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By G. A. Mancini, V. Bharucha, J. W. Spretnak, G. W. Powell

The characteristics of the motion of the a interface during the "down" transformation was studied in zone-refined iron and dilute binary alloys containing nickel and molybdenum by means of the thermionic emission microscope and high speed photography. The frontal movements were found in all cases to be definitely discontinuous with time and an appreciable number of incremental jumps were found to proceed in the reverse direction (a to b). Molybdenum was found to be particularly effective in increasing the frequency of the increments of transformation from the stable to the metastable phase. A knowledge of the mechanism by which alloying elements affect the hardenability of a steel is desirable from both the practical and scientific viewpoints. It is well established that microstructures consisting of tempered martensite and lower bainite exhibit the best performance in terms of toughness and resistance to crack propagation. The presence of some upper transformation products, namely ferrite and pearlite, is in general undesirable. Various researches have indicated that the ferrite matrix grain structure is a very important difference between the upper and lower transformation products, namely equi-axed vs acicular. Any comprehensive theory of the decomposition of austenite should explain the dependency of the morphology of the matrix on undercooling. The contribution of various alloying elements to hardenability has been determined experimentally and catalogued in considerable detail. A rationalization of the basic mechanism or mechanisms by which individual elements affect the kinetics of the decomposition of austenite to products other than the phase "martensite" has not been evolved as yet. Interest in this problem was stimulated by the effects of minute quantities of boron in hardenable steels. This paper deals with one aspect of this problem, namely the characteristics of the ?-a transformation in high-purity iron and in two carbon-free iron binary alloys. A detailed historical account of the scientific developments in the study of the decomposition of austenite would be a prodigious undertaking and will not be attempted here. There are several excellent reviews in the literature on the formation of pearlite, martensitic reactions, and kinetics of solid-state reactions. The thinking on reaction mechanisms has been influenced to a large degree by the "classical" Tammann nucleation and growth model, in which an embryo springs into being by a fluctuation, and grows to a critical size through atom by atom deposition. Such a process is expected, accordingly, to be diffusion controlled. Considerable research attempting to relate the contribution of alloying elements to hardenability on the basis of their effect on the diffusivity of carbon in iron has not been productive from a mechanistic viewpoint. The formation of pearlite and ferrite has been treated in terms of nucleation and growth processes in which presumably the lattice transformation also occurs by a diffusion process. The other prominently considered mechanism is the "martensitic" or cooperative shearing mechanism. It seems generally, but not entirely, agreed that the phase "martensite" forms by this mechanism, and that it is involved to some extent in

Jan 1, 1962

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By R. F. Hehemann, R. H. Goodenow

Thermal arrest, hot-stage microscopy, and transtnission electron microscopy techniques have been employed to study the transformations in low-carbon iron and Fe-9 pct Ni alloys. In continuous cooling experiments, each alloy transforms at an essentially constant temperature for cooling rates below the critical rate required for martensite formation. However, high-tenzperature transformation in pure iron takes place by a different mechanism than that in the 9 pct Ni alloys. Pure iron exhibits an equi-a a structure with a low and random dislocation density while the 9 pct Ni alloy exhibits a cell or lathlike substructure analogous to that of low-carbon martensite. This same substructure characterizes upper bainite in higher-carbon inaterials. UNTIL relatively recently, diffusionless transformations have been considered to take place by the same mechanism and have been termed mar-tensitic transformations.l-3 The most characteristic feature2 of this mode of transformation is the shape change produced by a shear deformation and growth of the product phase frequently occurs at an extremely high velocity approaching that of an elastic wave.4'5 A different mechanism of diffusionless transformation was recognized first in Cu-Ga and other copper-base alloys.6,7 From the absence of surface tilting in these alloys, it has been concluded that transformation is not accomplished by the cooperative shear displacements that occur in mar-tensitic reactions. Transformation presumably takes place by the rapid movement of an incoherent interface which is capable of propagating across parent grain boundaries. Although the transformation is diffusionless in the macroscopic sense, advancement of these interfaces is accomplished by an atom by atom rearrangement. Transformations of this type therefore require thermal activation and are generally operative only at high temperature. Although requiring short-range diffusion at the interface, propagation still occurs so rapidly that the reaction cannot be suppressed with normal cooling rates.7 The resulting microstructures exhibit large, irregular-shaped regions of the product phase, which are essentially free of crystallographic features. Consequently, these reactions have been termed massive transformations. Transformation by the massive mechanism has been reported to occur in ferrous systems involving pure iron and binary alloys of iron with nickel, chromium, and silicon by Gilbert and owen.' The Fe-Ni system is of special interest in that the massive transformation was observed in alloys with less than 15 pct Ni while alloys having more than about 28 pct Ni transformed by the conventional mar-tensitic mechanism. By employing cooling rates substantially higher than those used by Gilbert and Owen, Swanson and Parr have been able to suppress the massive transformation in alloys with 0 to 10 pct Ni9 and produce martensite as revealed by surface relief. The massive transformation in the alloys having less than 15 pct Ni was identified by the lack of surface relief and an irregular rather than clearly acicular microstructure.' Speich and Swann, using thin-foil electron microscopy, identified three distinctly different structures10 in quenched binary Fe-Ni alloys. From 0 to 4 pct Ni the structure consisted of blocky grains of a with a low and random dislocation density. Alloys with 4 to 25 pct Ni exhibited a cell structure with a high dislocation density; and at greater than 25 pct Ni the structure consisted of internally twinned plates. The structural change at approximately 4 pct Ni suggests that alloys with low nickel content transform by a different mechanism than those with intermediate nickel contents and the transition from the cellular to the internally twinned structures at approximately 25 pct Ni is analogous to the transition from needles to internally twinned plates that occurs over a narrow range of carbon contents in Fe-C martensites.11,12 Conventional bainitic and martensitic modes of austenite decomposition operate in ternary Fe-C-Ni alloys having less than 10 pct Ni. This investigation was conducted in order to explore the conditions under which the massive, bainitic, and martensitic transformations occur and the relationships between these modes of decomposition.

Jan 1, 1965

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By J. Nutting, J. W. Cahn

WITH the development of thin film techniques for the direct examination of metals in the electron microscope some new problems in quantitative metallography have become apparent. In order to obtain certain contrast effects in the electron optical image when examining thin films from alloys containing dispersed phases, it is essential to use films of a thickness at least two or three times greater than that of the mean particle diameter of the dispersed phase. From micrographs of such specimens it may be desired to obtain the volume fraction of the dispersed phase and the number of particles of the phase in a unit volume of the matrix. Under these conditions the particles sectioned by

Jan 1, 1960

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By H. K. Birnbaum

The termination of a twin lamella in the interior of a crystal requires accommodation of the strains at the tip of the twin which result from coherency of the twin and matrix. In zinc and magnesium crystals,

Jan 1, 1960

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962

By Robert E. Green, Robert A. Swanson

Ultrasonic attenuation and stress were measured simultaneously as a function of strain for aluminum single crystals tested in compression. The propagation mode and polarization of the ultrasonic waves were chosen with reference to the theoretical analysis presented in Part I. Good experimental agreement was found with this theory and with earlier experimental work in tensile tests. Support is given to the contention that ultrasonic -attenuation measurements are much more sensitive to the early stages of plastic deformation than are conventional stress -strain measurements. Dislocation meclzanisms are suggested which are compatible with both the present and the earlier experimental observations. A brief historical introduction of previous work concerned with the study of dislocation motion by ultrasonic-attenuation measurements has been given in Part I. The purpose of the present experimental investigation was to make use of the theoretical considerations from Part I in order to gain further knowledge concerning dislocation motions during plastic deformation. Emphasis was placed on the choice of propagation modes and polarization of the waves, such that interactions between these waves and dislocation movement on a specific slip system could be investigated. EXPERIMENTAL PROCEDURE Since the primary concern of this investigation was dislocation damping, other sources of damping were eliminated as much as possible. The test specimens were 0.5-in.-diam single crystals of 99.99+ pct pure aluminum grown from the melt by a modified Bridgman technique. Ultrasonic-attenuation measurements were made at a frequency of 10 megacycles per sec using a Style 56A001 Ultrasonic Attenuation Comparator manufactured by Sperry Products Inc. after a design by Chick, An- derson, and Truell.1 At this frequency the particle vibrations are essentially adiabatic and thermo-elastic damping should be absent. This frequency was selected since it was one of the frequencies used by Hikata et al.2 n conjunction with tensile tests on aluminum crystals, thus allowing direct comparison with this work. The use of quartz-crystal transducers insures that the amplitude of vibration is not sufficient to cause the break away of the dislocation loops from weak pinning points. The quartz-crystal transducers used all possessed a resonance frequency of 10 megacycles per sec and were thin circular discs 0.375 in. in diameter. X-cut crystals were used to generate the longitudinal waves and AC-cut crystals to generate the transverse waves. Aluminum was chosen as the basic material because it is a typical fcc metal whose deformation behavior is well-known and because the most recent work at the time the present research was initiated was that by Hikata et al. who used aluminum. The present tests were run in compression to see if such tests could be satisfactorily run in compression without being severely masked by grip effects.. A second reason was to compare the results in compression with those of the tension experiments of Hikata et at. Finally, shorter specimens could be run in compression with less over-all damping than in tension. All of the aluminum-crystal test specimens used were oriented for plastic deformation by single slip; i.e., they possessed the orientation having a maximum Schmid factor of 0.5. Because of the well-known time dependence 3 of plastic strain at constant stress, the test specimens were subjected to a quasi-static loading. Previous investigations4-&apos; have indicated that attenuation after plastic deformation is also time-dependent, so any continuous loading of the specimen would show that changes in attenuation were also a function of strain rate. By loading the specimen to a given stress level and holding it constant until the recovery process was essentially complete, the time dependence was eliminated. The quartz transducer was permanently bonded to the aluminum crystal using Eastman 910 cement. Excess cement was removed from around the quartz with DMF (dimethyl formamide). Eastman 910 was found to be far superior for bonding, especially with regard to the shear-wave transducer, since it formed a solid bond which readily supports shear-wave propagation. The solid bond formed by the Eastman 910 cement also insured that the quartz

Jan 1, 1964

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By C. S. Smith, Chih-Chung Wang

D. Turnbull—In the opinion of the writer the most interesting result described in this paper is that the distribution of tin with respect to solidification temperature has several fairly well-defined maxima. It appears that each peak may be associated with a catalytic impurity of some rather specific composition. Recently we have obtained some additional evidence in favor of this viewpoint in experiments on the supercooling of lead droplets coated with different surface films. The distribution of lead droplets, ostensibly coated with lead sulphate, with respect to solidification temperature exhibited two distinct and reproducible maxima, one at 20" supercooling and the other at 47". On the other hand, when the droplets were ostensibly coated with halide films, no solidification was perceptible until the aggregate was supercooled more than 55". Upon further cooling a single well-defined peak centering at 60" supercooling was observed. Since the particle size distribution was the same in these two sets of experiments it appears that the most reasonable interpretation of the results is that the sulphate surface film or its reaction products with lead are much more effective in catalyzing the nucleation of lead crystals than are lead halide films. C. S. Smith (authors&apos; reply)—Dr. Turnbull&apos;s experiments with lead drops coated with various surface films are most interesting. However, before drawing conclusions from the cooling curves described in the paper as to the existence of a few nucleus types effective at a few different temperatures, one must consider the state of subdivision of the liquid metal. In the A1-Sn alloy used, the tin was not in uniform droplets but tended to collect in three distinct shapes—in long interconnecting prisms along grain edges, in somewhat elongated interdendritic branching pools. and in isolated droplets. A single nucleus will solidify only the metal in contact with it, and the heat evolved will be proportional to the connected volume. A uniform distribution of nuclei of random effectiveness in such an alloy will cause peaks on the specific heat curve on cooling, which correspond to the volume distribution of tin and tell nothing about the nucleus type. In any real alloy both effects will be combined, and it seems impossible at present to distinguish between them. M. B. Bever—The thesis of this interesting paper is supported by a combination of positive and negative evidence. The authors have shown that under certain conditions a liquid phase may undercool, if it is dispersed in a thoroughly discontinuous manner throughout a solid matrix. They also found that undercooling

Jan 1, 1951

By L. D. Jaffe, D. C. Buffum

EARLIER the authors and coworkers had pre sented data on isothermal temper embrittlement of an SAE 3140 steel?&apos; In that work, however, attention was concentrated on embrittlement at 575°C and below. Preliminary measurements showed that embrittlement at 675 °C was much mote rapid than would be expected from the data at the lower temperatures: and indicated the need for further work above 575°C. The possibility of an upper nose in the time-temperature embrittlement diagram above 575°C was pointed out. Procedure The same heat of SAE 3140 steel was used as in the previous work, and experimental methods were the same. All blanks were austenitized 1 hr at 900°C and water, quenched. Groups were then tempered 1 hr at 675"C, water quenched, and given embrittling treatments for times of 5 min to 240 hr at 675" to 600 °C, as shown in Table I. Other groups, after the temper and quench, were embrittled 48 to 1440 hr at 550°C. Another series was tempered 240 hr at 675"C, quenched, and held for various times at 650" to 375°C (Table 11). For comparison, a series was tempered for these same times at 700°, 675", and 650°C (Table 111). The Ae, temperature for this heat of steel had been determined as approximately 690°C;1*a the treatments at 700°C were introduced to determine the effects of tempering in a range where a little austenite would fonn. A large number of other treatments, involving holding at two temperatures in succession after the temper, and occasionally slow cooling or heating, were also studied. These treatments are listed in the tables. Austenitizing was done in air; all subsequent treatments were in salt. Blanks were always water quenched after the last treatment. The heat-treated blanks were machined to standard V-notch Charpy specimens. A transition curve for each group was obtained by breaking the specimens at various temperatures on a 217 ft-lb impact machine having a striking velocity of 16.8 fps, and plotting the observed percentage of fibrous fracture vs the test temperature. From this plot, the transition temperature was taken as the lowest temperature at which the fracture appeared 100 pct fibrous; its accuracy is estimated as +5"C. Generally, hardness was measured on every bar. Since a decrease in hardness itself seems to decrease the transition temperature somewhat, a correctiona of —0.28"C per Bhn was applied to permit comparison of the transition temperatures on a uniform basis of 24 Rc. The transition temperature and hardness results are given in Tables I through VI. Where overlap of earlier work1.&apos; occurred, data were combined.

Jan 1, 1958

By Leslie Burris, J. C. Hesson

The diffusivity of uranium in liquid cadmium has been measured as a function of temperature by the capillary -bath technique. The diffusivity measurements were made at 4509 500°, 575º, and 650°C, over which temperature range the diffusivity of uranium varied from 1.3 to 2.3 x 10-5 sq cm per sec. The diffusivity of uranium in cadmium was less than that predicted by the Einstein-Stokes equation. VERY little information is available on the diffusivity of uranium in liquid metals. Bonillal has reported a single measurement of the diffusivity of uranium in bismuth. Measurement of the diffusivity of uranium in cadmium was undertaken, not only to supply data in an area in which a dearth of information exists, but also because of a need for this physical property measurement in connection with mass transfer studies now underway in the U-Cd system at Argonne National Laboratory. The capillary-bath method used in this work has been successfully used by other workers2"4 to obtain diffusivities in liquid metal systems. Although considerable experimental technique is required to obtain reliable diffusivity measurements, the basic information required is only that of temperature, capillary tube length, the initial and final compositions of the alloy in the capillary tube, and the composition of the bath into which the solute element is diffusing. From these measurements, diffusivities may be calculated using Fick&apos;s law. The diffusivity equations are presented in the Appendix. Equations which are often used to predict diffusivities in dilute solutions5 are the Einstein-Stokes equation: D= (kT)/(6pµr) and the Eyring equation: D = (?,kT/?y?zp), where D= diffusivity (sq cm per sec), k = Boltzman&apos;s constant, T= temperature ("K), p = viscosity (poises), r = radius of diffusing molecule or species (cm), and A,, Ay, and A, are the diameters of the diffusing molecule in the three axial directions. For round molecules, the Eyring equation gives values which are 37r times larger than the Einstein-Stokes equation. In this work, the experimental values were compared to the Einstein-Stokes equation. Experimental values of diffusivities in liquid metal systems usually lie between those predicted by the Einstein-Stokes and Eyring equations. The viscosity values for cadmium were obtained from the Liquid Metals Handbook.6 EXPERIMENTAL APPARATUS AND PROCEDURE The general procedure employed consisted of rapidly immersing in a molten cadmium bath containing a negligible amount of uranium a capillary

Jan 1, 1963

By A. H. Daane, A. S. Wilson

The U-Cr system is of the simple eutectic type with some solid solubility of chromium in r and ß uranium. The eutectic occurs at 20 atomic pet Cr and melts at 859°C. The maximum solubility of chromium in y uranium is 4 atomic pet at the eutectic temperature, and in ß uranium the solubility is estimated to be 1 atomic pet. y-ß and ß-a transformations were found to occur at 737°estimatedt° and 612°C respectively. DURING 1944 and 1945, the U-Cr constitution diagram was studied in this laboratory as a part of a research program on uranium metallurgy in the Manhattan Project, and the work was described in a Manhattan Project report issued in December 1945. This paper is based on that report, which has been declassified. Prior to this study, it had been shown by other Manhattan Project workers that the low Cr-U alloys could be quenched to retain the form of uranium. Experimental The uranium used in this work was massive metal prepared in this laboratory and contained less than 0.1 pct of other elements. The chromium was 200 mesh powder obtained from the A. D. McKay Co. and was found on analysis to be 99.5 pct Cr with 0.3 pct Fe the major impurity. Alloys, weighing 400 to 600 g, were prepared by induction heating the components to 1700°C in slip-cast ZrO, crucibles in a vacuum of 3x103 mm Hg. TO prevent too violent agitation of the melt by the induction field with subsequent crucible breakage and sample loss, the ZrO2 crucible was placed in a graphite crucible, which was surrounded by a layer of powdered carbon insulation 2 to 3 cm thick. Polished vertical sections of the alloys were examined microscopically to confirm their homogeneity. Heating and cooling curves were taken on the alloys by reheating them in ZrO, crucibles to 1200°C and inserting a mullite-protected chromel-alumel thermocouple into the melt by means of a slip seal in the vacuum head of the furnace. A recording potentiometer traced the curves which had a slope of from 3" to 6" per min. Samples of the alloys were prepared for metallo-graphic examination by conventional mechanical polishing techniques followed by an electrolytic polish in an ethylene glycol-phosphoric acid-ethyl alcohol bath. The structure of the alloys was brought out clearly by this procedure so that no further etching was required. Samples for chemical analysis were taken from drillings from the top, center, and bottom sections of the alloys. The uranium was determined by titra-tion with Ce(SO1)2, while the chromium was titrated with FeSO,; the uranium and chromium totaled at least 99.6 pct in all of the alloys prepared. X-ray samples were prepared by filing bulk specimens in a helium-filled glove box and annealing the resulting powder in a zirconium-gettered helium atmosphere. A 114.6 mm diam Debye-Scherrer camera and a Weyland nonsymmetrical self-focusing camera were used with filtered copper radiation to obtain the powder X-ray diffraction data. Results The data obtained in this study have been combined to construct the constitution diagram of the U-Cr system shown in Fig. 1 where the arrests observed in cooling curves are indicated by dots. The liquidus arrest was quite distinct in thermal data taken on alloys in the range 0 to 20 atomic pct Cr. The eutectic arrest was not observed in studies on the 2.5 and 4.5 pct Cr samples but appeared in the 7.5 pct samples, which suggested some solubility of chromium in y uranium. On quenching from 859 °C, the 2.5 pct sample showed but one phase while the 4.5 pct sample contained a small amount of the eutectic along the grain boundaries; see Figs. 2 and 3. From this the maximum solubility of chromium in r uranium has been set at 4 pct. X-ray studies on these samples showed that the r phase was not retained at room temperature by quenching, but in each case a pattern was observed .which has been identified with the ß phase of uranium. Thermal data show the y-ß transformation of uranium lowered to 737°C as a consequence of this solubility. On quenching from the ß range (660°C), precipitation of chromium in the primary uranium is observed in the 2.5 and 4.5 pct Cr samples (see Figs. 4 and 5),

Jan 1, 1956

By A. Kaufmann, B. Cullity, G. Bitsianes

T0 determine the bulk of the phase diagram, techniques for melting, thermal analysis, heat treatment, metallography, and X-ray diffraction that have already been described were used.&apos; It proved difficult to get definitive results for most of the alloy system because of the large number of compounds, their high melting points, and their extreme brittle-ness which made metallography difficult. The final phase diagram, essentially as shown in Fig. 1, was issued with considerable trepidation.&apos; The phase relationships at the two ends of the system were defined with satisfactory accuracy. In the central region between U,Si, and USi, there was great uncertainty concerning the melting points and even the composition of the compounds. At the uranium end of the system, it is quite clear that a eutectic exists at about 985 °C and approximately 8 or 9 atomic pct Si. The a-to-8 transformation is not appreciably altered by silicon, but the 8-to-y transformation is raised to about 795°C. There is appreciable solid solubility in y-uranium, as demonstrated by the micrographs of Fig. 2. The occurrence of the E phase was not suspected at first, since the alloys as melted and furnace cooled gave no X-ray diffraction or thermal arrest indication of it. However, suitable metallography revealed a rim around each of the compound particles as shown in Fig. 3. Heat treatment above 600°C revealed that the rim was another phase which formed by peritectoid reaction between uranium and U,Si,. This reaction proceeds slowly and it is difficult to get it to go to completion. Consequently, there is some uncertainty concerning the exact composition of P and the exact peritectoid temperature. On the basis of various metallurgical studies, it was decided that the most probable composition for t was about 23 atomic pct Si. Metallographic examination shows the closest approach to a single phase at this composition. Likewise, density and hardness measurements of heat-treated alloys shown in Figs. 9 and 10 show a change in slope at 23 pct Si. This is revealed most clearly by plotting the difference in hardness or density between chill-cast and heat- treated alloys as shown in Fig. 4. Zachariasen2 was able to index the diffraction lines of P and to determine the arrangement of the atoms in the unit cell. He concluded that the composition must be US. However, it is felt that the metallurgical studies are reliable and that Zachariasen&apos;s X-ray work does not furnish positive proof that the P phase exists exactly at the stoichiometric composition U3Si. There are many instances in alloy systems where a phase does not occur at the composition dictated by the molecular structure. It is possible that the chemical analyses used in the present work were subject to some systematic error. This seems unlikely, however, since recent work in several laboratories seems to show excess compound at 25 atomic pct Si.

Jan 1, 1958

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.&apos; In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/&apos; in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about &apos;/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955