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By Shiro Ban-ya, John Chipman

The effects of many alloying eletnents on the acticity coefficient of sulfur in liquid iron have-been studied by the equilibriutn in the reaction Sfin Fe) + Hz = HzS at 1550°C'. Results are expressed in terms of a concentration variable for a nonmetallic or for a substitutional metallic solute. Activity coefficient of sulfur, defined as increased by B, Al, C, Si, Ge, Sn, P, As, Sb, Mo, W, Co, and PI. It is decreased by Cu,Au, Ti. Zr, V, h'b, Ta, Cr, ,23n, and Ni. Irulues oj. the interaction coejficient 0i = 6 In are labulated. The same interactions are expressed also in terms of atom fraction and of weight percent. The thermodynamic properties of sulfur in liquid iron have been fairly well established. Our recent paper1 reported new determinations of activity coefficient up an atom fraction of 0.12 and equations based on a careful review of all published data. The effects of alloying elements on the activity of sulfur have been studied by several investigators,2"11 especially by Morris and Williams for silicon,' by Morris and Buehl for carbon,~ and by Sherman and Chipman for manganese. phosphorus, and al~minum.~ However, the effects of some important alloying elements remain to be determined. The purpose of this investigation was to determine the effects of many alloying elements on the activity of sulfur in Fe-S-j ternary systems. EXPERIMENTAL METHOD This study was based on experimental determination of equilibrium in the reaction at 1550°C: The same apparatus and procedure as described in our previous paper have been retained, and the same corrections were applied for dissociation of H2S. The alumina crucibles used in the experiments consisted of four separate compartments. In a given experimental run. kach of three alumina crucibles held four different samples of about 3 g each which reached equilibrium in the same gas atmosphere and temperature. The charges were made up of electrolytic iron, pure iron sulfide, and desired alloying elements, which were pure metal or master alloys made in the laboratory. The weighed samples were held for 4 to 12 hr in the prepared atmosphere at 1550°C. They were then low- ered to be cooled as quickly as possible. The quenched metal beads were crushed to avoid the errors of segregation in the ingot. The sulfur content was determined gravimetrically and alloy content by appropriate chemical analysis. CALCULATIONS The apparent equilibrium constants of Eq. [I] are expressed as follows from the corrected gas ratios and sulfur concentrations: The term K" is the observed equilibrium constant in any given ternary solution, K' is the value for the Fe-S binary solution. and the limiting value of K' in the infinitely dilute solution is designated by K, which is the true equilibrium constant in Eq. [I]. In the thermodynamic treatment of nonmetallic elements in a metallic solution, it has been suggested1' that the lattice ratio has certain advantages over other variables to express the concentration of solute. In interstitial solid solutions the lattice ratio zj is proportional to the ratio of filled interstitial sites to those which remain unfilled. The equations derived for the activity of the solute using zj as the concentration variable are found also to be applicable to liquid solutions containing nonmetallic solutes when the nonmetal is treated as if it were interstitial. For this purpose we adopt the following definitions: The quantity vj which is negative for interstitial solutes is taken as -1 for nonmetallic and +1 for metallic solutes. For purposes of calculation however ; j may be assigned a value which results in a linear relation such as shown in Figs. 1 to 15. The activity coefficient of sulfur, Qs, and equilibrium constant. K(z). are defined as follows: According to a Taylor series expansion. the logarithm of the activity coefficient of sulfur in Fe-S-j ternary system is: However, the value of 6 In */6zi remains constant through a broad range of dilute solutions and the terms of higher order are negligibly small. As a consequence, Eq. [6] is simplified as follows:

Jan 1, 1970

By R. G. Wheeler, J. W. Goffard

The Larson-Miller parameter was used to correlate time, temperature, and indentation creep of magnesium, aluminum, and some of their alloys. In the temperature range 300" to 450°C, the short-time Meyer hardness of pure magnesium was less than that of the magnesium alloys tested, but for long times the pure magnesium has greater indentation creep resistance. Aluminum (1100 alloy) had 1.5 to 2.5 times more indentation creep resistance than magnesium at 300" and 450oC, respectively. Hardening of aluminum with a dispersion of Al2O3 was effective in the time and temperature ranges studied. New technologies have required the development of new materials and the utilization of the more familiar materials for new and unusual applications. The use of magnesium and aluminum and some of their alloys, because of their desirable nuclear characteristics, light weight, low cost, and ready availability, has been extended to the 300" to 450°C temperature range. In this temperature range the basic consideration of these materials must be their rate of plastic flow rather than offset yield strengths. The indentation testing reported here arose from a need for design data for the load-holding ability of supports made of these materials. Test Procedure—Hardness indents were made with a 0.275-in.-diam quartz indentor and a 10.65-lb load. The indentor was made by fire-polishing a spherical surface on the end of a fused quartz rod. The samples were held at temperature in a graphite crucible controlled to ±2°C. A thermocouple was attached to the sample and test temperatures were recorded. The diameter of the spherical indentation was measured at the end of a test period and the compression stress (Meyer Hardness) was determined by: H___________load__________ m = projected area of indent Samples were 1 in. in diam and at least 1/4 in. thick. It was observed that at the higher temperatures and longer times, the quartz indentor would stick to the magnesium sample. The quartz indentor was, therefore, frequently inspected and fire-polishing repeated when necessary. The area of sticking was always a small fraction of the area of indent and was therefore considered to have an insignificant effect on results. Correlation of Hot-Indentation Test Data with Time-Temperature Parameter—Sherby and Dorn' have correlated creep or tensile data of a' solid solutions of aluminum with a temperature and strain-rate parameter suggested by Zener and Holloman. underwood2 used this parameter to correlate creep properties of some steels with hot hardness, and upon the basis of this correlation a means of obtaining creep properties from short-time (and inexpensive) hot hardness tests has been demonstrated. Since the validity of the correlation of creep properties with a time-temperature parameter and the correlation of creep properties with hot hardness have been shown, it follows that hot hardness may correlate with the time-temperature parameter. The hot-indentation data obtained was expressed as Meyer hardness, and was shown to be time and temperature dependent. Correlation of Meyer hardness, time, and temperature with the parameter was made using the relationship: Hm = Meyer hardness t = time, hours T = absolute temperature, OK K = constant A value for the constant K was calculated by equating In l/t + K/T at different temperatures and times but at the same hardness. The correlation was tested by plotting Hm vs the parameter, In 1/t +K/T. Since materials are being sought which have high hardness at low indentation creep, i.e., a high Meyer hardness for long time at high temperatures, low values of the parameter are ofthe most interest. TEST RESULTS Magnesium—Pure magnesium (99.98 pct) cut from extruded rod was indentation tested perpendicular to the rod axis at temperatures of 300°, 350°, 400°, and 450°C for times ranging from 6 sec to 112 hr. Fig. 1 shows the time dependency of Meyer hardness at the four constant temperatures. Fig. 2 shows the correlation of the Meyer hardness of pure magnesium with the time-temperature parameter using a K of 22,720 in Eq. [I]. At the bottom of Fig. 2, the effect of doubling the time of indentation t2 = 2(t1), on the abscissa for any time is shown graphically. This effect is of constant magnitude. Also shown graphically are the magnitudes of the effects on the

Jan 1, 1960

By W. D. Ludemann, J. E. Dor, L. A. Shepard

Recovery of the creep resistance of 99.99 pct pure Al was studied at temperatures 540°, 573°, 600°, and 611°K. Poly-crystalline specimens crept under a stress of 950 psi to a strain of 5.5 pct were allowed to recover for periods of from 1 min to 16 days under a residual stress of 4.4 psi. Increased creep rates upon reapplication of the 950 psi stress evidenced softening of the material. The activation energy for the recovery process was found to be 64,000 cal-per mol. THREE major observations have clearly revealed that the creep of polycrystalline aluminum above about 510°K is controlled by the rate of climb of jogged edge components of dislocations past the barriers impeding their motion: 1) Extensive polygonization, characteristic of climb, takes place during creep.'9' 2) The activation energy for creep equals the estimated activation for self-diffusion. 3) The stress law for creep coincides with theoretical predictions based on the climb mechanism.4,5 The decreasing rate during the primary stage of creep must be ascribed to the introduction of additional barriers to the glide of dislocations. During secondary creep the density of barriers must remain constant, the rate at which new barriers are formed being equal to the rate at which they recover. For this reason the nature of the barriers, and their rates of formation and recovery, are significant to a complete understanding of creep. It is proposed here to study the kinetics of the recovery of barriers to creep of high-purity polycrystalline aluminum in the climb range. The technique will consist of creeping a series of tensile specimens under a prescribed stress to given state following which the specimens will be recovered for various times and temperatures under approximately zero stress. The amount of recovery will be determined by comparing creep curves following the recovery. EXPERIMENTAL PROCEDURE The material used for this investigation was a 99.99 pct pure Al supplied by the Aluminum Co. of America in sheets of 0.001-in. thickness having an H-18 temper. The spectroscopic analysis of impurities gave Cu-0.004 wt pct, Fe-0.002 pct, Si-0.001 pct, others-0.000 pct. Creep specimens were machined with their tensile axes in the rolling direction of the sheets. Annealing in a molten potassium nitrate-potassium nitrite bath for 1 hr at 686K, followed by air-cooling, resulted in a grain diameter of from 0.22 to 0.27 mm. Creep machines were equipped with constant stress lever arms of the type suggested by Fullman, Carreker, and Fishher,' which maintained the applied stress to within 0.04 pct of the reported value of 950 psi. Creep strains were calculated from extensions over a 6-in. gage section to the nearest 3 X 10"5. The temperatures of testing, 540°, 573", 600°, and 611°K, were obtained by immersing the specimen and extensometer assembly in a molten KNO2-KNO3 bath. Temperatures during the periods of creeping could be maintained constant to within better than ± 1°K. Correlation of creep data at different temperatures of testing demanded the use of an appropriate temperature-compensated time 8. Previous investigations have shown that the creep of pure metals at temperatures above about 0.55 of their melting temperatures can be correlated by the functional relationship3" e=f(0), s= const. [1] where e = total plastic strain during creep f = a function that depends on stress a = stress 6 = te-Q/RT = a temperature-compensated time t = time under test Q = 35,500 cal per mol = activation energy for creep R = gas constant, and T = absolute temperature In the present series of tests all of the creep was conducted under the same stress of 950 psi. To provide identical initial conditions for the recovery all specimens were first crept to a temperature-compensated time of = 47 X 10-14 min which resulted in a creep strain of 0.055 + 0.005 regardless of the creep temperature. During recovery, a small stress (4.4 psi) was permitted to remain upon the specimens to maintain tautness in the pulling assembly and to prevent mechanical damage to the soft specimen. After each recovery period, the full stress was reapplied and

Jan 1, 1961

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.' Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.' Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo'sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. 'S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. 'A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. 'Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. 'J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; 'L. V. Al'tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

By R. J. McNally

THERE are three primary plant nutrients—nitrogen, phosphorus, and potassium—expressed in any fertilizer compound as percent N, percent P 2 O 5, and percent K 2 O, in that order. This article will be concerned with the first two. The chief source of P 2 O 5 is phosphate rock. As found in the western states phosphate rock is essentially tricalcium phosphate-calcium fluoride (fluor-patite). As such, it is quite water insoluble.

Jan 1, 1957

CONTENTS PAGE ANDERSON, ARVID E., and CAMERON, FRANK K.-Recovery of Copper by Leaching, Ohio Copper Co. of Utah. Discussed by Thomas B. Brighton, H. C. Goodrich, Arvid E. Anderson, Thos. P. Billings, Frank K. Cameron 2 BEESON, J. J.-Mining Districts and Their Relation to Structural Geology. Discussed by Charles Keyes, Chas. A. Porter 4 DOBBEL, CHAS. A.-Deep-hole Prospecting at the Chief Consolidated Mines. Discussed by G. W. Crane 10 CRANE, G. W.-Notes on the Geology of East Tintic. Discussed by G. W. Crane, H. E. Havernor, N. O. Lawton 11 SACKETT, B. L., BARDWELL, CARLOS, JACOBSON, SIMON, and JENSEN, N. H. Lead Smelting in Utah. Discussed by D. W. Jessup, B. L. Sackett, E. H. Laws 13 BARDWELL, E. S., and MILLER, Roy H.-Pulverized Coal as Fuel for Copper Refining Furnaces. Discussed by L. D. Anderson, E. S. Bardwell, C. P. Crawford 15 WIGTON, G. H.-The Chief Consolidated Volatilization Process and Mill. Discussed by Thomas Varley, S. G. Olmstead, V. O. Lawton, O. C. Ralston.... 16 JESSUP, D. W.-Evolution in the Preparation of Ores for Lead Blast Furnaces. Discussed by W. Spencer Reid, D. W. Jessup, Carlos Bardwell 19 ALLEN, H. P., and MADGE, WM. C.-Chloridizing Mill of the Standard Reduction Co. Discussed by Thomas Varley, H. R. Hanley, H. P. Allen, George H. Dern 20 TUCKER, E. L., and HEAD, R. E.-Effect of Cyanogen Compounds on Floatability of Pure Sulfide Minerals. Discussed by Blarney Stevens 24 Mix, B. E., and BARKER, L. M.-Method of Unloading Ores and Coarse-crushing Practice at Magna Plant of Utah Copper Co. Discussed by W. C. Madge,B. E. Mix 25 KEIGLEY, C. T.-The New Byproduct Coke Plant of the Columbia Steel Corporation. Discussed by W. M. Grant, C. T. Keigley, A. C. Feilder 25 JACKSON, P. W.-Blast Furnace Plant of the Columbia Steel Corporation. Discussed by W. R. Phibbs, H. M. Henton 26 OLDRIGHT, G. L., KEYES, H. E., and WARTMAN, F. S.-Production of Ferric Sulfate and Sulfuric Acid from Roaster Gas. Discussed by G. D. Van Arsdale William E. Greenawalt, G. L. Oldright 27 MAZANY, M. S.-Braden Copper Company Caletones Smelter. Discussed by A. B. Young, G. L. Oldright 36 HARRINGTON, D.-Safety Methods in Utah Coal Mines. Discussed by Edward K. Judd, Otto Herres, Benedict Shubart, A. C. Watts, D. Harrington 36

Jan 12, 1925

By Lawrence S. Darken

STAFF: Editor, Gerhord Derge Cornegie Institute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Longenberg, R. E. Lund, W. 0. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogal. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Qusneau, A. S. Russell, R, E. Shinkoskey, W. W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L.Seigle, Chair-man, P. A. Back, J. J. Backer, l.l. Bessen, J. 0. Betterton, Jr., J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Hager, A. A. Hendrickson, M. Harmon, J. N. Hobstatter, H. H. Johnson, Jr., H. 5. Kolish, R. R. Nash, T. N. Rhodin, R. H. Richman, W. Rostokar, P. G. Shawmon, C. W. Spencer, L. Slifkin, J. K. Stanley, C. D. Starr, R. Steinitz, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; 2. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription PetroleumEngineers,$30 per year for non-AIME members in United States and North, South, and Central America; 332, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1%1 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address; AIME New York ..Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts.. .Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 4.

Jan 1, 1962

MOWRY BATES, ? Tulsa, Okla.-In the first part of this paper the author says: "In an unpublished paper on Water Problem in the Augusta Field, S. K. Clark reaches the following conclusions: (1) That the great amount of water present is bottom water, occurring in the Varner sand, the main producing or the 2500-ft. horizon. (2) That the only striking connection between structure and water is in the area of the marked

Jan 4, 1919

Established as a Division March 13, 1935 R H Feierabend, Chairman T E Gillingham, Jr, Northeast Vice-Chairman W A Riggs, Southeast Vice-Chairman C F Clausen, Mid-Continent Vice-Chairman R H Wilpolt, Rocky Mountain Vice-Chairman J K Brooke, Pacific Southwest Vice-Chairman Leslie C Richards, Pacific Northwest Chairman V A Haw, Canadian Vice-Chairman J S Holland, Sec'y -Treas National Lead Company Mining Department 111 Broadway New York 6, New York

Jan 1, 1960

[Alphabetic Section (Page 1): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

[Alphabetic Section (Page 689): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute of Metals K-Council o f Economics]

Jan 1, 1961

[Alphabetic Section (Page 729): The letter following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

D. K. CRAMPTON, Chairman EDMUND M. WISE, Past-Chairman CYRIL S. SMITH, Vice-Chairman CARL E. SWARTZ, Vice-Chairman H. A. MALONEY, Treasurer Executive Committee 1942 1943 FRANCES H. CLARK ERIC R. JETTE W. L. FINK LOUIS W. KEMPF J. T. NORTON GEORGE SACHS 1944 WILLIAM C. ELLIS ALAN MORRIS KENT R. VAN HORN Finance JOHN L. CHRISTIE, Chairman J. R. FREEMAN, JR. H. M. ST. JOHN W. M. PEIRCE JEROME STRAUSS

Jan 1, 1941

By David Turnbull

STAFF: Editor, Gerhard Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W, Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Langenberg, R. E. Lund, W. O. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogel. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-Chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Queneau, A. S. Russell, R. E. Shinkoskey, W, W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L. Seigle, Chairman, Paul A. Beck, I. I. Bessen, J. 0. Better-ton, Jr., J. B. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Heger, A. A. Hendricksan, M. Herman, J. N. Hobstetter, H. H. Johnson, Jr., R. R. Nash, T- N. Rhodin, R. H. Richman, W. Ros-toker, P. G. Shewmon, C. W. Spencer, L.SIifkin, J. K. Stanley, C. D. Starr, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; R. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1961 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York .. . Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 3.

Jan 1, 1962

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th'vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1'2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS' and on GaAs doped with oxygen,5'" manganese,' and copper.' The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By Merton C. Flemings, Harold D. Brody

Analyses that include diffusion of solute in the solid phase are formulated to describe solute redistribution in dendritic solidification of metallic alloys. The analyses are based on conditions that include negligible undercooling before nucleation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the liquid over distances the order of dendrite spacings, and a plate-like dendrite morphology. The classical nonequilibrium freezing equation, Cs = kCo(I - fS)k-l accurately describes solute redistribution between dendrite arms for the solidification processes considered, provided diffusion in the solid is negligible. To account for the effect of diffusion in the solid, an analytic expression is given which is similar inform to the classical expression. 172 addition, a numerical-analysis procedure is etnployed to examine in more detail the effect of diffusion both during and after solidification. The analyses are intended for application to solidification of castings and ingots to describe a) final solute distribution after solidification and cooling to room temperature (microsegregation) and b) local fraction solid as a function of ternperatcre within the solidifying casting or ingol. SOLUTE redistribution in cellular and dendritic solidification has been discussed quantitatively in recent papers'-3 and in a series of earlier work.4-6 However, none of the analyses developed have permitted close correlation of theory with final solute distribution (microsegregation) observed in castings and ingots. In this paper, discussion is given of approximations which may reasonably be made in mathematical treatment of microsegregation, and analyses are presented based on these approximations. Numerical results are given for Al-Cu alloys. In a second paper the analyses will be compared with exeriment.7 CLASSICAL ANALYSIS The classical quantitative treatment of solute redistribution within a closed "volume element" has been derived repeatedly, for example by Gulliver,4 Scheil,' and Pfann.' This "classical nonequilibrium solidification equation" is written for constant partition ratio: where Cs = interface composition of the solid when the weight-fraction solid within the "volume element" is fs (weight fraction, wt pct); k = equilibrium partition ratio; Co = initial alloy composition within the volume element (weight fraction, wt pct). Assumptions of Eq. [11 are: 1) There is negligible undercooling before nuclea-tion, or from curvature or kinetic effects. 2) There is no mass flow in or out of the volume

Jan 1, 1967

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By J. B. Wagner, B. Swaroop

The atomic ratios of oxygen to iron in zlarious corn-posilions of wustite in the vicinity oj the reported p to n transformation were determined in the temperalure range between 950" and 1250°C. For these conditions, equilibrium vacancy concenrations have also been determined at vatious mixtures of C0,-CO. The data show a continuos introduction of iron vacancies as oxygen is introduced into wuistite. No phase change is observed with in the wuustite field. However, the value of n in the isothermal oxygen pressure dependence, the weight change shifts to 1ower values as the concentration of oxygen increases. WUSTITE is a metal deficit semiconductor with the majority lattice disorder being cation vacancies. Using the notation similar to that of Kroger and ink,' the dissolution of oxygen into wiistite using C02-CO mixtures is represented by, WHere v+! denotes a cation vacancy with k effective negative charges and kh • denotes k electron holes, h -. Applying the law of mass action and assuming a dilute solution of defects in the wiistite yields Where the square brackets denote concentrations. Furthermore, when k = 2 the cation vacancies are completely ionized, and both the concentration of cation vacancies and the concentration of electron holes are proportional to the third root of the ratio, PC /PCo. This analysis is valid for one particular mael based on an ideal solution at elevated temperatures (in this case t > 1000°C). At lower temperatures, it has been shown2 that the pressure dependence of the electronic conductivity changes in a manner which suggests that vacancies interact with or "trap" electron holes. At the very high concentrations of defects, 10'' to 10" per cu cm, these simple models no longer hold. Recently Tannhauser,3 Geiger et a1.' Bransky and Tannhauser; and Hillegas' have found an apparent p to n transformation in wiistite in the temperature range of 950" to 1300°C. This junction was found by thermoelectric and electronic conductivity measurements. Geiger eta1.' found that the electronic conductivity became almost independent of the oxygen pressure at high temperatures and oxygen concentrations within the experimental error. In addition, Vallet, Raccah, and coworkers6'7 have reported the existence of several "varieties" of wiistite which were reported to exist within what was heretofor presumed to be a

Jan 1, 1968

By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.''' This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-'

Jan 1, 1969

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940