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By N. Brown, H. Green

The effect of quenching temperature and of aging temperature and time on compression stress-strain curves of ß brass was investigated. Age softening occurs at a rate which decreases with decrease of quenching temperature below the critical temperature for ordering. The activation energy for softening is 15,400 cal per mol. No matter how rapidly brass is quenched or what the temperature from which it is quenched, practically complete order is obtained at room temperature. It has been demonstrated that with respect to the specific heat,',' electrical resistivity," X-ray diffraction, and microstructure, the slowly cooled and rapidly quenched specimens are the same and that complete long range order exists in both cases. However, Smith" showed that the hardness of ß brass depended upon the cooling rate and the temperature from which brass is quenched. Smith showed that the hardness was a maximum for specimens quenched from about 445 °C and that the as-quenched structure softened at room temperature at a rate depending upon the temperature prior to quenching. This softening after quenching is in this paper referred to as age softening. The results of this investigation are qualitatively the same as the findings of Smith. However, a more detailed analysis of these phenomena has been possible since the stress-strain curve offers a more sensitive index of the state of the metal than hardness. It is the purpose of this paper to show how the mechanical properties are related to the ordering of ß brass. A 200-lb ingot made from electrolytic copper and electrolytic zinc was extruded to 1/2in. rod. Chemical analyses at frequent intervals along the rod showed that the alloy contained 51.5 pct Cu with the greatest impurity being iron, at 0.01 to 0.001 pct. To obtain a constant test material, the 1/2in. extruded rod was warm-rolled to % in. diameter at 200°C and then recrystallized to a grain size of 2.0 mm. The specimens for the compression test were % in. high and % in. in diameter. The specimen ends were polished on 600 metallographic paper and coated with Molykote for a lubricant. The compression rig consisted of an anvil resting on the machined table of the Baldwin Southwark testing machine and a plunger fixed to the movable cross

Jan 1, 1954

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By Howard B. Bradley, Charles F. Weinaug

The phase behavior of a naturally occurring hydrocarbon system whose critical temperature is near the reservoir temperature has been described. The same volume per cent liquid was observed for the firkt time at three different pressures for isotherms immediately below the critical temperature. The shapes of the isothermal equilibrium constant curves necessary to predict this phenomena are discussed and illustrated. INTRODUCTION The phase behavior of a number of hydrocarbon systems has been reported; however, very little data are available on natural occurring hydrocarbon systems whose critical temperature is near the reservoir temperature. This appeared to be the case for the fluid studied here; therefore the pressure-volume-temperature data for this system were determined for preqentation. METHOD The PVT data were obtained with equipment similar to hat described by Weinaug and Katz,1 consisting principally of a two-section, double-windowed gauge mounted in a conktant temperature air bath. The procedure followed was essentially that used by Katz and Kurata5 except that a cathetom-eter, reading direct to 0.01 cm, was used to determine the height of each extreme phase limit. The system studied was formed by recombining -.vapor and liquid samples from the first stage separator of the well. Portions of these samples were displaced with mercury into the cell which had previously been filled with mercury. A predetermined amount of the liquid sample was introduced, while an excess of vapor was admitted. The resulting mixture was brought to equilibrium at the condition of the separator during sampling. By adding mercury to maintain the pressure, enough vapor was displaced to give a gas/oil ratio within the cell equal to that produced by the separator at the time of sampling. The remaining material was then considered to be equivalent to the reservoir fluid. An analysis of material in the cell, computed from analysis of vapor and liquid samples and the separator gas/oil ratio. is given in Table I. Table I — Composition of Hydrocarbon System Component Mole Per Cent Carbon Dioxide 0.13 Nitrogen 0.76 Methane 53.91 Ethane 14.20 Propane 9.64 Iso Butane 1.25 Normal Butane 4.29 Iso Pentane 1.12 Normal Pentane 1.87 Hexane 2.72 Heptanes + 10.11 hloleculal. Weight of Heptanes + 178.50

Jan 1, 1951

By Howard B. Bradley, Charles F. Weinaug

The phase behavior of a naturally occurring hydrocarbon system whose critical temperature is near the reservoir temperature has been described. The same volume per cent liquid was observed for the firkt time at three different pressures for isotherms immediately below the critical temperature. The shapes of the isothermal equilibrium constant curves necessary to predict this phenomena are discussed and illustrated. INTRODUCTION The phase behavior of a number of hydrocarbon systems has been reported; however, very little data are available on natural occurring hydrocarbon systems whose critical temperature is near the reservoir temperature. This appeared to be the case for the fluid studied here; therefore the pressure-volume-temperature data for this system were determined for preqentation. METHOD The PVT data were obtained with equipment similar to hat described by Weinaug and Katz,1 consisting principally of a two-section, double-windowed gauge mounted in a conktant temperature air bath. The procedure followed was essentially that used by Katz and Kurata5 except that a cathetom-eter, reading direct to 0.01 cm, was used to determine the height of each extreme phase limit. The system studied was formed by recombining -.vapor and liquid samples from the first stage separator of the well. Portions of these samples were displaced with mercury into the cell which had previously been filled with mercury. A predetermined amount of the liquid sample was introduced, while an excess of vapor was admitted. The resulting mixture was brought to equilibrium at the condition of the separator during sampling. By adding mercury to maintain the pressure, enough vapor was displaced to give a gas/oil ratio within the cell equal to that produced by the separator at the time of sampling. The remaining material was then considered to be equivalent to the reservoir fluid. An analysis of material in the cell, computed from analysis of vapor and liquid samples and the separator gas/oil ratio. is given in Table I. Table I — Composition of Hydrocarbon System Component Mole Per Cent Carbon Dioxide 0.13 Nitrogen 0.76 Methane 53.91 Ethane 14.20 Propane 9.64 Iso Butane 1.25 Normal Butane 4.29 Iso Pentane 1.12 Normal Pentane 1.87 Hexane 2.72 Heptanes + 10.11 hloleculal. Weight of Heptanes + 178.50

Jan 1, 1951

By R. R. Hart, B. C. Wonsiewicz, G. Y. Chin

In recent years there has been increased miniaturization of electromechanical devices to keep pace with current trends toward smaller electronic components. A major problem facing the designer, however, is the higher stresses encountered by the material as a result of shorter springs. Hence an improvement in the elastic limit, as approximated by the 0.01 pct offset yield strength, would be highly desirable. An increase of 25 pct in the yield strength, for example, will permit a 20 pct reduction in both the length and thickness of a cantilever-type spring while maintaining the same compliance. One technique of improving the yield strength that has received little commercial attention is crystal-lographic texture strengthening.1,2 Texture strengthening is expected to be most beneficial in materials of hcp structure, but considerable gain can also be expected in cubic materials. A wire with a (111) fiber texture, for example, is expected to be 20 pct stronger than randomly oriented material, and 50 pct stronger than wire with a (100) fiber texture.293 For sheet specimens with a {110}(112) texture, characteristic of many heavily rolled fcc alloys, the (111) transverse direction is expected to be the maximum yield strength direction, about 20 pct higher than that in the (112) rolling direction.&apos; In addition, the (111) direction is the direction of maximum modulus of elasticity for most cubic alloys. A large value of the elastic modulus could be desirable in designs where stiffer springs are required. To test the above idea, a 0.090 in. (-2.3 mm) thick commercial grade A (5 pct Sn) phosphor bronze sheet, a widely-used material for relay springs, was rolled from the spring-tempered condition (60.5 pct reduction) to various additional reductions up to a total reduction of 95 pct. Subsequently, additional material was obtained with a total thickness reduction of 97.3 pct Standard tensile specimens were prepared from the sheet material with the tensile axis parallel to and at 90 deg to the rolling direction. Tests were run on an Instron testing machine at a strain rate of about 0.050 min-l. Textures were determined by the use of the reflection pole-figure technique. Data were obtained using nickel-filtered CuKa radiation and with the aid of a Siemens pole figure goniometer. The X-ray pole figure studies show an incrzasing development of the texture toward the {110}(112) ideal

Jan 1, 1970

By Dorsey Hager

The possibilities of finding new oil pools in Oklahoma and Kansas are far from promising. In 1916, the only new pools of importance were the Franchot pool near Bixby, the Garber, and the Billings pools in Oklahoma, and the Virgil and Utopia fields in Greenwood County, Kansas. In the first 8 months of 1917, a small pool of unknown extent was opened south of the Stone Bluff pool in Oklahoma, and a pool near Casey, Paunee County, Oklahoma. In Eastern Kansas, interest has been caused by the sinking of new wells near the old Iola pool, but nothing of magnitude has yet been found. The outlook for new pools is far from encouraging, especially as geological surveys have covered all of Oklahoma and Kansas. There are a few areas where geological surveys throw little or no light on the subject, as exposures are poor, but the chances of finding new pools in such areas are slight indeed, if one can judge from the past history of such areas. So far the geologists have based their opinions largely upon the presence or the absence of geologic structure, such as anticlines, domes, and terraces, but some pools will most certainly be found where no surface structure exists, but where local changes in the sand body favor oil accumulations. However, the possibilities of new pools off structure are small, as fully 90 per cent. of the oil pools are on definite structure. In the past, it is estimated that one test in 150 "wild cats" or new tests has brought in a new field. The writer feels safe in asserting that the proportion will decrease still further, so that but one out of 500 new tests may bring in a pay well in a new area. Prom now on the principal field of work in Oklahoma and in Kansas will consist in developing the present pools. The years 1915, 1916 and 1917 saw the high peak of Oklahoma and Kansas oil production. The Eldorado and the Augusta oil fields present the largest possibilities for continued production in Kansas. These two pools have been scarcely more than one-third developed, and have greater potentialities than any of the present Oklahoma pools. In Oklahoma, pools of magnitude should

Jan 1, 1918

PAST AND PRESENT CHAIRMEN OF DIVISIONS Institute of Metals Iron and Steel Mineral Industry Industrial Minerals Year Division Petroleum Division Division Coal Division Education Division Division 1918 W. M. CORSET 1919 " 1920 W. H. BASSETT 1921 " 1922 W. B. PRICE RALPH ARNOLD 1923 E. DEGOLYER 1924 G. B. ELLIOTT 1925 F. JULIUS FOHS 1926 P. D. MERICA 1927 11 JOHN. M. LOVEJOY 1928 S. SKOWRONSKI A. W. AMBROSE RALPH H. SWEETSER &apos; 1929 " J. B. UMPLEHY G. B. WATERHOUSE 1930 ZAY JEFFRIES C. V. MILLIKAN W. J. MACKENZIE HOWARD N. EAVENSON 1931 SAM TOUR C. E. BEECHER F. M. BECKET 1932 C. H. MATHEWSON EARL OLIVER F. N. SPELLER THOMAS G. FEAR C. H. FULTON 1933 T. S. FULLER W. E. WRATHER JOHN JOHNSTON ELI T. CONNOR " 1934 J. L. CHRISTIE H. D. WILDE, JR. L. F. REINARTZ " T. T. READ 1935 W. M. PEIRCE HARRY H. POWER A. B. KINZEL JOHN T. RYAN SAMUEL H. DOLBEAR 1936 E. H. DIX, JR. HALLAN N. MARSH C. E. WILLIAMS EUGENE MCAULIFFE WILLIAM B. PLANK OLIVER BOWLES 1937 A. J. PHILLIPS M. ALBERTSON FRANCIS B. FOLEY J. B. MORROW " CHESTER A. FULTON 1938 R. F. MEHL G. B. CORLESS J. T. MACKENZIE PAUL WEIR FRANCIS A.THOMSON J. R. THOENEN 1939 R. H. LEACH W. H. GETS J. HUNTER NEAD C. A. GIBBONS " M. M. LEIGHTON 1940 E. M. Wise T. V. MOORE F. T. SISCO C. E. LA WALL W. R. CHEDSEY W. M. WEIGEL 1941 D. K. CRAMPTON E. A. STEPHENSON C. H. HERTY, JR. JULIAN E. TOBEY " PAUL M. TYLER 1942 CARL E. SWARTZ HARRY P. STOLZ E. C. SMITH NEWELL G. ALFORD A. F. GREAVES-WALKER B. L. MILLER

Jan 1, 1942

By Dorsey Hager

THE possibilities of finding new oil pools in Oklahoma and Kansas are far from promising. In 1916, the only new pools of importance were the Franchot pool near Bixby, the Garber, and the Billings pools in Oklahoma, and the Virgil and Utopia fields in Greenwood County, Kansas. In the first 8 months of 1917, a small pool of unknown extent was opened south of the Stone Bluff pool in Oklahoma, and a pool near Casey, Paunee County, Oklahoma. In Eastern Kansas, interest has been. caused by the sinking of new wells near the old Iola pool, but nothing of magnitude has yet been found. The outlook for new pools is far from encouraging, especially as geological surveys have covered all of Oklahoma and Kansas. There are a few areas where geological surveys throw little or no light on the subject, as exposures are poor, but the chances of finding new pools in such areas are slight indeed, if one can judge from the past history of such areas. So far the geologists have based their opinions largely upon the presence or the absence of geologic structure, such as anticlines, domes, and terraces, but some pools will most certainly be found where no surface structure exists, but where local changes in the sand body favor oil accumulations. However, the possibilities of new pools off structure are small, as fully 90 per cent. of the oil pools are on definite structure. In the past, it is estimated that one test in 150 "wild cats" or new tests has brought in a new field. The writer feels safe in asserting that the proportion will decrease still further, so that but one out of 500 new tests may bring in a pay well in a new area. From now on the principal field of work in Oklahoma and in Kansas will consist in developing the present pools. The years 1915, 1916 and 1917 saw the high peak of Oklahoma and Kansas oil production. The Eldorado and the Augusta oil fields present the largest possibilities for continued production in Kansas. These two pools have been scarcely more than one-third developed, and have greater potentialities than any of the present Oklahoma pools. In Oklahoma, pools of magnitude should

Jan 10, 1917

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.&apos; Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph&apos; (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,&apos; have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

Without having asked for it, the writer has apparently been drawn into the discussion regarding relative hoisting capacities which was started by Woodward Iron, egged on by Joe Haller of Cleveland-Cliffs [Mining Engineering, August p. 642] and Axel Kjelgaard [November p. 919], who took exception to Mr. Haller&apos;s remarks of tonnage hoisted and avers that they do better in Sweden. It does not appear to the writer that Mr. Haller was inclined to refer to the tonnage hoisted at Cleveland-Cliffs in a manner to imply that they claimed any hoisting record, but rather as a statement that they had hoisted a certain amount of ore during the year 1950. Mr. Haller has been in the mining game long enough to appreciate what Mr. Kjelgaard did not apparently take into consideration, that length of haul, shifts hoisted, nature of ore, method of loading and the many other factors which influence the hoisting cycle make a comparison of tonnages hoisted of two given mines almost an impossibility. Mr. Cheyette sent you .a copy of his letter to Bob Manegold relative to the capacities of the Orient #2 mine. There are several mines around the Country which constantly set up records about which little or nothing at all is ever heard. We cite the Snow Hill Coal Co. mine at Terre Haute, Ind., which has an automatic Nordberg hoist and which hoists 12 tons per trip or 700 tons per hr from 700 ft. This is a counter-weighted installation and a complete cycle is made every 62 seconds or 58 trips per hr. Another mine, The Potash Company of America mine at Carlsbad, N. Mex., has a Nordberg automatic hoist, hoisting eight tons per trip from 1150 ft on a one minute cycle. The materials hoisted in these two mines are ideal for automatic hoisting-they are free flowing so that no hang up is anticipated and hoisting is continuous. Multiplying out the above figures you will find that it is possible to hoist 11,000 tons in two shifts at Snow Hill or over 3 million tons in 300 days per year and over 2 million tons at Potash. Other mines have records which can be pointed to with pride. When a record for one year is established, it doesn&apos;t stand too long as here in America the ambition of all the men connected with the operation forces them on to larger tonnages. T. C. WIEDENHOEFER MANAGER MINE HOIST DEPARTMENT NORDBERG MANUFACTNRING CO. MILWAUKEE, WIS.

Jan 1, 1952

By M. B. Kasen

eralized strain equation appear quite different they are really identical. This identity can be shown in a simple mathematical rearrangement. Referring to Eq. [I], the substitution of ln(1 +?E) for ? (where ?E is the engineering strain) yields: a =s8- (s8?so)e?1/?c) ln(1 +s8??E) [4] or s =s8?(s8?so)(l +?E)-1 [5] Replacing (1 + cE) with its equivalent, (l/lo): s=s8?(s8?so)l/€c [6] Adding and subtracting the quantity (s8 - so) yields: s=s8?(s8?so)+ (s8-so) l-(^)l/£c [7] = s0+(s8?so)ri-(^0)1/^l [8] Letting n = 1/?c it follows that: This equation will be seen to be identical to the generalized strain expression in Eq. [3], the coefficients a and b being equal to so and (s8?so)/?c or n(s8?so), respectively. Confirmation of the relationship noted above was provided by fitting experimental stress-strain data5 for 304 stainless steel (total strain from 0.072 to 1.15) at room temperature at a true total strain rate of 4 x 10-3 sec-1 to Eqs. [I] and [3]. In this study nonlinear regression analyses were used to evaluate the equation constants. The results of this evaluation are presented in Table I. When these constants are used in Eqs. [I] and [3] the curves obtained are coincident. It will also be noted that the value of n is equal to YE,, the value of a is equal to so, and the value of b is equal to (s8 - so)/Ec. These equalities are illustrated in Table I where the Voce constants in parentheses were calculated from a, b, and n values. Excellent agreement is seen to exist. It is concluded, therefore, that the Voce equation is, indeed, identical to the linear expression involving generalized strain. In applying the generalized strain concept to stress-strain data, it has been noted3 that data within what was termed the transition region (first few points in the plastic flow region) must be excluded from the analysis in order to obtain the linearity in Eq. [3]. A similar exclusion applies in the use of the Voce equation since an expression which would describe the strain-hardening region would usually be found to be not too effective in the elastic-plastic fillet2 which connects the elastic line to the strain-hardening region. These considerations further substantiate that Eqs. [I] and [3] do indeed describe identical behavior. Note added in proof. Since this manuscript was submitted for publication, correspondence with Professor S. R. Davies, University of Edinburgh, (of Ref. 3) indicated that his associates have also confirmed the identity between the Voce equation and the generalized strain concept. It is sometimes desirable to obtain a small grain size in super-purity metals. Unfortunately, the absence of impurities, the low recrystallization temperatures, and the low activation energies for boundary motion result in rapid growth of relatively few grains when conventional recrystallization practices are used. For example, Arajs et al.1 were unable to obtain a mean grain diameter less than about 0.4 mm in iron containing 38 at. ppm of impurity. The <1 at. ppm purity range in many modern superpurity metals results in yet larger limiting grain sizes. It is the purpose of this communication to describe a technique by which mean grain diameters as small as 30 µ have been produced in aluminum having an impurity content < 0.5 at. ppm. The technique should be applicable to superpurity metals other than aluminum and has potential applications to grain refinement of commercial alloys. The necessary and sufficient requirements for production of a small grain size are as follows: a) a large number of potential nucleating sites must be created randomly within the cold worked material, b) sufficient thermal energy must be provided at a rate that will simultaneously activate a large fraction of the potential nuclei, and c) the grain growth must be stopped shortly after grain impingement.&apos; A high density of potential grain nuclei may be cre-

Jan 1, 1970

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick&apos;s first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank&apos; supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains&apos; Glasstone, et al&apos; treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity&apos; has shown how to convert the Onsager equations to a form very similar to Lamm&apos;s. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-&apos;Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By D. F. Kelsall

The hydraulic cyclone, in simple or modified form, is finding increasing application in metallurgical processing. In this article, the author considers several aspects of conventional applications, less conventional applications and some potential uses of modified cyclones. Information concerning the mechanism of separation within a cyclone and the effect of the major variables is summarized. During the past twenty years, and especially in the last decade, hydraulic cyclones have found increasing application in metallurgical processing as classifiers and, under special circumstances, as thickeners. To a more limited extent cyclones have been used to extend heavy, or dense, medium separation into the finer size ranges, and several attempts have been made to separate dispersions of immiscible liquids with a view to use in the field of liquid-liquid extraction. A large proportion of published work reports incomplete data, applicable only to particular systems. The more useful papers, covering data of relatively wide significance, have been reviewed recently in considerable detail1,2 and no attempt will be made to cover the same material in the present paper. However, before considering several aspects of conventional application, less conventional applications and some potential uses of modified cyclones, it is considered pertinent to summarize information relating to the mechanism of separation within a cyclone and the effect of the major variables. LIQUID FLOW PATTERNS At any point within a simple cyclone the liquid velocity may be resolved into three components, i.e., the tangential or swirling velocity (v), the vertical velocity (w), and the radial velocity (u). The relative values of these components at selected positions within a typical cyclone have been established for water. 3 The extent to which similar flow patterns exist in systems of considerably higher viscosity, or apparent viscosity, operating under conditions of reasonable pressure drop, is not known with precision, but indirect evidence indicates that up to approximately five centipoise there is no marked change. Beneath the bottom of the vortex finder, envelopes of constant tangential velocity are cylinders coaxial with the cyclone, and, at any horizontal level, starting from near the conical wall, this component of velocity increases with decrease in radius (r) according to the relationship vrn = constant (where 0 < n < 1) This holds to regions near the center of the cyclone where v reaches a maximum value at a radius somewhat smaller than that of the inside wall of the vortex finder. At this point, the centrifugal acceleration, v2/r reaches a maximum value. As the radius is further decreased the tangential velocity decreases so that v = r. Above the bottom of the vortex finder there is a tendency for the first relationship to persist to near the outside wall of the vortex finder, until v reaches a maximum and then decreases rapidly as the wall is approached. The two most significant features of the vertical velocity distribution are an approximately conical Table I. List of Symbols v = liquid tangential velocity at any point in the cyclone w = liquid vertical velocity at any point in the cyclone u = liquid radial velocity at any point in the cyclone r = radius from cyclone axis to any point ? = half angle of conical portion of the cyclone ?= fluid viscosity d = particle diameter s = liquid specific gravity p = particle specific gravity d50 = the particle diameter which distributes 5090 to overflow, 50% to underflow e = overflow diameter, in. b = feed diameter, in. G = gpm of feed slurry

Jan 1, 1963

By M. B. Bever, A. B. Michael

THE structure of cast A1-Si alloys is altered profoundly by modifying agents. Sodium, in particular, reduces the size of the silicon particles in the eutectic and tends to change their shapes from plates to nearly rounded grains. This refinement is accompanied by a shift of the eutectic to higher silicon concentrations and lower temperatures. Similar effects can be attained by rapid solidification. Hypotheses advanced to explain modification have involved the formation of a ternary eutectic,1 the removal of oxides by fluxing,&apos; and even a presumed allotropic transformation of silicon. Other hypotheses assume that the modifying agent causes an envelopment of the silicon particles by the aluminum-rich solid solution, but attribute this envelopment to different mechanisms. According to various explanations, the growth of the silicon particles is obstructed by an immiscible sodium-rich liquid," an adsorbed layer of sodium,&apos; or a ternary compound;5 his obstruction has been conceived as purely mechanical or as a colloidal action.&apos; It has also been proposed that sodium reduces the surface tension on the Al-Si interface, thus permitting the aluminum-rich solid to grow faster and to envelop the silicon particles.? Still other hypotheses stress undercooling and the attendant change in the rate of nucleation of silicon, but fail to ascribe any definite function to the sodium addition." &apos;" Procedure High-purity alloys of aluminum and 3 or 7 pct Si were treated with modifying agents containing radioactive sodium tracers. The experiments were intended to investigate the partition of sodium between the primary aluminum-rich solution and the eutectic, and, if possible, to determine whether sodium is concentrated in or around the silicon particles in the eutectic. Radioactive sodium fluoride, alone or mixed with stable sodium chloride, was allowed to react with the alloy for 5 min immediately before solidification in the crucible. Modification could not be attained with additions of less than the equivalent of approximately 0.1 pct Na. Some alloys were not completely modified, but comparison of the structures of treated and untreated specimens indicated a very considerable reduction in particle size of the silicon in all of the former. A treated alloy is shown in Fig. 1. Radioactive sodium fluoride was prepared by bombardment with deuterons having an energy of 14 mev. This bombardment (totaling, for example, 6 microampere-hours in one run) produced radioactive Na24 (half-life 14.8 hr) by the reaction 11Na23 (d,p) 11Na24. The radioisotopes of fluorine also produced have short half-lives and were not detected. A half-life determination by counting confirmed that the measured activity was due to Na24. The distribution of the sodium in the solidified alloys was determined by an autoradiographic technique by which a suitable stripping film is attached to a very thin metallographic specimen. After exposure and development, this emulsion remains superimposed on the specimen and may be examined microscopically or photographed by reflected light. The emulsion of the autoradiograph can be correlated directly with the underlying surface by simple adjustment in focus. The details of this technique have been described elsewhere." Results Fig. 2 is a micrograph of the autoradiographic emulsion ("autoradiograph") lying directly above the area of eutectic in Fig. 1. Fig. 3 shows a similar autoradiograph of a region consisting of primary solid solution. The small black dots (tracks) in these autoradiographs are developed grains in the emul-

Jan 1, 1954

By W. R. Clough, M. E. Shank

IT has been noted in a study of the flow and fracture of nodular cast iron under biaxial stress conditions (complete results of which will be published later) that when this metal is subjected to stress it may undergo a striking density change. Such behavior was first determined by strain gage measurements made on tensile test specimens, and has since been substantiated by other types of measurement. The chemical analyses and mechanical properties of several nodular irons to be discussed here are given in Tables I and 11. Tensile data for iron A was obtained from a hollow cylindrical combined stress specimen of the same dimension as those used by L. F. Coffin, Jr.1 in his investigation of gray iron properties. Standard 0.505 in. solid tensile-test bars were used for irons B and C. On each specimen type, A-8 wire resistance strain gages were used—two diametrically opposing gages in the axial direction, two in the tangential or hoop direction. By subtracting elastic strains from the measured strains, the plastic strains could be calculated. By assuming that radial and tangential strains are numerically equal, a measure of permanent volume change can be obtained by summing the plastic strains. This appears to be a good assumption, since the metal either fractured, iron A, or readings were discontinued, irons B and C, long before necking took place. This calculated variation of volume increase with stress is given for irons A and B in Fig. 1. Data for iron C is almost identical with that for iron B. The volume change indicated by Fig. 1 has been substantiated by a more direct type of density measurement. A method developed by S. G. Fletcher and&apos; Morris Cohen,&apos; and completely described in the discussion of their article, has been used. The accuracy of specific volume measurement has been estimated as 0.00002 cu cm per gram. Essentially the method consists of weighing a sample in air and then immersed in water. Measurements were made before and after straining the material. The results shown in Table I11 were obtained by means of half-size (0.252 in. diameter, 1 in. gage length, 3/8-16 threads) tensile specimens. Initial measurements were made on the whole specimen before stressing. After stress-

Jan 1, 1955

By Russell G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses.

Jan 2, 1951

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By P. R. Schmidt, N. J. Themelis

A study zvas made of the deoxidation of copper at 1170°C by injecting a jet of carbon monoxide vertically upwards into the melt. The effects of submersion depth (2 to 20 cm), orifice diameter (& to 5 in.), and gas velocity (100 to 3650 ft per sec) were examined. In the oxygen range 0.1 to 1.0 pct 0, the overall rate was conlrolled by gaseoLcs mass Lransfer. The results were interpreted in terms of a rate coefficient per unit depth which was found to be constant with distance along the jet axis and nearly proportional to the orifice Reynolds number in the range 1000 < NReo < 9100. AS the gas flow rate through an orifice submerged in a liquid is progressively increased, at least three regions of bubble formation may be distinguished. At very low rates, the formation of bubbles is practically a static phenomenon, depending on the orifice diameter, the liquid surface tension, and the densities of the two phases. In this region, the bubble size is constant while the frequency of bubble formation increases with gas flow rate.&apos;-3 At higher flows (500 < NR~, < 2100), the frequency of bubble formation reaches a steady value and the bubble size increases with gas flow rate; when the bubbles issuing from the orifice become so large that they start coalescing to form larger bubbles, the turbulence induced in the liquid by the passage of previous bubbles shatters them into small bubbles of varying size. Finally, for gas velocities in the intermediate and turbulent regions of flow (NR,, > 2100) a tangential separation surface is created around the jet and momentum transfer takes place between it and the surrounding liquid medium. The entrainment of liquid and the resulting deceleration of the gas-liquid dispersion causes the jet to expand forming a characteristic jet cone. The large velocity and density differences between the jet and the liquid result in a high degree of instability and the jet envelope fluctuates rapidly.The characteristic jet cone can be observed by means of time exposure photographs such as those shown in Fig. 1 for an air jet introduced vertically upwards in a water bath. High-speed photography has showns that the gas-liquid dispersion within the cone consists of small bubbles the size of which depends mainly on the jet orifice diameter and Reynolds number. In the laminar region of flow, the following correlation was obtained by Leibson: The results of Liebson et a1.&apos; are plotted in Fig. 2. It can be seen that the region 2000 < NReo c 10,000 is not well-defined experimentally. In the entrance to the fully turbulent region of flow (NR,, = 10,000), the mean bubble diameter decreased to about 0.4 cm and varied only slightly from there on according to the correlation:

Jan 1, 1968

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948