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By J. W. Spretnak

It is well-established that decohesions occurring at the interface of the matrix and rigid inclusions and second-phase particles are prime causes of ductile fracture initiation. It is not clear, however, how these decohesions occur. The idea that the interface bond is broken in tension is not particularly attractive when one considers the strength of such interfaces and the fact that plastic flow is not restricted under conditions of continuing flow required to initiate and propagate ductile fracture. A suggestion as to the mechanism of decohesion arises if one takes the position that, as the dislocation density increases with plastic flow and reaches some critical range of density, the phenomenon of flow can be regarded as fluidlike instead of the crystallographic motion of dislocations. As the spacing between dislocations decreases, the matrix becomes increasingly disordered in terms of loss of periodicity. At some critical degree of reduction of the periodicity, it is suggested that flow can be regarded as hydrodynamic, rather than crystallographic. Such a state has been referred to by rheologists as the "plasticized state", or the "fourth state of matter", between the liquid and solid state. A similar argument pertains qualitatively with the increase in equilibrium vacancy concentration as the temperature approaches the melting point. Taking the viewpoint that at larger strains the flow may become hydrodynamic in nature, a mechanism of decohesion is suggested. A well-known phenomenon in boundary-layer flow is that of "separation" locally of the boundary layer from the substrate.' Under certain conditions, the flow in the immediate neighborhood of the substrate becomes reversed, causing the boundary layer to separate from it. The exact condition for separation is that the velocity gradient normal to the substrate vanishes there, or It is of interest that blunt particles such as spheres and circular cylinders are most likely to give rise to separations because of unfavorable pressure distributions behind them. The source cited gives solutions for positions of separations for various geometries. In principle, such separations can also take place when metal is flowing over a "dead zone" of stagnant metal. This may explain the initiation of fracture at the elastic-plastic boundaries of plastic enclaves under a notch.

Jan 1, 1967

By T. H. Alden

BaCKOFEN, Avery, and Turner have shown"2 that the large tensile elongation in superplastic metals is correlated with a high strain-rate sensitivity of the flow stress. At present, the reported superplastic materials are complex eutectic or eutectoid systems with a large solubility range in at least one of the terminal phases. This note describes the behavior of a solid-solution alloy (at 22°C)5,= Sn-1 wt pct Bi, which has been processed in order to produce a fine grain size.2,3,6 The chill-cast, 1/2-in.-diam ingot was homogenized for 1 week at 130°C, extruded at O°C to 0.083 in. diam, quenched within 15 sec, and stored at -196°C. Samples were warmed to room temperature 16 hr prior to mechanical testing or metallography. During tension testing at room temperature, it was found that the flow stress reached a steady-state value which depended on the imposed elongation rate and was independent of strain to an error of about ±5 pct. In Fig. 1 is plotted log a vs log e where a is the measured steady-state flow stress and i the imposed strain rate. These quantities were calculated using "instantaneous" area and length to an accuracy in the sample diameter of ±5 x 10-4 in. The log a-log 1 curve is sigmoidal. The strain-rate sensitivity, which may be given by d log old log 6,' has a maximum value of about 0.48 between i = 5 x 10-4 and 5 x 10-3 per min. The value is well above frequently measured values for metals at creep temperatures (0.1 to 0.3) and comparable to the rate sensitivity for Pb-Sn solder: which has been shown to be superplastic.2,3 Note, however, that below or above the strain rate of 10-3 per min the rate sensitivity of Sn-1 pct Bi decreases and at high rates is more nearly like that of conventional metals. The grain size of this material is relatively uniform, Fig. 2, and may be specified by an average linear intercept i.' Grain growth occurs at room temperature but after 16 hr, L = 5. Tensile elongation was measured on finer-grain-size specimens, which had been at room temperature 15 min prior to testing. After 15 min, the samples are fully recrystallized. Three strain rates, 5 x 10-3, 10-2, and 2.5 x 10-2 per min, were employed for which the measured elongations varied from 425 to 500 pct. These results would seem to justify the term superplastic, applied to this alloy, although the ductility is inferior to that of the Sn-Bi eutectic.3 The Sn-1 pct Bi alloy, which is a single-phase material with equiaxed, fine grains, is an excellent one on which to make an estimate of the Nabarro-Herring9 creep rate. According to the model of Avery and Backofen2 a substantial part of the deformation must be accomplished by N-H creep in the strain rate-temperature regime in which d log a/d log 1 = 0.5. The maximum N-H creep rate is given by9 L2kT where v is the atomic volume and D the self-diffusion coefficient. For this test v = 3.O x 10-23 cu cm, D = 1.4 e-23,300/RT = 2.5 x 10-l7 sq cm per sec,7 L = 5x 10+4 cm, T = 295°K, and a = 2000 lb per sq in. = 1.38 x 10' dyne per sq cm. The calculated creep rate is E= 4 x 10-11 per sec which may be compared with the measured creep rate at this stress, Fig. 1, of 6.7 x 10-5 per sec. The N-H creep rate is seen to be negligible. Earlier consideration2 of this question was in error because incorrect diffusion coefficients were used. The assistance of R. R. Russell in metallography is acknowledged gratefully.

Jan 1, 1967

By William D. Klopp, Joseph R. Stephens

ThE phenomenon of high ductility associated with a phase transformation, termed super plasticity, has been reported for a number of alloy systems. Abnormally high ductility has been observed during tensile testing of cast eutectic alloys of Pb-Sn and Mg-cu.1 Brasses of Cu-37 at. pct Zn and Cu-40 at. pct Zn elongate up to 180 pct when tested near their transformation temperature.' Enhanced ductility was also observed in Cu-47 at. pct Zn tested near the order-disorder transformation temperature. The most remarkable super-plastic effect reported to date is for the eutectoid alloy A1-60 at. pct Zn, where elongations up to 1000 pct have been reported.3 underwood4 has recently summarized the conditions that normally accompany the superplastic effect which are: 1) a phase transformation or allotropic change or order-disorder transformation; 2) an externally applied stress; 3) presence of an interface between two phases; and 4) a metastable structural condition. In addition, higher ductility is observed when the specimen is tested at slow deformation rates rather than under impact. The purpose of this note is to present evidence of the superplastic effect in a Cr-30 at. pct Co alloy. In addition, low-temperature bend ductility data are given for the alloy in the quenched, metastable, single-phased condition and in the slow-cooled, two-phased, near-equilibrium condition. Sixty-gram alloy ingots were prepared by noncon-sumable arc melting of iodide chromium and electron-beam-melted cobalt. These were cast into rectangular ingots and fabricated to 0.035-in. sheet by rolling at 2300°F. Attempts to roll at slightly lower temperatures invariably resulted in severe cracking, apparently due to presence of the brittle a phase below the transformation temperature of 2230°F. Tensile specimens with a 0.25 by 1.0 in. reduced section were cut from the sheet by electrical discharge machining. The specimens were heated at 2400°F for 1/2 hr to obtain a recrystallized, bcc, single-phased structure. Temperature of the specimens was subsequently raised or lowered to the desired test temperature and held for 10 min prior to testing at a crosshead speed of 0.01 in. per min. Fig. 1 shows the chromium-rich side of the Cr-Co phase diagram.6 The alloy composition investigated is near the point of maximum solubility of cobalt in chromium, and the alloy is two-phased when in equilibrium at temperatures below 2230°F. The results of tensile tests conducted at temperatures indicated by X's in Fig. 1 are summarized in Figs. 2, 3, and 4. Tensile elongations shown in Fig. 2 increase from 11 pct at 1900°F to a maximum of 160 pct at 2250°F. The elongation then decreases to 44 pct as the test temperature is further increased to 2600°F. The proximity of the temperature of highest elongation and the solvus temperature suggests that a superplastic effect is present in Cr + 30 at. pct Co similar to that observed for other alloys that show anomalous ductility. The variation of upper yield stress with temperature is shown in Fig. 3. A small peak in yield stress occurs at 2250"F, coincident with the maximum in

Jan 1, 1967

By J. M. McCormack, R. K. Saxer, J. R. Myers

ThE Knudsen effusion technique was used to determine the chemical activities of copper and platinum in binary Cu-Pt alloys in the temperature range 1542" to 1673°K. Wiebke and Matthes1 previously obtained chemical activities of copper and platinum in this system at 673° and 923°K by the electromotive-force measurement method. They reported that the copper activities exhibited negative deviation from Raoult's law at all compositions. The chemical activities of platinum were found to change from a positive to a negative deviation at 923°K. Myles2 recently studied this system in the temperature range 1265° to 1356°K by means of the torsional-effusion technique. His results indicated that both copper and platinum exhibited negative deviation from ideality at all compositions. The use of the Knudsen effusion technique to obtain the vapor pressure of metals and alloys is well-known.3 In this work, Knudsen cells were fabricated from seamless tantalum tubing of 1-in. OD and 0.020-in. wall thickness; cell bases and covers were cut from 0.010-in.-thick tantalum sheet and welded to the cells in an argon atmosphere. Orifices were drilled and reamed to approximate a knife-edge of 30-deg included angle. Calculation based on Balson's4 derivation showed the orifice to be nearly ideal. All temperature measurements were made with a Leeds and Northrup disappearing-filament-type optical pyrometer at the orifice of the cell, which closely approximated black-body conditions and eliminated the need for emissivity corrections. Details of the experimental techniques used, and the necessary correction factors required during this investigation are essentially those previously described.5,6 Before investigating the Cu-Pt alloys, vapor-pressure measurements were obtained over specimens of pure (OFHC) copper. The pure-copper data5 served to assure the accuracy of the experimental apparatus and technique.

Jan 1, 1967

By N. S. Stoloff, R. G. Davies

The annealing behavior of a heavily cold-worked FeCo-V alloy has been studied at temperatures both above and below Tc, the critical temperature for ordering. It was found that re crystallization and grain growth can take place below Tc in the ordered state and that, in agreement with results for fcc alloys, order retards grain growth. The activation energy for pain growth is -55 kcal per mole in the disordered condition; it was not possible to assign a value to the activation energy for grain growth below Tc because the degree of order is changing rapidly over the temperature interval investigated. Precipitation of an fcc y phase was observed upon annealing the cold-worked alloy at temperatures of 675°C and below. SINCE it is known that diffusion constants are greatly affected by long-range order,' it is not unreasonable to anticipate that order will influence the diffusion-controlled phenomena of recrystallization and grain growth. In the course of a study of strain aging of ordering alloys around the composition Ni3Fe Vidoz, Lazarevic, and cahn2 noted that a disordered cold-worked alloy annealed at a temperature T1 just below Tc will order but not recrystallize; Tc is the critical temperature for order. The same alloy annealed at a temperature T2 just above Tc, or an alloy of different (nonordering) composition annealed at either T1 or T2, will recrystallize after equivalent amounts of cold work. Initially Selisskii and coworkers,3,4 who examined a series of cold-worked and annealed bcc Fe- Co alloys, reported that alloys forming the B2 FeCo super lattice could not be recrystallized below Tc. However in a later paper5 it was shown that FeCo ordered alloys could be recrystallized below Tc. Thus the first question to be answered by the present investigation was whether or not a heavily cold-worked Fe-Co-V alloy could be recrystallized below Tc. When it was found that the alloy would indeed re-crystallize below Tc, the influence of long-range order upon subsequent grain growth was studied. EXPERIMENTAL PROCEDURE The grain-growth measurements were made upon FeCo-2 pct V wire of 0.031 in. diam; the alloy was the same as that used in an earlier study of the mechanical properties of FeCO-v.6 The wire was produced by cold swageing and drawing a rod 0.125 in. diam that had been quenched into iced brine from 850°C to disorder the alloy; the initial grain size was 0.05 mm. Rates of grain browth were measured after isother-mally annealing the wire in the temperature range 675° to 825°C; T, is -720°C. Grain diameters were measured on the transverse cross section of the wires. The line-intercept method of determining the grain diameter was used; conventional light photomicrographs were taken when the grain size was greater than 10 . Carbon replicas were produced and examined in the electron microscope if the grain size was less than Dislocation configurations after recrystallization anneals were studied by electron transmission microscopy of foils produced by cold rolling a 0.125-in.-thick strip of the quenched material to 0.012 in. The foils, after heat treatments similar to the wire samples, were thinned by electropolishing in a chromic-

Jan 1, 1967

By R. G. Davies, R. H. Richman

Several techniques, X-ray diffraction, transmission electron microscopy, conventional, metallography, and mechanical property measurements are combined to investigate decomposition in the suPersaturated solid solution Fe-27 at. pct Be. The following sequence of structures for aging temperatures below 400°C is established: massive short-range order, pseudo-FeBe (L2o) order, Fe3Be (DU3) order, sinusoidal modulation of composition, general or continuous precipitation, and discontinuous or cellular precipitation. In addition to this sequence itself, several features of the individual stages are noteworthy; for example, when coherent modulations occur, their development is parallel to (100) everywhere in the specimen apparently without incubation, and both the wavelength and the composition amplitude of the modulations increase with aging time. Two types of discontinuous reaction are observed, depending upon the aging temperature. At low temperatures (<550°C) the boundary-nucleated variety of discontinuous precipitate predominates; but at higher temperatures (>600°C) the crystallographic variety occurs instead. Hardness and flow-stress measurements clearly reflect the quoted structure sequence. Some qualitative aspects of the structure changes and of the relationship between mechanical properties and structure are discussed. BERYLLIUM in solid solution markedly strengthens iron.&apos;" A recent study demonstrated that not only were supersaturated single crystals of Fe-27 at. pct Be very strong, but they deformed primarily by mechanical twinning.3 Such behavior, coupled with the decrease in solid solubility of beryllium in a Fe from about 33 at. pct at 1165°C to about 10 at. pct at 500°C4 as shown in Fig. 1, leads naturally to questions about property changes with aging in this system. In 1929 roll,1 and later Seljesater and Rogers,5 reported that useful increases in strength could be obtained by aging quenched Fe-Be alloys, but it was not until quite recently that any of the details of precipitation in these alloys were studied. Richman6 observed that both an Fe3Be superlattice (with a DO3 crystal structure the same as Fe3A1, illustrated in Fig. 2) and a modulated structure preceded the appearance of a discrete second phase in the 20 at. pct Be composition. Here, a modulated structure refers to a periodic composition fluctuation within one crystal, while its lattice remains coherent. Subsequent work on a Fe-Be alloys by Heubner7 and von Heimendahl and Heubner8 confirmed the existence of the modulated structure, although only an FeBe (L20) ordered structure was detected (also shown in Fig. 2). Both Rich-man and Heubner corroborated the large increases in hardness during aging reported earlier, but other mechanical properties were not examined. Since modulated systems are encountered relatively infrequently, the influence of coherent modulation upon mechanical properties is not well-known. With the accumulation of information about age-hardening systems, it has become clear that many precipitation reactions cannot always be described by the concept of heterogeneous nucleation at some lattice discontinuity followed by diffusional growth. Rather, complex sequences involving prior "preparation" of the matrix are quite common; that is, a transition structure occurs in the parent phase, instead of in some "nucleus" form. Delineation of such subtle sequences appears to be a worthwhile step toward the understanding of solid-state precipitation. Since not many structural progressions of comparable nature have been reported, the objectives of the present survey are to identify and elucidate the various

Jan 1, 1967

By Bengt Helmerson

A new tankhouse was started in January 1959 at the Copper Refinery of the Boliden Co., Skelleftehamn, Sweden. In early 1961 a semiautomatic machine for looping and straightening of starting sheets was introduced to substitute previous manual operations. The machine as well as consequent, racking and handling is described. Finally, economic benefits achieved and new constructions for the future are discussed. HISTORY Tankhouse operations at the Boliden Co. &apos;s Smelter in Skelleftehamn started in 1932 on a scale that since then has been gradually increasing. In order to rationalize the operations, a new tankhouse was erected. It went into production in January 1959 and was designed for a yearly production of 35,000 metric tons at a current density of 16 amps per sq ft. Already from the beginning, however, the tankhouse has been run with a current density of 21.5 amps per sq ft, corresponding to a maximum capacity of 50,000 tons a year. During the time of planning of the new tankhouse, due consideration was given to the possibilities of mechanizing the operations. New ideas could be and were actually tested on full or pilot plant scale in the old tankhouse. In that way we developed a system for the cathode handling including washing, weighing, and transportation. A system using forklift trucks in combination with trailers and overhead cranes has been developed for transportation and racking of anodes and also for handling of anode scrap. With respect to the electrolyte, circulation and temperature control are partly automatic. Special attention was paid to the production of starting sheets, which operation normally requires a great number of man hours, and it was made the object of a particular survey as to the best ways of straightening starting sheets, attaching loops to the sheets, and so forth. As a result, a machine was designed during 1957-58 and built in our own shops. After a period of tests, the new equipment was put in operation commercially on the 10th of April, 1961. Since this date the machine has produced about 2 million starting sheets without interruption and has been the only source of looped starting sheets for the tankhouse. GENERAL DESCRIPTION Fig. 1 shows all the major parts of the system. These parts are: slitting machine with feeding table (I), standard roller leveler, type Ungerer (2), tilting roller table (3), conveyors for sheets and suspension bars (4, 7), storage of suspension bars (51, punching and stitching machine (6), two lift-turn-tilt tables (8) for discharging the starting sheets, two rack conveyors (9) for sheet assemblies. Included are a hy-daulic pump station and panels for pneumatic and electric controls. SLITTING AND STRAIGHTENING The machine is fed by hand by a man sitting in front of the slitting-machine table, Fig. 2. This operator inserts one sheet at a time into the slitter. After being trimmed, the sheet is automatically conveyed to the following step of handling, straightening. The slitting machine cuts away about 8 mm of the upper and lower parts of the sheet (in relation to its original position in the stripper section) for two reasons. The first one is to give the machine sheets of uniform dimensions; the second one is a matter of quality. Normally the starting sheets as stripped have a thick edge at the bottom end. This part would collect anode slimes and might also cause short circuits when inserted in the cells without trimming. The straightener used is of German construction

Jan 1, 1967

By E. D. Levine

A study was made to delineate the dislocation mechanistns controlling prismatic and basal slip at low temperatu.ves in titanium containing approximately 100 ppm interstitial impurities. Mechanical tests were performed on single crystals prepared from electron-beam zone-refined crystal bar by a thermal cycling technique. Measurements were made of critical shear stress and activation volume as functions of temperature. The study revealed that, for prismatic slip, two overlapping thermally activated processes aye rate-controlling below 300°K. From absolute zero to 220°K, reasonable agreement is obtained between experiment and the mechanism which involves overcoming 01. the Peierl&apos;s stress by the formation of double kinks in dislocation lines lying in close-packed directions. Between 220°and 300°K prismatic slip is controlled by a difierent thermally activated process which is characterized by a stronger temperature dependence of critical shear stress. Above 300OK, prismatic slip is controlled by an athermal process. Basal slip is controlled by a thermally activated process between 195&apos; and 400°K. An approximate analysis suggests that it is the Peierl&apos;s mechanism that is rate-controlling in this range. Below 195°K, the occurrence of mechanical twinning obscures the features of basal slip. Above &apos;400 X, basal slip is controlled by an athermal process. TITANIUM, an hcp metal with a less-than-ideal axial ratio of 1.587, deforms primarily by {1010}( 1210) slip at low temperatures.&apos;-3 The critical shear stress is strongly affected by the presence of interstitial impurities. For example, churchman3 reported that a decrease in the combined nitrogen plus oxygen content from 0.1 to 0.01 pct decreased the critical shear stress for prismatic slip from 9.19 to 1.4 kg per sq mm at room temperature. Basal slip, however, is less strongly affected by interstitials; Churchman&apos;s data for {0001}( 1210) slip show a smaller decrease in critical shear stress from 10.90 to 6.3 kg per sq mm at room temperature, for the same decrease in interstitial content. In the present study, an attempt has been made to delineate the dislocation mechanisms controlling prismatic and basal slip in titanium. In view of the strong effects that impurities may have on at least some of these mechanisms, experiments were performed on material of reasonably high purity, so that comparisons could be made with investigations on material of both lower and higher impurity contents. EXPERIMENTAL PROCEDURE Single crystals were prepared from 1/4-in.-diam electron-beam zone-refined crystal bar, furnished by Materials Research Corp. The analysis of the zone-refined material is given in Table I, indicating that the interstitial content is of the same order as the purer of the two materials investigated by Churchman. The Vickers diamond pyramid hardness number of this material was 85.6. This value agrees quite well with the correlation between hardness and interstitial content proposed by Ogden and Jaffee.4 On the basis of hardness, the material investigated in this study is, therefore, intermediate in purity between that studied by Churchman (Vpn = 97) and that studied by Spangler and Herman (Vpn = 62.4).5 Single crystals were grown by thermal cycling through the a-ß transformation. Two-in.-long by 1/2-in.-diam bars were heat-treated in vacuum for 4 hr at 1160°C. The temperature of the furnace was then lowered to 865°C, and the specimens were maintained at this temperature for 7 days. This procedure was repeated several times, resulting in the growth of individual crystals up to 14 in. in length. Specimens for testing in direct shear along either {l010}(1210) or {0001}(1210) were obtained by electrical-discharge machining. The specimens were in the form of cylinders 1/4 in. in diam by approximately 1/2 in. in length, with a reduced section 1/8 in. in diam and a in. in length. All specimens were electropol-ished subsequent to electrical-discharge machining. The ends of the test specimens were cemented in stainless-steel collars. Shear tests were conducted in an Instron Tensile Tester at various temperatures from 4.2° to 508°K. Measurements were made of critical shear stress and activation volume. The latter measurements were performed by measuring the change in flow stress upon cycling the strain rate between ?1 = 2.62 x 10-3 per sec and ?2 = 2.62 x 10-4 per sec. Activation volume, I)*, is defined as u* =ßkT [11

Jan 1, 1967

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,&apos; a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By W. M. McKewan, R. G. Olsson

In order to improve the understanding of the iron oxide reduction mechanism, the rate of equal molar diffusion of hydrogen and water vapor was measured through disks of porous iron and alumina. The measuretneizts were made at atmospheric pressure at 800°, 900- , and 1000°C. It is shown tint the reduction of dense hematite pellets with hydrogen at these temperatures and at atmospheric pressure is to a great extent limited by gaseous diffusion between the bulk-gas phase and the iron-wustile interface. THE investigation of the reduction of iron oxides with hydrogen has been the subject of numerous papers. Although the effects of temperature, pressure, and gas composition on the rate of iron oxide reduction have been studied, the actual mechanism of the reduction process has not been definitely determined. As a means of improving the understanding of the mechanism, the rate of equal molar counterdiffusion of hydrogen and water vapor was measured through porous iron and porous alumina disks at reduction temperatures. The alumina was used as a basis of compari-son because its pore structure is homogeneous and independent of temperature. The porous iron was prepared by the reduction of dense hematite disks with hydrogen at the temperature of the subsequent diffusion experiment. The hematite disks were made from pellets that were identical to those used by McKewan1,2 in his study of iron oxide reduction with hydrogen. In these investigations the weight loss and rate of movement of the various interfaces were measured as a function of the reduction temperature and gas composition. With these reduction data and the presently reported diffusion data it is possible to determine the importance of H2-H2O transport between the bulk-gas phase and the Fe/FeO interface to the reduction of dense hematite. APPARATUS AND PROCEDURE A porous iron or alumina sample was held in the base plate of a sealed canister containing porous granular wustite, as illustrated schematically in Fig. 1. The canister was suspended from an automatic recording balance in a vertical tube furnace through which flowed hydrogen and water-vapor mixtures of known composition at atmospheric pressure (0.96 atm). Hydrogen from the gas stream diffused through the porous sample, reducing the wustite in the interior of the canister. The water vapor that was formed diffused back to the gas stream. The rate of diffusion was determined from the recorded weightloss data. The furnace, automatic balance, and gas-metering equipment have been described previously.2 The main body of the canister and the tubing extension were made of stainless steel while the base plate was made of high-purity iron. The main body of the canister was % in. in diam. It held approximately 6 g of porous granular wustite that was prepared by reducing 0.1- to 0.2-cm-diam specular hematite particles at 900°C with an H2-H2O mixture of a composition near the iron-wustite equilibrium value. The upper end of the 1/8-in.-diam tubing extension was sealed with a segment of plastic tubing and a tubing clamp. The temperature at the top of the furnace was sufficiently high so that no water vapor condensed inside the extension. In the experiments with porous iron, iron oxide samples were prepared from reagent-grade hematite that was pressed and sintered in a manner previously described.&apos; The resulting pellets had a density of 5.15 ± 0.05 g per cu cm. Each pellet was centerless-ground

Jan 1, 1967

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.&apos; The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young&apos;s modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.&apos;-&apos; While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß&apos;-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,&apos; alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0&apos; phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By L. C. Brown, C. St. John, C. C. Sanderson

The diffusion rate in Cu-Te couples is very sensitive to compressive stress, with a load of 20 psi making a significant difference to the width of the diffusion zone. At zero stress, two phases appear in the diffusion zone (Cu4Te3 and CuTe). Under compressive loading the third stable phase (Cuz Te) also appears, and its thickness increases progressively with increasing stress. The results are explained on the basis of an incipient Kirkendall porosity which restricts the transfer of atoms from the copper into the diffusion zone. DURING a study of the Kirkendall effect in Cu-Te couples prepared by clamping together the two components, it was found that the diffusion-zone width and shape in the plane of contact were not reproducible. Although the stresses involved in clamping are not normally sufficiently high to affect diffusion rates, preliminary tests established that the Cu-Te system is particularly stress-sensitive. The phase diagram for the system Cu-Te given in Hanssen1 shows that there is practically no solid solubility at either end of the phase diagram. Many areas of the diagram are not fully substantiated, but there appear to be three intermediate phases: Cu,Te—hexagonal in structure, having a grey luster; Cu4Te3—a tetragonal defect structure, having a red-purple luster; CuTe—orthorhombic in structure and having a golden-green luster. The existence of a fourth phase, the X phase at 37 at. pct Te, is considered doubtful. The composition ranges of the three stable phases are small, and are not accurately known. The phase diagram changes little with temperature up to 305°C, at which temperature a polymorphic transformation takes place in Cu2Te. The nature of the Cu-Te phase diagram indicates that the diffusion zone in a Cu-Te couple would consist of a series of layers of intermediate phases. The relative thickness of any one phase will depend on its diffusion coefficient and composition range.&apos; In this type of diffusion couple it is often found experimentally that some phases are not visible at all in the diffusion zone due either to a small diffusion coefficient or to a restricted composition range.3 Since the composition ranges of the phases in Cu-Te are not known, it is not possible to determine diffusion coefficients in this system from a knowledge of the phase thicknesses. Several investigations have been carried out to determine the effect of compressive stress on diffusion rates in multiphase systems. Diffusion couples of Ni-A1 have been investigated by Storchheim et al.4 and by Castleman and Seigle.5 Two phases (ß and ?) appear in the diffusion zone under zero stress and the thickness of both phases is progressively reduced with increasing stress. According to Storchheim et al.4 a stress of 25,000 psi reduces the thickness of the diffusion zone by 50 pct. In a-brass—?-brass couples the thickness of the 0 phase formed in the diffusion zone was reduced by 20 pct at a stress of 20,000 psi.6 In other investigations the compressive load has been observed to increase the width of the diffusion zone. In A1-U, several investigators3,8 have found the width of the whase UA13 to increase with stress. According to casileman,8 the rate of formation of UA13 at 520°C is 75 pct faster at a stress of 20,000 psi as compared with a stress of 2500 psi. In Cu-Sb the effect of stress is greater than in the other systems described. According to Heumann9,10 only one phase (y) appears in the diffusion zone at a stress of 500 psi, but at a stress of 850 psi two phases (y and k) are present. If a diffusion couple containing both y and k phases is annealed at a low stress level, the y phase grows at the expense of the k phase. EXPERIMENTAL The diffusion couples were prepared from electrolytic copper bar stock with a nominal purity of 99.92 pct and from tellurium of 99.7 pct purity. The tellurium proved difficult to machine because of its brittleness and a technique was developed for casting the tellurium into a graphite slab mold and spark-machining specimens from this slab. Both the copper and tellurium were produced in the form of discs 2 in. diam by approximately 1/4 in. thick with surfaces ground flat to 3/0 emery paper. The diffusion apparatus is shown in Fig. 1. Auni-axial compressive stress was applied to the system through a simple lever system. A stainless-steel rod actuated by the lever arm lay inside a stainless-steel tube. The diffusion couple lay on top of the steel rod, and pressure was applied to the couple between the rod and a plug welded into the center of the tube. To ensure a uniform stress across the couple, a hemispherical boss and cup were used to transmit the load to the diffusion couple. A 400-w tube furnace with a uniform hot zone 3 in. long slid around the stainless-steel tube and maintained the assembly at temperature. A thermocouple situated 3 in. from the specimen operated a proportional temperature controller which maintained the specimen temperature constant to ±2°C. Most diffusion runs were carried out at 250C although a few tests were made at other temperatures in the range 235° to 300°C. The specimens were inserted and removed with the furnace at operating temperature, and took only 2 min to reach diffusion temperature—a time small compared with the total diffusion time. All the diffusion experiments were carried out in a hydrogen atmosphere, since consistent results were obtained in hydrogen and nitrogen atmospheres and in

Jan 1, 1967

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By M. J. Mullikin, J. B. Conway

Equations capable of representing combined first -and second-stage creep behavior include the Andrade, Cottrell-Aytekin, Garofalo, and de Lacombe equations along with a third-degree polynomial in t1/3. Employing some recent high- temperature creep data for arc-cast tungsten the effectiveness of these expressions was evaluated. It was found that, in this instance, the most accurate representations were afforded by the third-degree polynomial in t1/3 and the de Lacombe equation. Also noted was the fact that the Andrade equation gave results just slightly inferior to those obtained with the third-degree polynomial, definitely better than those due to the Cottrell-Aytekin equation, and slightly superior to those furnished by the Garofalo equation. EXPRESSIONS designed to describe combined first -and second-stage creep behavior must possess certain specific characteristics. At time zero the equation must reduce to a strain value corresponding to the instantaneous deformation on loading. Then in the early moments following load application transient-creep behavior must be described to reflect a creep rate which constantly decreases with time. And finally at larger time values linear (or at least nearly linear) strain-time behavior must be accounted for to yield the steady state or minimum creep rate. Some equations, such as the one based on the parabolic creep law, yield fairly satisfactory results in transient analyses but are not effective at all when combined first- and second-stage data are to be analyzed. Other equations give equally accurate results in both instances although in general the complexity of the equation is slightly increased. For example the Andrade1 equation: has found fairly general application in expressing first-stage creep behavior. Furthermore the contribution of the exponential term becomes more and more prominent as the time increases and causes this equation to exhibit a point of inflection at large values of time. With a proper selection of equation constants the curve can be made fairly flat in the region of the inflection point indicating a desirable equation form for combined first- and second-stage creep analysis. Another equation form with the proper characteristic is that of Cottrell and Aytekin:2 e =a +bt1/3 +ct [2] Obviously as time increases the first derivative of this expression approaches a constant value to suggest application to combined first- and second-stage creep analysis. Similarly a third-degree polynomial in t1/3: e -a + bt1/3 + ct2/3 +dt [3] has the same characteristics. Expressions of this type have been shown3 to be very effective in the analysis of transient-creep behavior and the fact that the first derivative has the same characteristic as Eq. [2] suggests use in the combined analysis.

Jan 1, 1967

By A. M. Adair

The effect of cathodically charging zone-refined iron with hydrogen and the resultant yield stress-grain size relationship has been investigated by tensile testing at -31°C. The resulting Petch plots (using a least-squares analysis) reveal a significant reduction in the slope and an increase in the intercept for specimens cathodically charged with hydrogen, regardless of whether the hydrogen is present during testing or is removed by evacuation. Other than surface blistering, the major effect of cathodically charging this material is to create occasional grain boundary cracks and thus presumably a large number of free dislocations at grain boundaries. These results are consistent with the hypothesis that the slope of the Petch plot is related to the stress required to activate dislocation sources at or near pain boundaries. While there is no significant effect of the presence of hydrogen on the lower yield stress of this material, the ductility is considerably reduced. After hydrogen removal by evacuation, the ductility recovers substantially and almost complete recovery of ductility is experienced by the smaller grain size specimens. THE influence of hydrogen on the mechanical properties of ferritic materials has received much attention throughout the history of the metallurgy profession. This interest has stemmed from the obvious importance of preventing the catastrophic failure of parts in service, and from the desire to determine what mechanism is responsible for the observed behavior. The various mechanisms proposed for hydrogen em-brittlement have been discussed in detail by Tetel-man,&apos;who concludes that a combination of the applied stress and hydrogen pressure within voids best accounts for the many experimental observations reported. From a quite reasonable correlation of the strain aging and delayed-failure behavior of a variety of materials,2-7 Troiano and coworkers are of the opinion that the delayed-failure mechanism (slow strain rate embrittlement as well) is better explained as a lattice effect; solute elements diffuse to regions of high triaxial stress, form uncondensed atmospheres there, and effect a reduction in the cohesive strength of the lattice. Since hydrogen yield points8,9 have been observed in ferritic materials, and since the hydrogen embrittlement process may be related to strain aging, one further contribution to embrittlement could be hydrogen-dislocation interactions which make crack blunting by plastic deformation a more difficult process. The etch" relationship offers a means of comparing the relative ease of initiating and propagating plastic deformation in metals and alloys. In the present study, this relationship was used to compare the behavior of zone-refined iron in three conditions: uncharged, cathodically charged with hydrogen, and cathodically charged with hydrogen and evacuated. These Petch plots and the observed ductility parameters allowed a separation of the effects of the very presence of hydrogen and the act of cathodically charging hydrogen into this material. MATERIALS AND EXPERIMENTAL PROCEDURE An ingot of zone-refined iron was obtained from Battelle Memorial Institute which contained the following (typical) interstitial impurities in ppm: carbon, 10 * 5; nitrogen, 1; oxygen, 22; hydrogen, 0.9. The ingot was cold-reduced to a 1/2-in.-sq cross section, recrystallized 1 hr at 575°C, and then straight-rolled to a thickness of about 0.105 in. Tensile specimens were milled from the strip having a 1-in. gage length

Jan 1, 1967

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of&apos; the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak&apos;s theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967