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By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,' Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)' from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By S. R. Maloof

In 1945, Hollomon' showed that after plastic yielding and prior to necking under simple tension, both ferrous and nonferrous materials are approximated by an equation of the following form: where, a = true stress K = strength coefficient 5 = true strain n = strain hardening exponent If a material is stress free, a plot of log o vs log 6 would be expected to be a straight line, the slope of which is the strain-hardening exponent (n) and the intercept on the ordinate axis for 6 = 1. is the logarithm of the strength coefficient K. It can be easily shown that the strain-hardening exponent in the above equation is equal to the total uniform elongation prior to necking. Thus, one can determine the total uniform elongation prior to necking from such a plot and, as pointed out by C. W. MacGregor, 2 it is the amount of strain prior to necking which determines the extent to which a material may be deep drawn. In the view of the current interest in the fabrication of beryllium shapes, it was thought that a knowledge of the strain-hardening exponent of cross-rolled beryllium sheet would be of general interest. Load-strain data after yielding and prior to necking was taken from the work of Greenspan,3 converted to true stress and true-plastic strain, and plotted on log-log paper as shown in Fig. 1. The value of Young's modulus E for beryllium was taken as 43 . l06 psi. The slope of this plot gave a value of 0.212 for the strain-hardening exponent (n) and the intercept on the ordinate axis a value of 105,000 for K. The total uniform elongation is thus 21.2 pct, in excellent agreement with the value estimated by Greenspan (about 20 pct). Furthermore,

Jan 1, 1960

By B. B. Betty

H. L. Burghoff.*—Have the authors any information on the effect of grain size in these materials? There is a material difference in the grain sizes shown for the Monel and the Inconel. Is a wide range of grain size normally found for each material, and, if so, what is its effect upon creep strength? 11. L. Eiselstein.—The grain size for Monel shown in the micrograph is the usual size found in that product. The grain size of Inconel is about the same as that, too. However, we have run tests on Inconel at higher temperatures than those reported in this paper, and have found that the coarser grain size has a better creep resistance; and that the grain size that gives the best creep resistance at 1600°F. is about 0.005 in. in diameter. We have no test on Monel with varying grain size. J. J. KANTER.†-It has been known for a long time that Monel metal exhibits ductility anomalies at elevated temperatures. Even in short-time test, it can be demonstrated in the range of 900°F. that there is a distinct falling off of the ability of Mone1 metal to elongate, and in rupture tests this shortcoming is still further accentuated. Knowledge of this rupture anomaly of Monel metal may be one of the reasons for which designer's approach certain high-temperature applications with reservations. The authors of this paper have merely demonstrated that for 900°F. the alloy has an ability to elongate 1.7 per cent over a period of some 2700 hr. Before any conviction can be expected from designers that Monel metal is applicable to stress design in such range of temperature, I think it is desirable to demonstrate the capacity for the material to elongate over a longer period of time than has been done in this presentation.

Jan 1, 1945

By J. D. Audley Smith

Heine's " blue test" for copper, as described by the authorities generally, calls for a set of standard colors; and there has been some discussion concerning the relative superiority, for this purpose, of sulphate and nitrate solutions. The whole matter evidently hinges on the preservation of the standard colors in well-stoppered bottles. The apparatus described by Q. L. Heath* cannot be much improved, when very accurate readings are required. The following method was devised for the purpose of doing away with preserved sets of standard colors, by making a fresh standard for each batch of assays. The solutions are prepared in the usual way, each ammoniacal solution being filtered into its separate bottle, and then filled up to the containing-mark and thoroughly mixed. A similar color-bottle, with an " S " etched upon it, to distinguish it from the other bottles, which are numbered to correspond with the samples, is kept to run the standard. About 150 C.C. of water is put into it, and then the amount of acid (sulphuric or nitric) present in each determination, followed by 30 C.C. of ammonia (s. g. 0.90), which should make the mixture strongly ammoniacal. The liquid is now made up almost to the containing-mark (200 c.c.), say within 1 C.C. The lowest assay is selected first and placed alongside the standard, which, at the beginning, contains no copper. A copper-solution is then dropped into the standard from a burette ; and after each addition the bottle is well shaken and compared with the assay-sample. This operation is repeated until the two shades match exactly, when the burette is read and the assay-result is calculated. The assay next in order of depth of color is now taken and treated in the same way, and so on, until the batch is completed. It

Jan 1, 1901

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

A. 0. ASHMAN, Palmerton, Pa. (written discussion *.).-Mr. Newcomb's paper has interested me greatly, as I have had numerous experiences along this line. I do not think enough emphasis can be put on his warn-ing to keep platinum couples free from contact with quartz tubes, as silica shows a tendency to alloy with platinum to a surprising degree even at low temperatures. I have frequently had evidence of silica contamination in a perfectly good tube, in which there was seemingly no possibility of a reducing atmosphere. This is rather important as it seems to be common practice to insulate, as well as protect, the wires by means of- capillary silica tubing, thus allowing the entire wire to be in contact with the silica. The best way to mount a couple in a silica protecting tube is by means of double-bore porcelain insulating tubes, the protecting tube being slightly longer than the couple so as to leave a space between the couple and the end of the tube. In this way there is no possibility of contamination from silica. In no case should silica capillary tubes be used to insulate platinum wires. Mr. Newcomb states that there is still much to be desired in pyro-meter protecting tubes; this is in keeping with my experience. From a practical standpoint there is not a satisfactory pyrometer tube on the market for high temperatures; with all clue respect to the many improve-ments and good work recently done in this line. I believe that the whole future development of pyrometry is dependent on the development of suitable refractories. With suitable refractories, for example, Darling's1 work with liquid couples could be developed to a practical basis, making possible the use of base-metal couples to replace platinum.

Jan 12, 1919

By W. Spencer Hutchinson

It is the purpose of this paper to describe a method used to determine the corundum contents of samples of hard crystalline gneiss containing both corundum and red garnet. A chemical analysis of the rock for alumina would not fix the amount of corundum became at least three other constituent minerals of the rock, mica, feldspar, and garnet, contain alumina combined with silica. Following are the principal minerals found in the samples, together with their specific gravity and hardness as given by Dana: The corundum occurred in crystals of a gray or bluish gray color, in minute grains and coarser up to 0.5 in., and no massive or block corundum was observed. The larger crystals were commonly quite slender, well defined, and the normal hexagonal form clearly developed. They lay with the structural planes of the gneiss, and sometimes appeared prominently in relief on weathered surfaces. In some cases these crystals had suffered partial or total alteration to mica, margarite, or other soft minerals, a condition illustrated by sample D, which appeared to be studded abundantly with corundum on the flat faces. Garnet, a striking feature of nearly all the samples, was present in small rounded crystals of a pink to red color. The samples were first broken to pass a No. 4 mesh screen. This was done with a hammer on an iron plate, particular care being taken to avoid the breaking of the crystals finer than need be to pass the screen. A portion of the sample weighing 500 g. was then taken and, with a little water added, was scoured round and round in an iron bucket with a wooden block, until the coarse crystals of corundum were cleaned of adhering pieces of mica. The bucket was then re-

Jan 1, 1914

By Alexander N. Mitinsky

Up to a certain limit, the increase of pressure on the diamond-drill increases the rate of progress in drilling. That limit is set by the resistance of the diamonds to compression; and beyond it, the destruction of the stones will involve an economic loss, both in time and in money. It is, therefore, important to all diamond-drillers to know what is the resistance mentioned. In Europe, operators usually follow an empirical rule, which directs the maintenance of a pressure, on the area of the bottom of the drilling-tool, of 12 kg. per sq. em. For the tools in ordinary use, this is equivalent to 1 kg. per sq. mm. of the diamonds set in the tool. So far as I know, American drillers are using pressures as high as 50 to 60 kg. per sq. em. of the total area of the drill, and the consumption of diamonds (on Denny's authority, 0.2 carat per meter bored) is greater in America than in Europe. But the reason for this diffrence may be the comparatively larger size of the diamonds commonly used by American drillers. With the assistance of my friend, the late S. Woisslaw, who was the pioneer of diamond-drilling in Russia, I selected from his stock a number of black diamonds, which I subjected in my laboratory to compression-tests, To prepare regular cubes for such tests, as is generally done with other stones, would have been not only costly, but, what is more important, practically useless. I therefore determined, in order to assimilate as nearly as possible the conditions of actual use, to place each sample between a hard plate (corresponding to the rock) and a softer plate (corresponding to the bottom of the tool), into which it would be pressed during the test.

Jan 1, 1907

By D. S. Greig

There was a decline in the Italian oil production in 1933 and also in the footage drilled. A total of about 194,500 bbl. of crude oil was produced in the Emilia district of northern Italy from the same fields in production as in 1932. New drilling to the extent of 80,700 ft. failed to find new production to compensate for the decline in old wells, and no new fields were discovered in spite of an active exploration campaign by the government-owned company A.G.I.P., which has just completed the first year of a five-year exploration program. This company drilled a total of about 33,000 ft. The majority of its tests were drilled in the Po Valley upon locations selected by geophysical methods. This company is changing over to the rotary system for all future wells. It produced about 16,600 bbl. of oil from wells near Salsomaggiore and in the Po Valley. The Petroli d'Italia, which operates the old fields of Montechino, Valleja and Gratera south of Piacenza, has been doing normal development drilling in the endeavor to extend its present fields. Also it was drilling two exploration wells in the Torino district. It drilled a total of about 13,930 ft. and produced approximately 12,645 bbl. of very high-grade oil (specific gravity about 0.765). The Societa Petrolifera Italiana was occupied chiefly in exploratory drilling in the endeavor to extend its producing fields at Salsomaggiore and at Vallezza, south of Parma. It was also drilling one exploration well at Rile dell7Olio near Voghera on the line Milan-Genoa. It drilled a total of 33,849 ft. and obtained a production from its two fields of 165,273 bbl. It also produced 123,220 gal. of casinghead gasoline from Vallezza field absorption plant.

Jan 1, 1934

By J. E. Hanlon, J. D. Wolf

The relaxation peaks observed in plastically deformed materials at low temperatures have been reviewed by sack1 and Niblett and wilks. 2 In particular, the dislocation-relaxation in columbium has received considerable study.3-6 The present work deals with the lower-temperature dislocation-relaxation peak (referred to by Chambers and Schultz as the a peak) in columbium and Cb-5 pct Zr. The columbium and Cb-5 pct Zr specimens were machined to 3/8-in.-diam by 7-in.-long rods from bars hot-extruded at 1200°C. The internal friction and resonant frequency of the samples were measured in torsion at kilocycle frequencies at a maximum strain amplitude of -10-6. The interstitial content of both materials was approximately 70 ppm N and 200 ppm 0. The dislocation-re laxation peaks were measured in the hot-extruded state and after successive anneals. Fig. 1 is a compilation of the data. The resonant frequencies for the columbium and Cb-5 pct Zr samples were, respectively, 5.5 and 6.5 kc. Other workers have noted that the dislocation-relaxation peaks in columbium are not characteristic of a single relaxation time. As can be seen in Fig. 1, the zirconium addition further broadens the spectrum of relaxation times. The magnitude of the modulus defect as computed from resonant-frequency data also reflects this extension. The occurrence of the low-temperature a peak at a position 20°K higher in Cb-5 pct Zr as compared to pure columbium, in the hot-swaged state, suggests a decrease in the average dislocation mobility for the alloy. The authors do not feel that these data are sufficient to permit an interpretation in terms of any detailed models.

Jan 1, 1967

By T. S. Lundy, C. J. McHargue

HE diffusion rate of v48 in single crystals of bee vanadium has been determined at temperatures from 1002° to 1888°C. Standard techniques of lathe sectioning were used for specimens annealed above 1500°C while sectioning by grinding was used for specimens annealed at lower temperatures. As will be seen, the lower-temperature data is enhanced on an Arrhenius-type plot relative to values expected by extrapolation of the high-temperature data. Single crystals were obtained from Linde Co. In Table I the analysis supplied by the vendor is compared with an analysis at Oak Ridge National Laboratory of a sample after a diffusion anneal. The isotope v4' was prepared by the Isotopes Division of Oak Ridge National Laboratory. Proton bombardment of a titanium target in the 86-Inch ORNL Cyclotron was followed by a carrier-free chemical separation. Nineteen specimens, 1/2 in. diam and 3/8 in. long, were cut from the as-received vanadium single crystals. Each specimen was machined with the flat face perpendicular to the longitudinal axis. Specimens were polished through 1/0 emery paper and were etched with 25 pct HF-10 pct H2SO4-10 pct HNO3-55 pct H2O. The polishing and etching steps were repeated until a satisfactory surface finish was achieved. The isotope was electroplated onto the specimens from a neutral solution. Counting rates of the deposited layers were approximately 100 counts per sec. At temperatures above 1200°C specimens were annealed in a tantalum resistance furnace under an argon atmosphere. Temperatures were measured with a Pyro micro-optical pyrometer and a Pt-Pt 10 pct Rh thermocouple. At lower temperatures the specimens were sealed in evacuated quartz ampoules and annealed in Kanthal wire-wound horizontal tube furnaces. A severe reaction occurred at 1200°C between the quartz and the vanadium. This

Jan 1, 1965

By S. L. Sass

DURING an electron microscope study of the w phase in zirconium-base alloys,1 a stereographic technique was devised which allows the synthesis of high energy electron diffraction patterns from a single crystal containing several variants of a second phase. The technique will be described using as an example the w phase which forms in a bcc matrix. The w phase was suggested by Silcock et al.2 and Bagaryatskii et al.3 to have a hexagonal structure with (0001)111(111)^, [001]B//[110]B* *The subscripts B and 1 are used to refer to the bcc phase and one particular orientation of the w phase, respectively. and with cell parameters aw = v2aB, where a^ is the lattice parameter of the bcc struc-ture. Since there are four <lll>B directions there should be four orientations of the w phase. In approaching this problem the question to be answered is, "What reciprocal lattice vectors from the B phase and the four w variants lie in the particular reciprocal lattice plane of interest?" One may restate the question in the form, "What plane normals from the B phase and the four w variants lie in the particular reciprocal lattice plane of interest?" The question is answered and the desired diffraction patterns are plotted using the following stereographic technique. Knowing the cw/aw ratio (=0.613 for the as-quenched form of the w phase), a stereographic projection of plane normals from one w variant can be constructed relative to a cubic projection using the above orientation relations, with the direction of the projection along the [001]B direction, Fig. 1. Let us now synthesize the diffraction pattern observed by looking along

Jan 1, 1970

By W. W. Mullins, F. A. Nichols

Solutions are developed, assuming surface diffusion and both internal and external volume diffusion, for the relaxation of bodies slightly perturbed from spherical and cylindrical geometries. Combined with those previously published for the nearly planar case, these results provide a means of gaging the relative contributions of the two diffusional proc-cesses in any given case. It is shown that in all sintering experiments to date, and probably in any attainable in practice, surface diffusion has played the dominant role, although most previous authors have assumed otherwise. It is also shown that surface diffusion predominates in normal field-emission tip blunting and also for the coalescence of gas bubbles introduced into metals by a bombardment. The surface-diffusion solutions for a perturbed sphere are combined with previous results for volume diffusion to show that the inclusion of interface diffusion permits considerably larger spheres to develop in diffusion-controlled precipitate growth before the onset of instability. A mechanism is also proposed for the spheroidization of precipitate platelets as well as rods. In a previous paper1 the relaxation of a nearly plane surface to flatness by the combined action of the transport processes of viscous flow, evaporation-condensation (in a closed system), volume diffusion, and surface diffusion has been analyzed under the assumption that all surface properties are independent of orientation. In this treatment, criteria were developed for deciding which process predominates, and solutions valid in the latter stages of the sintering of small wires and particles to a plane were obtained. A numerical solution, valid throughout the entire particle-sintering process for the case of surface diffusion, was subsequently obtained by the present authors.&apos; It was found that the analytic solution (which assumed small slopes everywhere) is accurate to within -10 pct when the maximum slope of the profile is less than 0.3; the wire-sintering problem has also been solved nu- merically for the case of surface diffusion and here again the results converge to the analytic small-slope solution at late stages of the process, the two solutions agreeing in this case to within 10 pct when the maximum slope of the profile is less than -0.6. The purpose of this paper is to extend the perturbation solutions to nearly spherical and nearly cylindrical geometries. We treat only the two principal diffusional processes, i.e., surface and volume, but for these geometries we discuss volume diffusion both inside and outside of the solid. Our results, when coupled with Mullins&apos; solutions1 for nearly planar surfaces, provide criteria for gaging the relative contributions of surface and volume diffusion to the over-all transport process in three basic geometries. A very interesting feature in the cylindrical case is the occurrence of instability for longitudinal perturbations with wavelengths greater than the cylindrical circumference, a classical result. This instability of the cylindrical surface is applied to give a quantitative explanation for the often-observed "erratic" pore closure in the late stages of the sintering of wire compacts; also, the theory previously presented for the spheroidization of rod-shaped precipitates by surface (interface) diffusion&apos; is expanded now to include volume diffusion inside and outside of the particle. The results for circumferential perturbations on a long cylinder allow quantitative estimates for gaging the relative importance of surface or volume diffusion in the early stages of the sintering of spheres or wires. The results here demonstrate clearly that surface diffusion has played a very important, if not dominant, role in all sintering experiments discussed in the literature, although the surface-diffusion contribution to the kinetics has usually been ignored. The results for the sphere (surface-diffusion case) are added to the results obtained previously by Mullins and sekerka3 concerning instabilities of a growing spherical precipitate particle (with interface diffusion disallowed) to obtain a general solution to this problem including interface diffusion. The inclusion of interface diffusion is found to increase significantly the range of stability of a growing spherical precipitate for typical metallurgical cases. The following assumptions are made: (i) the initial surface lies everywhere near and has a slope differing only slightly from that of the reference

Jan 1, 1965

By W. A. Nagel, R. P. Alger, H. Sherman, J. Tittmann

A sidewall epithermal neutron tool has been developed to substantially reduce environmental effects that have previously complicated neutron log interpretation. Designed for operation in uncased wells, the device provides increased accuracy in both liquid-filled and empty holes. A brief discussion of neutron moderation, diffusion and capture shows that logs using epithermal neutron detection depend on a smaller number of formation-characterizing parameters than those using thermal neutron or capture gamma ray detection. Thus, they come closer to providing an unambiguorls determination of hydrogen content. In this new device a directionally sensitive epithertnal neutron detection system has been incorporated in a side-wall source-detector skid to minimize borehole effects. The effects of variations in borehole size and shape, mud type, temperature and salinity are greatly reduced. Small residual borehole effects are then computationally accounted for in the surface control panel to provide a borehole-corrected neutron log. The log presents a direct recording of neutron-derived porosity on a linear scale. With corrections for borehole effects already applied, this direct recording of porosity simplifies log interpretation. Furthermore, comparison with a linear porosity presentation of a formation density log permits sandstones, limestones and dolomites to be readily identified. Thus, in complex or variable lithology, porosity is determined with greater accuracy and reliability than heretofore. Laboratory data and field results demonstrate the improvements in neutron logging afforded by this new side-wall epithermal neutron logging device. INTRODUCTION The new Sidewall Neutron Porosity (SNP) logging system, designed for use in uncased wells, provides reliability and accuracy never before achieved with neutron logs. The effects of variations in borehole diameter and shape, fluid salinity, mud weight and temperature—parameters that have long complicated neutron log interpretation— are suppressed or corrected for by this sidewall epithermal neutron detection system. Furthermore, to simplify interpretation the SNP log presents a direct recording of computed porosity on a linear scale. The performance improvements achieved by this new system arise primarily from the combination of two im- portant design features. First. though not unique to this new tool, an epithermal neutron detection system is used,&apos;,&apos; Epithermal neutron detection substantially reduces the perturbing influences of the thermal neutron absorption properties of rock matrices and water salinity. Second, the neutron detection system is mounted in a directionally sensitive sidewall skid to greatly minimize borehole effects. The purpose of this paper is to explain briefy the advantages offered by the detection of epithermal neutrons, to describe the SNP equipment and the log, to present calibration and correction data and to give examples of interpretation methods made especially convenient by this new system. ADVANTAGES OF EPITHERMAL NEUTRON DETECTION Epithermal neutron detection, of all the neutron methods in current commercial use, provides the simplest determination of formation hydrogen content. Advantages of epithermal neutron detectors, as compared with thermal neutron and gamma ray detectors, are probably best explained by a brief review of the life of a source-emitted neutron. A fast neutron from the source will eventually be cap-tured by the nucleus of an atom. However. before capture is likely to occur, the fast neutron (energy of 100,000 electron volts (ev) or more) will be slowed down until it is in thermal equilibrium with its surroundings. The neutron is then considered to be a "thermal" neutron (average energy of 0.025 ev at 25C). The overwhelming majority of the slowing down thus occurs in reaching epithermal energies (energies just above thermal—0.5 to several ev). After reaching thermal energy. the neutron will "diffuse" through the formation with, on the average, no further energy change until capture. Upon the capture of the thermal neutron, relatively high energy gamma rays arc usually emitted. Hydrogen plays a very important role in the process of slowing down fast neutrons. On the other hand, the absorption effects of water salinity and low concentrations of other strong thermal neutron absorbers—relatively unimportant in the moderation process-—are very important in thermal diffusion, capture and the production of gamma rays. Thus, by detecting only epithermal neutrons with the SNP, spurious effects due to these thermal neutron absorbers are greatly minimized as compared to the effects on tools using thermal neutron or gamma ray detectors. The epithermal neutron detection system affords another important advantage. Log response in various litho-

Jan 1, 1967

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.&apos; He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger&apos;s study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By L. E. Tanner

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

Jan 1, 1962

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;&apos;-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.&apos; For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella&apos;s reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.&apos; An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,&apos; however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500&apos; with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

By R. W. Kraft

A back- reflection precession-type X-yay camera for determining the crystallographic orientation of the crystallites of both phases in small areas of thick specimens of polyphase alloys is described ad the geometry, advantages, and limitations of the apparatus are discussed. Metallographic obseg-vations of interfacial angles (or habit planes or growth direction are made on the same specimen so that the crystallographic and metallographzc orientation data call be directly correlated. An example of the application of tile technique to a unidi-~~ectionally solidified CuA12-A1 eutectic specimen is presented. The interfacial planes ad growth directions of each phase were established, and the orientation relationship between the phases was observed and found to be approximately intermediate between two previously reported relationships. The crystallographic interfacial relationship between two solid phases is an important parameter in a variety of metallurgical phenomena because of the energy associated with the interface and because this energy is at least partly associated with the way in which the two space lattices are in contact along the interface. In order to describe the interfacial planes in the crystallites of both phases it is necessary to determine the crystallographic orientation of each phase in a specimen relative to each other, and to directly correlate these data with met-allographic measurements from which the interfacial planes can be determined on the same specimen. The back-reflection Laue technique is the easiest way to determine the orientation of thick single crystals or large grains and the method can be combined with metallographic techniques to provide the necessary data, provided the reflections from each phase can be distinguished from one another. However, if the crystallites are small or of varying orientation or if one or both phases has a unit cell with less than the maximum symmetry, many overlapping and complex Laue patterns are recorded simultaneously and it becomes impractical if not impossible to interpret the photographs. All of these complexities were present in a unidirectionally so- lidified A1-CuA12 eutectic alloy1 for which a crystallographic analysis was desired. Consequently the method described here was developed since no known X-ray or electron diffraction technique had all of the following attributes which were required. 1) Method should yield data from which the crys-tallographic orientation of every crystallite or diffracting unit in the irradiated area can be determined. 2) Method should be adaptable to the study of small areas. Depending upon the degree of preferred orientation in the specimens, it should be possible to obtain reliable data in a reasonable length of time on irradiated areas as small as 1.0 or even 0.1 mm in diam. 3) Method should permit direct correlation of crystallographic data with microscopic orientation data pertaining to crystallite axes, habit, morphology, and growth directions as determined by optical microscopy. 4) method should be such that selected areas of large specimens can be easily studied. Trepanning of a small specimen (such as an electron microscope specimen) from larger specimens was undesirable since it would greatly increase the problem of correlating the crystallographic and microscopic directional data. Requirements 3 and 4 dictated that an X-ray back-reflection pinhole technique should be used on large samples, such as metallographic specimens which had previously been examined and analyzed for their microscopic characteristics. Similarly, requirement 2 could be satisfied by choosing a collimator of appropriately small diameter. Exposure times would not be excessive provided the detector were close enough to the specimen. Because of space limitations film was chosen in preference to a Geiger counter. Requirement 1 was fulfilled by using monochromatic radiation and providing enough additional degrees of freedom in specimen rotation to compensate for Bragg law restrictions on diffracted beams. DESCRIPTION OF APPARATUS The apparatus shown in Fig. 1 consists of a pin-hole collimator, (a), projecting through a rotatable circular film in a holder, (b), which records X-ray reflections in the back-reflection region. The specimen, (c), is mounted on the end of a shaft, (d), which is provided with an adjustment, (e), so that the specimen surface can be placed accurately on

Jan 1, 1962

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer&apos;s data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW&apos; determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965