, constitute a special volume, published by the Institute, and full of useful suggestions. If Dr. Dudley could be induced to resume this investigation, he would doubtless be able to solve many points still uncertain or disputed. But I cannot undertake to review the history of this subject, as represented in our Transactions—still less to restate all the contributions to it which have been made in books or in papers before other technical societies, since the initiative was taken by the Institute. My more modest purpose is to indi-

Jan 1, 1899

By Alexander L. Field

IN a previous paper,' the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of " red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the rettetion between zirconium and sulfur in molten steel may be represented by the simple equation, Zr + 25 = ZrS², and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion. Hot-rolling Properties of High-sulfur Steels with and without Zirconium The chemical composition of twenty-eight steel ingots embracing eleven heats made in a basic-lined electric furnace is shown in Table 1. The practice followed in the manufacture of these high-sulfur steels was described in the previous paper. Table 1 also gives the behavior of the

Jan 1, 1924

By D. J. McAdam

As shown in three recent papers by the author, in two papers by McAdam and Mebs, and in a paper by McAdam, Mebs, and Geil," the technical cohesive strength of a metal, in any particular state as regards mechanical treatment and heat-treatment, cannot be represented by a single stress value, but must be represented by a diagram with the principal stressest as coordinates. Each point on the boundary of such a diagram represents a technical cohesion limit. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing fracture under a specific stress combination. Moreover, neither the yield strength1 nor the ultimate strength can be represented completely by a single stress value, but must be represented by a diagram with the principal stresses as coordinates. All combinations of the principal stresses may be classified in three groups as illustrated by Fig. I. Fig. Ia shows three typical stress combinations with no two principal stresses equal. The magnitude of each principal stress is indicated qualitatively by the length of the arrow. Arrows pointing away from the cube indicate tensile stresses; arrows pointing toward the cube indicate compressive stresses. Typical stress combinations with two principal stresses equal are illustrated in Figs. rb and Ic. Such stress combinations would be produced by subjecting a cylinder to combinations of uniform axial and radial stresses. The uniform radial stress may be resolved into two equal principal stresses. with the mutually perpendicular directions rotatable around the axis of the cylinder. Fig. ib shows stress combinations with Sz equal to The greatest principal stress is in the axial direction, and the stress combination tends to cause either absolute or relative increase in length.* Fig. u shows stress combinations with S2 equal to St. The greatest principal stress is in the radial direction, and the combination tends to cause either absolute or relative decrease in length. The complete representation of either technical cohesive strength, yield strength, or ultimate strength generally requires a three-dimensional diagram. When two of the principal stresses are kept equal, however, the strength of a metal may be represented by a two-dimensional diagram with the coordinates representing the axial and radial stresses.6-II In this paper, attention will be confined almost entirely to stress combinations with two of the prin-

Jan 1, 1945

By Oliver Bowles

Slate is a fine-grained rock that has a more or less perfect natural cleavage, permitting it to be split readily into thin, smooth sheets. According to a definition established by the American Society for Testing Materials, slate is "a microgranular crystalline rock derived from argillaceous sediments by regional metamorphism and characterized by a perfect cleavage entirely independent of original bedding, which cleavage has been induced by pressure within the earth." Origin and Character Slates have originated from sedimentary deposits consisting largely of clay. Such materials were carried by streams and deposited in seas or lakes in successive horizontal beds. Other materials such as calcium carbonate, sand, or gravel may have been deposited over the clays, and the pressure of these superimposed materials gradually consolidated the materials below into bedded deposits of shale. Shale is a stratified rock formed by recrystallization of the clay plus adsorbed potash into the mica, sericite. Shale has neither the strength nor the splitting properties of slate since the mica is fine and the flakes unoriented, and the quartz grains do not interlock. Many shales, however, have been subjected to intense metamorphism. Mountain-building forces ever at work in the earth's crust may crumple, squeeze, and fold the shales. At the same time, accompanying high pressures and temperatures changed the original minerals into mica, interlocking quartz, or chlorite. Both mica and chlorite consist of minute tabular sheets or flakes with perfect cleavage. The intense pressure and movement tend to orient these flakes in parallel positions normal to the direction of pressure. The parallelism of the flakes results in the tendency to split with ease in one direction, which has been termed "slaty cleavage," and which is the outstanding characteristic of slate. Actually, the cleavage is through the cleavages of the individual micaceous plates. The original bedding of the slate is often folded and contorted, and the slaty cleavage commonly cuts across it at sharp angles. Composition MINERALOGICAL COMPOSITION The most abundant mineral in most slates is white mica (sericite), a hydrous silicate of potash and aluminum. It is present in very small flakes recognizable only with a microscope. Small grains of quartz (silicon dioxide) are also abundant and are regularly distributed among the mica flakes. The mica-like mineral, chlorite, is usually present in considerable quantities. Chlorites are of several kinds, the more common being hydrous silicates of aluminum and iron or magnesium. Other common minerals present in small quantities are rutile, clay, hematite, pyrite, carbonaceous matter, feldspar, zircon, tourmaline, calcite, dolomite, and siderite. The general range of the chief constituents is about as follows: Sericite, 38 to 40; quartz, 31 to 45; chlorite, 6 to 18; hematite, 3 to 6; and rutile, 1 to 1 ½ pct. CHEMICAL COMPOSITION Results of many analyses indicate that clays, shales, and slates differ little in chemical composition. The changes that take place during metamorphism are confined largely to rearrangement of the elements into new minerals with accompanying changes in physical properties such as hardness and cleavage. The general

Jan 1, 1960

By A. D. Marriott, J. V. N. Dorr

This paper reviews recent developments in the application of classification practice to the origination of fine-grinding flow sheets and traces the history of the mechanical classifier from its initial application for separating cyanide process sands and slimes down to its present six or more distinctly different applications at copper concentrators; it undertakes to show also, by reference to diagrammatic fine-grinding flow sheets and accompanying operating data from nine copper concentrators in western North America, the advantages gained from improved classi-ficiation flow sheets at these properties in terms of reduced grinding costs, improved flexibility of operation or increased recovery. Comparison is only made between different fine-grinding flow sheets at a given plant and no attempt is made to compare different concentrators, on account of ore variations and differences in metallurgical objectives sought,. The adoption of the flotation process in recent years, and especially the development of selective flotation, has brought a demand for much finer grinding than formerly. This has caused much thought to be given to grinding efficiency, and today there is hardly a mill where the grinding flow sheet is not under close study and subject to frequent changes. When closed-circuit grinding was introduced into metallurgy some years ago, its value was recognized at once, and since then the combination of mills and classifiers has been regarded and operated as a grinding unit. Apart from variations in both the grinding and classifying elements of this unit, there have been many variations in grouping tried by different mills to suit varying conditions of ore and plant limitations. Although operators feel that in most cases their present flow sheets are on trial, and the data on present work are often incomplete, we have felt that a discussion of the progress that has been made and an endeavor to show present trends and their results should be of use to the profession. We have therefore prepared flow sheets of some of the larger mills with which we have been in contact and present them with available data as to their results, in the hope that they may be of service now rather than later when practice may have become more standardized and more complete records and analyses have been made. We believe that the data given,

Jan 1, 1930

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By R. D. Pehlke, J. V. Gluck

The effect of small additions of silver on the actiziity of zinc in dilute solution with molten bismuth has been determined ill the range 450° to 650°C. Experimental measurements were made in a multi-electrode galvanic cell. All zinc activities showed large positive deviations from Raoult's Law. The results are expressed in terms of the interaction parameter EJ, as defined by Wagner. In the binary Zn-Bi system, Henry's Law was followed at zinc concentrations below 5 mol pct, thus indicating that the binary or self-interaction parameter of zinc in bismuth is essentially zero. The Henry's Law con- THE determination of thermodynamic interaction parameters requires accurate knowledge of solute activities in the dilute-solution region. Dealy and Pehlke1 have summarized the basis for interaction relations, discussed some theoretical implications, and presented a compilation of interaction parameters calculated for molten nonferrous alloys from stant ranged from 2.43 at 650°C to 3.96 at 450°C. The binary zinc activities were consistent with published data for higher zinc concentrations . The ternary interaction parameter ranged from -1.90 at 650°C to -3.30 at 450° C, varying linearly with the reciprocal of the absolute temperature. The negative value for the parameter reflects the fact that addition of silver decreases the activity of zinc in solution with bismuth. data available in the literature. Most of the data were for two-component systems from which only the self-interactions, Ei, could be calculated. Concentration ranges were often such that a considerable extrapolation was required for calculations at lnfinite dilution. The data for ternary systems were quite limited and often unavailable in suitable systematic fashion—thus few values of the parameter e| could be obtained. Knowledge of both the binary and ternary interaction parameters is necessary for the estimation of the activity coefficient of a given dilute solute in

Jan 1, 1965

By W. A. Wood, H. M. Bendler

Cylindrical fatigue specimens of OFHC* copper were subjected to alternating torsion while under axial tension. The superimposed tension strongly influenced the fatigue life of the specimens as well as causing characteristic changes in the structure of the fissures that form and develop throughout the life of the specimen. A further effect of the superimposed tension is a continuous extension of the specimen throughout its life in a manner formally similar to creep at elevated temperatures. RECENTLY, studies of the structural changes leading to fracture of metals by fatigue have been made by a technique which reveals, in section, the lattice distortion arising from slip movements inside the metal and the disturbances built up by these slip movements at the metal surface.1'2 According to this approach, fatigue develops as follows: a) fine slip movements concentrate in bands, producing little strain-hardening and thus permitting abnormal totals of plastic strain before fracture and, therefore, abnormal amounts of lattice distortion along each slip band; b) both forward and backward slip movements occur in each band which, according to their distribution across the band, may build up surface disturbances that include sharp notches; c) these notches early in the life of a specimen penetrate the distorted slip zones and transform them into deep, fine fissures; d) the fissures on continued cycling locally saturate the metal and cause local collapse in the form of a microcrack. Thus, the significant consequence of fatigue or cyclic

Jan 1, 1962

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By R. S. Goodrich, G. S. Ansell

The microstructure of three Al-Al2O3 SAP-Type alloys (containing 2.0, 3.0, and 5.7 wt pct alumina, respectively) was studied utilizing transmission electron microscopy. These alloys were fabricated from aluminum powders by powder-metallurgical techniques, cold-rolled into thin strips, and recrys -tallized. Thin foils suitable for an electron-transmission study were then prepared from the strip material by electropolishing. The microstructure of these alloys is shown to consist of small (0.1 mean diameter) plate -shaped alumina particles finely distributed in an aluminum matrix. In the higher-oxide content alloys the platelets are somewhat larger and more irregular in shape. The distribution of oxide particles is not uniform and there is an increasing tendency toward clumping SINCE the discovery by Irmann1 that aluminum alloys produced by compacting, hot pressing, and extruding fine aluminum powders possess remarkable high-temperature mechanical properties, the Al-A12O3 SAP-Type alloys have been utilized extensively as model dispersion-strengthened alloys in both experimental and theoretical invest igations.2-8 The use of the SAP-Type alloys as model dispersion-strengthened alloys implicitly assumes that their microstructure has been completely delineated. This is, however, not the case. with increasing oxide content. In all the alloys studied, the mean center-to-center spacing of particles was quite small (0.2 u) due to the very fine oxide debris present. Selected-area diffraction of the specimen identified the oxide as either y Al2O3 or y' Al2o3. The re crystallized MD-5100 alloy exhibited a mean grain diameter of only 0.7u, while the grain size of the other alloys was several hundred microns. Severe pinning of the grain boundaries by oxide particles was rarely observed, and the grain boundary triple points in the small-grained MD-5100 alloy were often particle -free. Diffraction contrasts visible around the particles are attributed to elastic strain fields set up by differential thermal contraction during cooling from the recrystallization anneal. Early investigation demonstrated that optical metallography did not possess sufficient resolution to observe the microstructure of the SAP-Type alloys.' Later, extensive use was made of replication techniques to study the microstructure by means of electron microscopy.7-9 These studies indicated that the SAP-Type alloys consist of a dispertion of irregular Al2O3 platelets, approximately 150A thick 9 and a micron or so on edge,9 distributed in a matrix of commercial-purity aluminum. These oxide platelets tend to be oriented in the aluminum matrix, with their largest dimension parallel to the extrusion direction. 8,9 A study employing polarized-light techniques1' indicated that the grain size of a series of as-extruded SAP-Type alloys was several microns in diameter, while the grain size after re-crystallization was several millimeters in diameter. A more recent study 12 utilizing surface-replication techniques examined the particle morphology,

Jan 1, 1964

By C. A. Winkler, V. Hospadaruk

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

Jan 1, 1954

By R. J. Stevens

The Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft ('934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (I) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory furnaces in terms of tons of copper produced per ton of coal burned is high. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table I shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is suficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 22 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1949

By M. W. Cox, V. F. Hollister

EXPLORATION for metallic mineral deposits is carried on by those special adaptations of methods which the explorer believes will yield most economically or satisfactorily the particular answer sought. In this project the usual methods of geologic observation, recording, and interpretation, when combined with magnetic geophysical methods and geochemical soil sampling, led to disclosures of appreciable zinc mineralization where none was visible in surface exposure. Since 1945 considerable work has been done with geochemical prospecting methods, chiefly in determining the presence and distribution of various elements existing in minor amounts in rocks, soil, vegetation or waters of mineralized areas. Such work, in which the U. S. Geological Survey has taken the lead, finds a ready place in the field repertoire of the exploration geologist as a supplement, not a substitute, for other methods. The Chollet project was carried out in 1951 by the American Smelting & Refining Co. near its Van Stone mine in northern Stevens County, Wash., in the area shown in Fig. 1. The Van Stone mine is located in the Onion Creek drainage of the Selkirk Mountains, midway between the towns of Colville and Northport, Wash., and some twenty airline miles west of the Metaline mining district. Its zinc-lead orebodies, currently yielding about 1000 tpd of ore, occur as bedding replacement deposits in the middle Cambrian Metaline formation near an intrusive granodiorite contact. The target of exploration at the Chollet prospect was a similar geologic environment along the intrusive contact about 5 miles west of the mine. Geographic Setting The Chollet ground covers a north-facing slope at 3000 to 4000-ft elevation. Second-growth jack pine and tamarack with some hemlock and yellow pine make a thick forest cover. A heavy under-forest of alder, willow, and lesser shrubs occupies the draws, see Fig. 2. Grassy slopes appear at higher elevations. The lower slopes are underlain by a thick blanket of glacial till and alluvium so that outcrops are scarce; however, perhaps 50 pct rock exposure prevails at higher elevations. This part of northern Washington annually receives about 25 in. of precipitation, which largely falls as snow in the winter months. Summers are dry with occasional rainy periods. General Geology The Van Stone mine and the Chollet prospect lie along the southern margin of a westerly extending lobe of the Kaniksu batholith, one of the series of granodioritic masses that are intrusive into Cretaceous and older rocks in northern Washington and southern British Columbia. The margin is composed of complexly deformed Paleozoic sediments ranging in age from the lower Cambrian Maitlen phyllite on the east, through middle Cambrian Metaline formation (limestone and dolomite), to Ordovician Ledbetter slate on the west. In general the formations strike N10 to 50E and dip steeply northwestward, although dip reversals and minor folding occur. This general rock distribution is shown on Fig. 3. In this area the Metaline formation, which is the host rock for mineralization, appears to be of about 4000-ft thickness that can be conveniently divided into the same three units defined by Park and Cannon' for the Metaline area. The basal part consists of 1000 ft of interbedded white limestone, argillaceous limestone, and gray silty argillite. The middle part, approximately 1500 ft thick, consists of fine-grained black, gray, and white dolomite. This unit also contains minor interbedded limestone. The upper part is a gray massive limestone about 1500 ft thick that grades upward into slaty limestone and slate capped locally by a thin black jas-peroidal dolomite which is either the uppermost member of the Metaline formation or the basal member of the overlying Ledbetter (Ordovician)

Jan 1, 1956

By Donald E. Garrett

The processing of brines from Searles Lake, California, yields one of the world's largest supplies of borax and boron chemicals, second probably only to the massive deposit at Boron, California. Two companies produce from this deposit, the American Potash & Chemical Corp. and the West End Chemical Co., a division of the Stauffer Chemical Co. Two processes are employed in recovering borax from the brines; one is used by both companies and consists of carbonating the brine to form sodium bicarbonate, removing this, and then cooling the liquor to crystallize a crop of borax. Only American Potash uses the second process, evaporating the brine to concentrate it and remove (crystallize) much of its NaCl, Na2CO3, Na2SO4, and NaLi2PO4 content, quick cooling the remaining liquor to remove KCI, and then seeding the filtrate to remove borax. Both methods will be briefly described. Searles Lake is a large evaporite body formed during the most recent two Sierra Nevada ice stages, the Tahoe and the Tioga. Runoff waters from the Sierra Nevada Mountains collected in the large Owens Valley drainage basin and from there overflowed into the Indian Wells basin and then into Searles Lake. In each Lake, evaporation took place. To a large extent the Owens and Indian Wells lakes acted as settling basins, for much of the mud, and insoluble calcium and magnesium precipitates were deposited there. Recent volcanic activity in the mountains to the north and east of Owens Lake had scattered considerable mineral-rich volcanic ash and debris throughout the drainage area, and several hot springs were formed that contained boron and other salts. The present flow rate and concentration of several springs, and the known age of at least the Tioga zone, can fairly well account for all of the boron present in Owens and Searles Lakes.1 The tungsten content can be accounted for in a similar manner.2 Most of the salts thus originally present in the fresh water runoff-from ice, snow, and rain-accompanying these two ice stages were ultimately deposited in Searles Lake. During the Tahoe period, from 25 to 40 ft of massive, mixed salts were deposited, along with six interspersed layers of mud (four inches to two feet thick) representing comparatively brief interglacial periods. Before the final desiccation of the lake, from 10 to 14 ft of new mud was deposited, representing the Tioga stage. The crystals subsequently deposited were from 70 to 90 ft thick, and form the present lake surface. The extent of the salt body is about 34 square miles, of which 12 square miles are exposed salt; the remaining area is covered by recent alluvial deposits (chiefly mud). The present lake is generally dry on the surface but floods to a shallow depth following heavy rains. The crystal body of both zones consists of continuous clusters of salts, and the voids between crystals (about 45 pct of the total volume) are occupied by brine. The level of this brine never recedes more than several inches below the salt surface. The brine pumped to the plants for processing is generally saturated with all of the solid phases present in that area, and thus is a complex mixture containing about 35 pct solids (see Table 3). The brine composition varies somewhat at different areas of the lake and from upper to lower structures, so wells are drilled in the areas and to the depths desired. A casing is cemented in the hole to within a short distance from the bottom, and pumps with about 14-ft suctions are mounted on the casing to pump the brine into the plants. The evaporation process of the American Potash & Chemical Corp. treats upper structure brine, evaporating all of the water from

Jan 1, 1960

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson' have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry' estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,' the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

By E. H. Dix

The work of Merical and other investigators indicates that the phenomenon of age-hardening in alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum Company of America to determine the functions * Metallurgist, Aluminum Research Laboratories. f Metallurgical Division, Aluminum Research Laboratories. Formerly with Metallurgical Division, Aluminum Research Laboratories. 1 P. D. Merica, It. G. Waltenberg and H. Scott: Heat Treatment of Duralumin. U. S. Bur. Stds. Sn. Paper 347 (1910). 2 M. Gayler: Constitution and Age-Hardening of Alloys of Aluminum with Copper, Magnesium, and Silicon in the Solid State. Jnl. Inst. Met. (1922) 28, 213. W. Fraenkel: Vergutbare Aluminiumlegiengen. Ztsch. Melallkunde. (1920) 12, 427. E. H. Dix, Jr.: Note on the Microstructure of Aluminum-Iron Alloys of High Purity. Proc. Amer. Soc. Test. Mat. (1925) 26, Pt. 2, 120. E. H. Dix, Jr. and H. H. Richardson: Equilibrium Relations in Aluminum-copper Alloys of High Purity. Trans. A. I. M. E. (1926) 73, 560. E. H. Dix, Jr. and W. D. Keith: Equilibrium Relations in Aluminum-manganese Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1927) 315. E. H. Dix, Jr. and A. C. Heath, Jr.: Equilibrium Relations in Aluminum-silicon and Aluminum-iron-silicon Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1928) 164. E. H. Dix, Jr. and F. Keller: Equilibrium Itelations in Aluminum-magnesium Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1920) 351. E. H. Dix, Jr., F. Keller and R. W. Graham: Equilibrium Relations of Aluminum-magnesium Silicide Alloys of High Purity. Trans. A. I. M. E., Inst. Met. Div. (1931) 404. W. L. Fink and K. R. Van Horn: Constituents of Aluminum-iron-silicon Alloys. Trans. A. I. M. E., Inst. Met. Div. (1931) 383.

Jan 1, 1932