Search Documents

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By David Phillips, George Jura

WHEN Bridgman1 determined the volume-pressure relationships of bismuth to 100 kg Cm-2, he found two small volume discontinuities at 45 and 64 kg em-2. Probably every investigator in high pressures has determined the electrical resistivity of bismuth in this pressure range. Until Zeitlin and Brayman2 reported discontinuities in the resistance of bismuth at these pressures, no one had found resistance discontinuities

Jan 1, 1968

By R. B. Gavert, David J. Mack

ROOM- and elevated-temperature compression tests were made on the binary 3/2 electron compounds AuZn, CuAu, AgZn, AgMg, AuCd, and NiA1. These compounds possess either the B2 CsC1-type ordered structure or the A2 bee disordered structure represented commonly as ß and ß on equilibrium phase diagrams. In testing at room temperature, cylindrical specimens 0.508 cm by 0.330 cm diam were seated directly on an instron compression load cell (CF 0 to 10,000 lb). At elevated temperatures, testing included a special apparatus with a furnace heat source and a protective atmosphere.' The specimens were strained at a rate of 1 pet per min. The compounds were prepared from 99.99 pet or better high-purity elements. Vacuum and/or argon cover gas was used throughout the mixing, melting, and specimen drawing processes. The generally equi-axed specimen grains varied in size from 0.5 to 1.5 mm for the five different compounds. The stress-strain curves in compression showed

Jan 1, 1968

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By Charles J. McMahon

In a recent paper, Floreen and Hayden report that additions of the noble metals iridium, rhodium, ruthenium, and platinum to Fe-C alloys containing 0.03 to 0.08 wt pct C act to significantly reduce the ductile-to-brittle transition temperature in a notched-bar impact test. They compare these results with the similar, well-known effects of nickel and manganese additions, and they note that this supports the hypothesis that addition of austenite stabilizers enhances notch toughness. Although not attempting to offer an explanation for this, they suggest that it might be found in an alteration of the bonding characteristics of the bcc lattice of iron by additions of elements which tend to stabilize the fcc lattice. While this suggestion appears to have some merit, it should perhaps be held in abeyance until two more likely possibilities have been explored. It is now fairly clear that the beneficial effect of manganese derives from its ability to promote a globular carbide morphology instead of the platelike form found in grain boundaries and pearlite patches in Fe-C al10~s.' Previous work14 has also shown that cleavage fracture in Fe-C alloys of the type tested by Floreen and Hayden originates almost exclusively in the cracking of cementite platelets, and that the ductile-brittle transition temperature is very sensitive to the volume density and size of these carbides. Treatments which lead to development of nonlamellar carbides or fine dispersions of carbides, such as quenching and tempering or appropriate alloy additions, promote toughness by removing the primary mode of cleavage initiation. The effectiveness of manganese in this regard has long been known. Nickel appears to behave in a similar manner, though the effect is perhaps not as dramatic as with manganese.15 However, nickel additions do lead to a definite refinement of ferrite grain size following a given transformation heat treatment, and this in itself acts to greatly enhance notch toughness.'' (The grain sizes of the various heats tested by Floreen and Hayden were not reported, so it is not known how much influence this factor exerted in their results.) In conclusion, it is suggested that one should consider the well-established effects of alloying elements on carbide morphology and ferrite grain size before resorting to more complex possibilities, such as modification of interatomic bonding.

Jan 1, 1969

By P. S. Katval

It is interesting to note that an attempt has been made to rationalize the effect of prestrain on the strength of Hastelloy X-280 after various aging treatments. However, two points raised by the authors seem to be somewhat unclear. 1) Concerning their Fig. l(a), the authors state: "Extensive dislocation networks are still in evidence. The 24-hr aging at 1500°F and the 15-min soak at 1350°F did not eliminate the dislocations introduced by the 20 pct cold reduction." This is, of course, to be expected since complete "elimination" of dislocations would require recrystallization which does not occur at 1500°F in Hastelloy X. However, recovery

Jan 1, 1969

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By R. E. Hummel, J. W. Koger

SINCE the first report about a diffusionless transformation of bcc p1 brass to tetragonal p" in 1936 by Kaminski and Kurdjumov,' a series of papers have been published about this transformation, mainly dealing with the temperature range of the martensitic-start temperature (M,) and with the crystallographic structures of the parent and product phases .s In the

Jan 1, 1969

By G. A. Josey, T. P. Floridis

INFORMATION on the effect of alloying elements on the solubility of sulfur in solid iron alloys is limited to the effects of carbon,' manganese,' and Silicon.Refs. 3 to 5 provide information on the combined effects of silicon and manganese also. In the investigation reported in this communication, the effect of chromium, copper, nickel, and vanadium on the solubility of sulfur in solid iron was determined at 1000". The specimens for this investigation were prepared by melting electrolytic iron and reagent-grade alloying additions in an induction furnace under an argon atmosphere. The melts were allowed to solidify in

Jan 1, 1969

By E. F. Koch, J. L. Walter

In a study of the structure and properties of tungsten wire used for lamp filaments, it became desirable to perform transmission electron microscopy on the wire in the annealed as well as in the drawn condition. Wire used for lamp filaments is generally drawn to diameters less than 0.010 in. which is too fine for the preparation of transmission samples from single wires. Thus, it is clear that some assembly of wires must be used to form a "wire sheet" similar to that used by Glenn and Duff.' Also, because recrystallized tungsten wire is brittle at room temperature, the "wire sheetJ' must be rigidly contained during any subsequent grinding and polishing operation. With these conditions in mind, a technique was devised for thinning tungsten wire of 0.001 to 0.010 in. diam for transmission electron microscopv. Sample Preparation. The commercially doped (218) tungsten filament wire was obtained from the Lamp

Jan 1, 1969

By D. J. Mottern, F. Wald

SEVERAL systems have been investigated by Bates, Wald, and weinstein&apos; to determine the compatibility of pure PbTe with various metals. This was accomplished by experimentally determining the direction of the reaction given by Eq. [I]: The direction of this reaction is very important if alloys of the PbTe system are to be used in thermoelectric generators because the presence of free lead in the matrix, followed by incipient melting in the vicinity of the hot junction, could cause a bonding failure. According to anssen,&apos; the Au-Te system contains only one stable compound, AuTez. The initial alloy which was reacted was therefore of the composition AuTez + 2Pb. Ten-gram samples of PbTe plus 1, 10, 20, 30, 40, 50, and 70 at. pct Au were encapsulated in carbon-coated quartz capsules in vacuo. All materials were of semiconductor (99.999+ pct) purity. Carbon coating was used to prevent reaction of the quartz with any of the alloying constituents (the solubility of carbon in the constituents of the alloys is negligible). Each capsule was then placed in a thermal analysis furnace, melted, and cooled through the transformation region. Thermal arrests were monitored on a strip chart recorder. Each sample was subsequently examined microscopically after standard grinding and polishing techniques were applied. For better contrast between the phases, the samples were etched in Murakami&apos;s etch; however, both phases could be identified without etching. Several of the samples were ground into powder, stress-relieved, and X-rayed in a Debye-Scherrer camera using nickel-filtered Cu-Ka radiation. The phase diagram shown in Fig. 1 indicates that the pseudobinary system exists as a simple eutectic with no measurable (<I pct) solid solubility at either limit. Figs. 2,3, and 4 are photomicrographs of the structures obtained with 20, 40, and 50 at. pct Au, respectively. At higher concentrations of gold (>40 pct) slight divorcement of the eutectic occurred, apparently due to a) the difference in density between gold and PbTe (19.6 and 8.25 g per cu cm, respectively) or b) the nonideality of the liquid as noted by the curvature of the liquidus lines. The eutectic temperature was determined to be 742° ± 5°C. The composition of the eutectic was determined by extrapola-

Jan 1, 1969

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,&apos; cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott&apos; seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .&apos;i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched &apos;(super dendrites&apos;&apos; shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By E. J. Rapperport, J. P. Pemsler

We have made calculations to evaluate the sensitivity of atomic absorption as a technique to measure vapor pressure changes with temperature. Our conclusion, supported by the experimental findings presented in this work, is that the ultimate sensitivity of the technique is well below lo-&apos; Torr. This magnitude of vapor pressure sensitivity makes the method extremely attractive for thermodynamic studies. Atomic absorption techniques have been used previously in this connection by Scatchard and Boyd&apos; and by vidale2 with a much lower sensitivity reported. Scatchard and Boyd&apos;s work measured cadmium pressure over Ag-Cd alloys in the range 0.02 to 0.3 Torr, and Vidale estimated that sensitivities of only 10"5 to 10"6 Torr are to be expected. Atomic absorption appears to be particularly well-suited to thermodynamic studies for several reasons: A) It is extremely sensitive; our experiments indicate an ability to measure vapor pressure changes of 10"9 Torr. B) It is highly selective; there is seldom interference among the resonant wavelengths of the various species. C) It may be performed in an absorption cell under static conditions. This alleviates such problems as surface impoverishment of alloys, attainment of equilibrium, and temperature measurement and control. D) Simultaneous, or near-simultaneous, vapor pressure measurements may be made for several elements in a given system. Experimental. The physical basis of the technique is the highly selective absorption of particular wavelengths by specific atomic species. In most atomic absorption work the element of interest is incorporated into a hollow cathode lamp to provide a characteristic spectral source of high intensity. The spectra lines characteristic of the element in the cathode are attenuated by atoms of that element in the radiation path. Radiation from silver or cadmium hollow cathode lamps was directed along a path containing a 10-cm evacuated silica cell. The cell was positioned within a silica windowed furnace and contained silver, cadmium, or an Ag-Cd alloy. As the furnace temperature was elevated, the number of atoms of the absorbing element in the vapor phase within the cell rose, and the resonant radiation was increasingly absorbed. Intensities were measured by passing the radiation through a Techtron Model AA-4 one-half meter grating atomic absorption spectrometer equipped with a photo-multiplier detector. In order to minimize instabilities in the source, the hollow cathodes were allowed to warm up for several hours and were run at only 2 5 to 30 pct of their maximum rated amperage. In addition the attenuated beam was monitored before and after each reading. The attenuation of resonant wavelengths may be related to vapor pressure by the following relationships.

Jan 1, 1969

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,&apos; Kniippel et &apos;a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell&apos;s&apos; investigation and comparisons are made with his observations. Torssell&apos; studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10&apos; per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10&apos; per cu cm, is of the same order of magnitude as found by ~er~h.&apos; This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~&apos; The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht&apos; studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969

By K. H. Adams, T. Vreeland

The basal stress-strain behavior, dislocation density, and strain vale sensitivity of the flow stress uqere measured at room temperature on single crystals oj-zone-refined zinc , 99.999 pct Zn, and zinc containing 0.0025 and 0.02 wt pct Al. No significant change in the stvain rate sensitivity of the flow stress occurs with the addition of aluminum. Changes in dislocation substructure and nonbasal dislocation density were obserrled with the addition of aluminum. The effect of aluminum on the basal slress-strain behavior is explained in terms of changes in nonbasal dislocation density which determines the separation distance of junctions between basal and nonbasal dislocations. The onset of basal slip is associated with the breaking of attractive junctions. The chunge in basal dislocation density was found to be proportional to the one-third power of the plastic shear strain, indepedent of purity. THE effect of impurities in solid solution on the stress-strain behavior of single crystals has been the subject of many theoretical studies. These studies have generally concentrated on the interactions between impurities and dislocations to explain the hardening effeet of impurity additions. The theories that have been proposed include those of yott and Nabarro,&apos;l&apos; Cott-re11; Suzuki; and Fisher. In practice, it is generally difficult to predict the relative importance of the vari- ous effects due to impurities. In addition, secondary effects of impurity additions such as induced changes in dislocation density and substructure in the as-grown crystals have received little attention. Many experimental investigations have been conducted on the effect of impurities on the stress-strain behavior of fcc crystals. Hcp crystals have not received much attention except for the extensive work of Levine et a1.= on magnesium alloy crystals. Stuwe~&apos;&apos; has studied the effect of copper impurity on the critical shear stress of zinc crystals and has interpreted the results in terms of the impurity atmosphere model of Cottrell and Jaswon. This report presents the results of an experimental study of the effect of aluminum additions to zinc on the basal stress-strain curve and the strain rate sensitivity of the flow stress. Etch pit techniques were used to measure and characterize the dislocation density and substructure in the zinc alloy crystals. EXPERIMENTAL PROCEDURE Specimen Preparation. Compression test specimens of four different purities of zinc were prepared from CP grade zinc of 99.999 pct purity obtained from the New Jersey Zinc Co. An analysis of this material furnished by the supplier indicated the following impurities in wt ~ct: Pb = 0.0002; Fe = 0.0002; Cd = 0.00005; other <0.60011. A quantity of material of this grade was further purified by zone refining. Zone refining was carried out under a helium atmosphere by passing a double &apos;One furnace Over a 6-ft-10ng charge at the rate of 2 in. Per hr. * total of ten double zone passes were made before the charge was removed from the furnace. The first one third of each charge was used to grow single crystals. Quantities of two

Jan 1, 1969

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain&apos; extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami&apos;s reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969