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By Beall, John V.

THIS is not simply the story of how a water filled shaft was developed into a million-ton- a-year producing mine in the space of four critical years, although it is reason enough for telling it, but it is also the saga of an engineering achievement in which knowledge nurtured by years of experience in coal and ore mines was blended together and the best from each type of mining selected. The entire system of mining was detailed on maps by the mining engineering department before the shaft was unwatered, and subsequent development followed these plans nearly to perfection. The selection of machinery was particularly critical as it was necessary to push production from only a few headings in the early stages of development and metal mine machinery was being used in a coal panel-system of mining. At the start of World War I1 the demand for iron ore to supply Woodward blast furnaces, and rapid exhaustion of the main source of Wood- ward ore, No. 3 Red Ore mine, necessitated speedy opening of the Pyne mine. The mine is three miles southwest of Bessemer and is responsible for 80 pct of Woodward ore, the rest coming from the Songo mine. The Woodward Iron Co. is one of the old producers of the Birmingham district. S. H. Woodward, an iron-master of Wheeling, overheard two Union soldiers conversing about ore and coal lands in Alabama, which lead to the acquisition of the first ore lands of the Woodward Co. in 1869. Development was not begun until after the death of S. H. Woodward; his two sons, W. H. Woodward and J. H. Woodward, formed the Woodward Iron Co. in 1881 and purchased a tract of land midway between the ore vein on the southeast and the coal field on the northeast about 12 miles southeast of Birmingham for the

Jan 1, 1950

By Paul M. Tyler

THE winning of metals from Nature has been advanced to a degree of efficiency that commands admiration even in this Machine Age. Economy of human effort underground, in surface plants, and in treatment works, and better means of performing all manner of operations have cut costs and im¬proved products to an extent that seems far beyond the wildest imagin¬ings of those that labored in the days of hand mining and muscular metallurgy. Principles and methods borrowed from other professions and sciences - mechanical engineering, chemistry, and physics-all have con¬tributed to the rapid development of ore production and treatment, but no small part of the achievements must be credited to the free exchange of ideas within the industry itself and mass attack upon problems of mutual concern. The esprit de corps or class consciousness that has contributed so effectively to the progress of the metal industries has been less apparent among nonmetallic mineral producers. As a class they have been handicapped by inadequate contact with the metal-mining fraternity as well as among themselves.

Jan 1, 1935

By H. N. Lawrie

Introduction. THIS study was undertaken on account of the lack of definite knowledge concerning the influence of bismuth on wire-bar copper, and the small elimination of bismuth from copper-matte during the smelting-operations. The early workers who studied the influence of bismuth on copper confined their investigations to malleability and ductility-two physical properties which are related to the others so intimately that their determination is of primary importance. Karsten ' and Levol,2 using bending- and mealleability-tests, seem to have been the first to take up the subject, and while their results are incomplete, they agree in the main with the later work of Hampe.3 The bending-tests used by the first investigators consisted in bending the specimen until it failed. The malleabilitytests were made by beating the material to a knife-edge with a hammer. Hampe not only determined the percentage of bismuth which would cause red-shortness and cold-shortness of the alloy, together with other influences of bismuth on the malleability and ductility of copper, but also took up the influence of the bismuth protoxide, BiO, on copper, and of bismuth sesquioxide, Bi2O3, on the copper protoxide, CuO. Hampe's conclusions of the influences of these two latter compounds of bismuth on copper are as follows "If the protoxide of bismuth be alloyed with metallic copper, it is not changed to metallic bismuth, but remains mechanically distributed throughout the copper.

Sep 1, 1909

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d') and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.' These have been designated' as the a, ß, y, d, d', and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d', and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

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 Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-&apos;, a lo-&apos;-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10&apos; cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell&apos;s law that where = critical angle, n - index of refraction of air, n&apos; - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,&apos; and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert&apos;s law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP&apos; have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By C. G. Dunn, P. K. Koh

THE primary recrystallization texture in cold-rolled silicon iron, which is the matrix texture for developing the Goss texture or the cube-on-edge texture by secondary recrystallization at temperatures near 900°C,1-5,21 has not been adequately described. Thus from the present available information, it is not possible to explain satisfactorily both the grain-growth selectivity of the matrix and the often observed magnetic torque curve, which itself provides some information on the texture. Also lacking is information on the special annealing texture that develops in this material when the annealing temperature is 1200°C or higher and the rate of rise to temperature is extremely rapid. From the work of May and Turnbull5 and from unpublished work, it was known that isothermal annealing near 1200°C tends to reduce the extent of secondary recrystallization and that a much weaker cube-on-edge texture results if appreciable normal grain growth replaces secondary recrystallization. Koh and Dunn6,7 have obtained additional information on complex primary recrystallization textures from further studies made after normal grain growth. In these instances the initial textures were retained during normal grain growth. A similar result reasonably could be expected in the present study except for the presence of a grain growth ihibitor1-5,8,9.21 and its tendency to allow only a few grains to grow. However, any information on the orientations of grains in the special annealing texture, even if far from representative of the initial matrix texture, would provide useful information on the nature of the matrix texture. In the present texture study the method of Newkirk and Bruce,10 which is based on the methods of Geisler" and Schwartz, 12 is used to obtain a complete (110) pole figure of the primary recrystallization texture. The high-temperature annealing texture is determined simply from the orientations of a large number of selected grains. The kinetic nature of the process that produces the annealing texture is treated elsewhere13 and it is shown that a form of secondary recrystallization with a very high rate of nucleation occurs during rapid annealing at high temperatures. EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon iron strip (3.16 wt pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Me-tallographic studies indicated complete recrystallization. Short-time anneals at 900° C and at higher temperatures proved that secondary recrystallization had not begun at 800°C, in fact, the short additional anneals were still in the induction period of secondary recrystallization. A rapid rise to an annealing temperature of 1260°C (2300°F) was obtained in a BaC12and NaCl fused salt bath. The structures that resulted from anneals in the range 12- to 1000-sec duration were relatively finegrained, even though the growth was a form of exaggerated grain growth13 or secondary recrystallization with a high nucleation frequency.= Many of the grains were large enough for an X-ray study using a 5-mil X-ray beam. A transmission Laue Camera and an optical-mechanical stage for moving the grains into the X-ray beam were used. A total of 325 grains were X-rayed in this manner and the grain orientations determined. Complete (110) pole figures were obtained for the primary recrystallization texture using CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and Bruce.10 The low voltage serves to reduce the spurious white radiation to a minimum. A filter of 0.001-inch iron foil was located in front of the detector slit for transmission and in front of the beam slit for back reflection. A new and improved specimen holder extended the useful tilting angle range for transmission to 70 deg instead of 60 deg as previously reported.&apos; A torque magnetometer was used to obtain the magnetic torque curves for a number of l-in. diam disk specimens. RESULTS The (110) pole figure of the material after recrystallization at 800°C is shown in Fig. 1. The positions of the pole concentrations are found to be

Jan 1, 1961

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5&apos; is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester&apos; have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5&apos; is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.&apos; The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" &apos; were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations&apos; and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)&apos;0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir&apos;e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5&apos;11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard&apos;s method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

By R. F. Mehl, R. F. Bunshah

A fast amplifier technique has been developed for the measurement of the rate of propagation of martensite in an Fe-29.5 pct Ni alloy. The time of formation of one plate of martensite is 3x10 sec and the rate of propagation is 3300 ft per sec approximately. IT has been known for some time that the plate-like structural unit of martensite forms from austenite with great rapidity. Wiester1 and Hane-mann, Hofmann, and Wiester took motion-pictures of the transformation as it occurs in a 1.65 pct C steel; they demonstrated that a single plate formed fully in the time interval between successive frames, viz., 1/20 sec, thus setting an upper limit. Forster and Scheil,3 using an Fe-Ni alloy with 29 pct Ni, recorded the sonic characteristics of the process electrically, upon an oscillograph, setting the upper time limit at 0.002 sec. Forster and Scheil,~ measuring the change in electrical resistance in the same alloy upon a cardiograph, set a limit of 0.02 sec. Forster and Scheil5 later, employing the same alloy, improved their technique, reporting an upper limit of 7.10 sec. In studying signals of such short duration, it is an important question whether the frequency response of the electrical system used is high enough compared to frequency of the pulse measured, or, put differently, whether the system is able to reproduce without distortion the signal arising, in this case, from the formation of a single martensite plate. Forster and Scheil (referring only to their last paper) obtained signals of a frequency of 30 kilocycles (hereinafter kc); this was about the frequency response of the equipment used; thus, if the signal had a frequency higher than 30 kc, it would still appear as a signal of frequency 30 kc. All of these results thus provided upper limits only. Recent developments in electronics have made available equipment with very high frequency response, very high sweep-speeds, high gain, etc. The electrical characteristics of such equipment, used in the present study, are given in Table I. Such equipment offers obvious attraction in the study of the rate of propagation of a martensite structural unit—and perhaps of other structural alterations proceeding at a very high rate. This paper reports an attempt to develop a technique employing such equipment to measure the time of propagation of a martensite structural unit and the variation of this with temperature, with the mode of formation—athermal and isothermal—in both polycrystalline and single-crystal samples; and from such measurements to obtain the rate of propagation. As will be seen, the results obtained are useful theoretically. Materials All data presented here are for an Fe-Ni alloy of the following analysis: 29.5 pct Ni, 0.027 pct C, 0.135 pct Mn, 0.094 pct Si, balance Fe. There were several reasons for choosing this alloy: 1—it is substantially the one used by previous investigators; 2—it exhibits both the athermala and the isothermal&apos; mode of formation of martensite, both studied in detail by Machlin and Cohen; 3—the subzero temperatures of transformation in this alloy are experimentally very convenient; 4—it exhibits the "burst phenomenon";" 5—the change in electrical resistance upon the formation of martensite, a decrease, is great, approximately 50 pct.&apos; The polycrystalline specimens were in the form of wires of 0.025 in. diameter; the single crystals were 1x1/4x1/4 in. Experimental Methods Electrical Apparatus: Fig. 1 is a schematic drawing of the electrical circuit used. The principle used in these measurements is the same as that used by Forster and Scheil." A small direct current, about 1 to 2 amp, is passed through the sample. When a martensite plate forms, the resistance of the sample changes and a high frequency signal is generated. This signal is picked up by the probes attached to the sample, fed into the bank of amplifiers and thence to the vertical deflection plates of a cathode-ray oscilloscope. The signal itself triggers the oscilloscope trace which flashes across the tube face and is photographed by means of a 35 mm movie camera at the end of a light-tight hood. The camera has no shutter. As soon as the signal flashes

Jan 1, 1954

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3&apos;, as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10&apos;* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965