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By J. S. Kirkaldy, G. R. Purdy

THE formation of ferrite in supersaturated aus-tenite has been the subject of considerable speculation and investigation. Aaronson has recently reviewed the data pertinent to this reaction.' Since these data in all cases refer to ternary or high-order alloys it is not possible to put them to the test of simple binary diffusion formalism. It has not, therefore, been possible to make a certain statement as to the controlling mechanisms in the process. An assessment of the difficulties inherent in the conventional statistical metallographic approach suggested that a study of the problem by means of a macroscopic two-phase diffusion couple might contribute useful information. Accordingly, such a couple was synthesized, and the rate of motion of a ferrite-austenite phase boundary (the growth of an austenite layer at the expense of a ferrite layer) was determined. Wagner originally produced a diffusion solution applicable to the motion of a planar phase interface in a binary diffusion couple, assuming local equilibrium throughout the diffusion zone. This solution, which is stated free of typographical error* in Ref. where a is the position of the interface in A space (A = x/fi), C; and CL1 are the equilibrium inter-facial concentrations in phases I and 11, C: and C*1 are the initial bulk concentrations in phases I and 11, and & and are diffusion coefficients (assumed constant). If a diffusion couple consisting of homogeneous layers of ferrite and austenite in equilibrium is raised to a higher temperature, the austenite layer will grow at the expense of the ferrite. Provided that the thickness of the ferrite layer is much less than the diffusion length of carbon in ferrite, we can set , so that Wagner's solution reduces to

Jan 1, 1963

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By Jack Washburn, E. R. Parker

Kinking in zinc single-crystal tension specimens was observed under conditions of low stress and high temperature. Kinking is discussed in relation to other plastic bending phenomena on the basis of dislocation theory. Experiments on the stress-induced motion of small angle boundaries are reported. KINKING was first reported by Orowan1 as a new deformation mechanism. He observed the phenomenon in cadmium single crystals loaded in compression. Glide lamellae in a local region of the rod were observed to snap over suddenly to a tilted position, resulting in a sudden shortening of the specimen. Between the tilted portion and the rest of the crystal there were fairly sharp boundaries, with the slip plane assuming approximately mirror image positions on opposite sides of these boundaries. Orowan considered the boundaries to be regions where dislocations had concentrated. Hess and Barrett' observed the formation of kinks in critically oriented zinc compression specimens. It was found that the sudden snapping over of the tilted region was not an essential part of the kinking phenomenon but rather was associated with the method of loading. Kinking was explained on the basis of the accepted mechanisms of slip and flexural glide. It was also suggested that a kink can be considered as a special type of deformation band. During a recent investigation of the effect of surface condition on creep of zinc single crystals," a similar phenomenon was observed in crystals which were loaded in tension. The specimens were 0.4 in. diam cylindrical rods with a free length of 4 in. between end connections. All of the crystals were tested at a constant load. adjusted to give an extension rate of approximately 0.05 pct per hr. Kinking, as shown in Fig. 1, occurred in some of the tests performed at temperatures above 200°C. Kinking was observed in specimens varying widely in initial orientation, scattering about a 45" angle between the slip plane and the specimen axis. The condition leading to kinking in tension appeared to be non-uniform distribution of flow along the gage length combined with the restraint imposed by the tensile load. At low temperatures and fast strain rates, the distribution of strain throughout the midsection of tension specimens was generally quite uniform; therefore, bend planes developed only near the ends as described by Miller.4 However, at high temperatures under creep conditions it was difficult to obtain specimens in which the distribution of flow was uniform. Some of the factors which may have caused differences in flow stress along the length of the crystals are: Nonuniform distribution of impurities, accidents of growth (lineage structure), slight bending or other damage during handling, surface conditions, and strain-aging characteristics due to dissolved nitrogen." Plastic flow, once started in a local region, often continued to a relatively large strain before other parts of the gage length became active. Under these conditions a series of kinks, such as those in Fig. 1, were produced. Fig. 2 illustrates how a nonuniform distribution of slip produces bending moments which- are responsible for kink formation. If no plastic bending were to occur while the rod extended by pure slip in two separate sections of the rod, it would assume a shape such as that in Fig. 2a. A specimen having this shape and being subjected to a tension load would have concentrations of stress at the concave surfaces C and lower than average stress would exist at the convex surfaces D. Therefore a bending moment is superimposed on the average stress in the regions between C and D. The positions of potential bend planes under these conditions are shown as dotted lines. Actually no such shape as Fig. 2a develops because plastic bending in the region C-D occurs simultaneously with pure slip in the intervening regions. The observed structure of a tension kink is indicated by Fig. 2b. Perhaps the best approach to an understanding of kinking as well as other related plastic bending phenomena, such as the bend planes discussed by Miller,' cell formation studied by Wood et al.,6 and polygonization,7 is consideration of the dislocation model of a bent lattice. Current theories of the slip process postulate generation or multiplication of dislocations at certain lattice imperfections. The mechanism proposed by Frank and Read8 results in continuous generation of concentric dislocation loops which spread out

Jan 1, 1953

By S. S. Cole, D. L. Armant

The smelting of titaniferous ores for the past hundred years has not been successful because of thickening of the slags in the furnaces. The interest in the utilization of these iron bearing materials has been due to the extensive deposits which have been found in various parts of the world.1 The literature contains references2 to the use of titaniferous ores in blast furnaces. None of these attempts has met with success due to the lack of sufficient information as to the cause of failures and to economic considerations. Evaluation of the published information, as to the probable cause of failure in various attempts, has indicated that the presence of lower valence titanium oxide and formation of titanium carbide contributed to the failure. It was apparent that severe reducing conditions which are present in a blast furnace had been one of the factors for such failures. The previous smelting operations had as a primary objective the recovery of iron from these ores. Under these conditions the highest recovery of iron could only occur with severe reducing conditions. Application of Melting Point Data The application of the melting point data, from the system CaO-MgO-Al2O3-TiO2 reported in another paper,3 to the smelting of titaniferous ores required an extrapolation of these melting points due to the presence of other impurities from the ores. Likewise, a study of the effect of varying FeO and reduced titanium content of the slag was necessary before the data could be fully applied. The melting point data under oxidizing conditions had clearly indicated that a fluid slag with a melting point in the temperature range of 1370°C could be obtained. The smelting of a titaniferous ore had as a primary objective the production of a high titanium slag which was fluid and substantially free of iron and low in trivalent titanium. Since production of a high titanium slag was of primary importance, rather than the recovery of iron from these ores, the smelting concept could be altered to a marked degree. The ferrous oxide could be maintained at higher levels than is the normal practice in iron ores slags without being detrimental to the slags, although a loss in iron recovery resulted. During the reduction of the molten mixtures of ferrous iron and titanium, carbon acts as the reductant for changing the valence of the titanium and iron. The reaction can go further than in the case of the reduction which occurs in iron-titanium solutions. The formation of metallic iron removes iron from the system, so that the titanium oxide can be reduced to trivalent and divalent titanium oxides and also form titanium carbide which removes the titanium from the slags as a soluble constituent. The problem, therefore, resolves itself into maintaining the proper amount of ferrous iron in the slag thereby avoiding the formation of appreciable amounts of trivalent titanium and no divalent titanium oxide or titanium carbide. The latter two have been found in the viscous

Jan 1, 1950

By K. A. Jackson, G. A. Chadwick, A. Klugert

The diffusion field ahead of a lamellar interfnce is analyzed using an electrical analog. A self-consistent solution is obtained for the shape of the interfnce and the diffusion field by an iterative process. The solutions presented here are for a 50-50 eutectoid or eutectic, The shape of the interface is found to he independent of growth velocity and lamellar spacing, and to depend on the relative values of interfacial free energies at the phase houndaries . The mode of growth of lamellar eutectics and eutectoids has been a subject of much interest for many years.1-4 Mehl and Hagel 1 have shown photomicrographs taken by Tardif when he attempted to determine experimentally the shape of an advancing pearlite interface; the results are completely ambiguous. Brandt' and schei13 have made approximate calculations of the composition ahead of a lamellar growth front. The shape of the advancing front and the composition distribution ahead of the front are difficult to calculate because one depends on the other. It is the purpose of the present paper to describe a method by which this calculation has been done. Lamellar-eutectic growth usually occurs under conditions where the growth is fairly rapid, and the interface temperature is close to the eutectic temperature. The growth rate is usually determined by heat flow. Eutectoid growth, on the other hand, can best be studied by quenching to some temperature, and allowing growth to proceed isother-mally. In both cases the growth is believed to be controlled by diffusion* rather than by the atomic kinetics of the transformation. This being the case, a single treatment of the diffusion equation will apply to both cases, provided the region of the interface in a eutectic may be considered to be isothermal. If a part of the interface could appreciably change its thermodynamic driving force by advancing ahead of or lagging behind the mean interface, then the two cases would not be similar. Eutectics normally grow in temperature gradients of the or-der of a few degrees per centimeter. The normal eutectic spacing is the order of a few microns. Part of the interface would have to extend many lamellar spacings ahead of the mean interface before it experienced sensibly different conditions. The interface temperature is usually a few tenths of a degree below the eutectic temperature so that temperature differences of the order of one-thousandths of a degree (a displacement of one lamellar spacing) would be unimportant. Protrusions large compared to the mean spacing do occur when one phase only grows into a eutectic liquid. This is usually a dendritic type of growth, and easily distinguishable from the lamellar mode of growth. A single treatment of lamellar growth will apply equally well to both eutectic and eutectoid decomposition. At the interface, which as shown above is essentially isothermal, the difference between the equilibrium eutectic temperature Teu and the actual interface temperature Ti, can be divided into two parts: 1) the composition varies across the interface, so that the local equilibrium temperature is not Teu; and 2) the interface is curved, so that the local equilibrium temperature is depressed according to the Gibbs-Thompson relationship. This undercooling can be written as Teu-Ti =?T = mAC(x) + a/r(x) [1] where ?C(X) is the departure of the composition at a point x on the interface from the eutectic composition, see Fig. 1, r(x) is the local radius of curvature at a point x on the interface, m is the slope of the liquidus line on the phase diagram, and a is a constant given by where s is the interfacial free energy, TE is the equilibrium temperature, and L is the latent heat of fusion. The calculations in this paper will be made only for the case where the phase diagram is symmetric, that is, the eutectic occurs at 50 pct, the liquidi have the same magnitude slope m at the eutectic temperature, and C,, the amount of B rejected when unit volume of a freezes, see Fig. 2(a), is the same for both phases. As shown in Fig. 2(b), the composition ahead of the a phase will be rich in B, the composition ahead of the ß phase will be rich in A. The composition at the phase boundary is the eutectic composition. The difference between the local liquidus temperature and the actual tempera-

Jan 1, 1964

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,' the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*' specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955

By C. E. Armantrout, J. A. Rowland, D. F. Walsh

THE close-packed-hexagonal structure of mag-J- nesium is converted to a ductile and malleable body-centered-cubic lattice by the addition of lithium in excess of 10 pct. Further, the density of magnesium or magnesium-base alloys is decreased by additions of lithium. The practical possibilities of such alloys as a basis for uniquely light, malleable, and ductile structural materials were pointed out by Dean in 1944' and by Hume-Rothery in 1945.2 It was apparent to these investigators, however, that more complex compositions would be required if strengths sufficient for structural applications were to be developed in these alloys. In a search for strengthening additions, various investigators w have examined a number of the ternary and more complex alloys containing magnesium and lithium. An investigation of the fundamental characteristics of these alloys was undertaken by the Bureau of Mines. The investigation was initiated with a study of the magnesium-rich corner of the equilibrium diagram for the ternary system, Mg-Li-Al. The following data from published investigations of Mg-Li-A1 alloys were available: 1—a description of isothermal sections at 20" and 400°C through the Mg-Li-A1 constitution diagram by F. I. Shamrai;' 2—a diagram by P. D. Frost et al." showing approximate phase relationships at 700°F for a number of the Mg-Li-A1 alloys; and 3—diagrams showing the constitution at 500" and 700°F for the Mg-Li-A1 alloy system published by A. Jones et al.' Where compositions and temperatures permit comparison, these diagrams show disagreement. The 700°F isotherms of Frost and Jones differ only in the placement of the phase boundaries. But Sham-rai's 400°C (752°F) isotherm shows a variation in phases as well as in phase boundaries. Although rigid comparison of these different isothermal sections might not be justifiable, it seems impossible to reconcile Shamrai's construction with the isotherms of Frost or Jones. The isothermal sections presented in this paper were prepared to determine compositions which might be suitable for age hardening and to develop the general slope and placement of the various phase boundaries in the magnesium-rich corner of the diagram. Sections at 375", 200°, and 100°C were selected for investigation. In constructing these sections, the solubility of aluminum in magnesium, as reported by W. L. Fink and L. A. Willey Vn 1948, was used at the binary Mg-A1 boundary and the solubility of lithium in magnesium was obtained from the equilibrium diagram for that system as reported by G. F. Sager and B. J. Nelson" in the same year. The solubility of magnesium in lithium was determined experimentally and conforms in general to data reported by P. Saldau and F. Shamrai." Parameters for AlLi and MgI7A1, were taken from American Society for Testing Materials X-ray diffraction data cards. Experimental Procedures Although the isothermal sections presented in this paper are not unusually complex, the experimental techniques involved in their construction are made extremely difficult by the relatively high vapor pressure of lithium and the great chemical activity of both magnesium and lithium. Because of these characteristics, which make precise control of the composition of equilibrium-treated filings practically impossible, the disappearing phase method was used in preference to the parametric method in conjunction with metallographic studies. The alloys used in this investigation were melted and cast in an atmosphere of helium using a tilting-type furnace which enclosed a steel crucible and mold in a single unit. Each portion of the charge (500 to 600 g) was cleaned carefully just before placing it in the crucible; and the charge, crucible, and entire melting apparatus were evacuated and then washed with grade A helium while preheating to approximately 100°C. The alloys were melted and chill cast in an atmosphere of helium. Alloys prepared in this way were relatively free from inclusions and a fluxing treatment was considered unnecessary. The cylindrical ingots obtained were scalped and then reduced 96 pct in area by direct extrusion, yielding % in. diam rod. Sections of the rod, approximately 3 in. long, were given equilibrium heat treatments and then sampled for metallographic examination, X-ray diffraction study, and chemical analysis. The surface of each equilibrium-treated rod was machined to a depth sufficient to insure removal of contaminated material before samples for chemical analysis or X-ray diffraction study were obtained, and all decisions on microstructure were based on the examination of the central portion of the metallographic specimen. All specimens homogenized at 375°C were analyzed after this equilibrium heat treatment. When the composition of an alloy placed it in a critical area of the 200" or 100°C isothermal section, a check chemical analysis was made on a sample taken from the alloy specimen as-heat-treated at the particular temperature. Standard chemical procedures of gravimetric analysis were used in the determination of magnesium and aluminum; lithium, potassium, and sodium were determined by flame photometer methods

Jan 1, 1956

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By C. G. Dunn, F. W. Daniels, M. J. Bolton

J. P. Nielsen—The data that Dr. Dunn and his associates have been obtaining are welcome checks on the theoretical aspects of grain boundary energies. With reference to the comments on the validity of the inter-facial tension concept, I should like to say that I have been having considerable difficulty myself in untangling the confusion between "interfacial tension" and "interfacial energy." The confusion however resolved itself for me when I learned that "interfacial tension" for solids, or at least crystals, is used with two distinct meanings. One meaning12. ' "hat is implied for "interfacial tension" is the work necessary to produce or increase the surface of the solid in question by a unit area, temperature and pressure held constant. This comes from the somewhat surprising but simple fact that surface tension and surface energy in the case of liquids are identical quantities. This synonymity has carried over to crystals, where it should be kept in mind that the tension connotation has meaning only by analogy with liquids and that no real stresses are being referred to. The only reason that there is apparently a set of stresses acting at a grain boundary junction is the optical illusion that liquid interfaces are being observed for the grain boundaries. The other meaning3,14,15 for the term has to do with actual states of stress in the surface of a material as would be measured by a system of forces applied to the surface to equate the surface stress state with that in the body of the crystal. J. B. Hess—Since the authors have proposed that the surface tension concept should be discarded in order to deal with the general case of interface energies in solids, their attention should be called to a recent paper by Gurney." The latter has shown, from a thermodynamic argument, that surface tension is a valid concept in solids. In fact, Gurney has rejected the idea that surface tensions are merely mathematical fiction and, instead, has given an interpretation of their physical reality. Finally, he has concluded that, as long as appreciable atomic migration takes place, specific surface energies and surface tensions must be equivalent in solids as well as in liquids. Accordingly, the authors' eqs 2 and 3 can be written with equal accuracy in terms of interface tensions, simply by replacing each E,! with its numerically and dimension-ally equivalent Interfacial tension ?,,. If the interfacial tensions (or specific energies) are independent of interfacial orientation, as is true in liquids, then the general equations that define the geometry at equilibrium of the common junction of three interfaces reduce to eq 1. However, neglect of the effect of boundary orientation is never completely justified theoretically' in dealing with crystalline solids; hence, use of eq 1 in such cases must always be considered as an approximation, though clearly a reasonable one for many purposes.1,2 At the same time, one should not be surprised that the assumption that interface tensions in solids are free from orientation

Jan 1, 1951

By J. J. Pye, J. B. Drew

Mzasurements of the surface diffusion coefficients of metals have been made. Diffusion profiles for the Ag-Ag system were obtained by means of a radioactive point source and a precision auto-radiographic technique. The activation energy for silver self diffusion (=8.1 kcal per mole) is lower than that previously reported (-10 kcal per mole) on poly crystalline wire by Nickerson and Parker. The bresent data indicate an effect due to parasitic volume diffusion at temperatures above 500°C. RELATIVELY few measurements have been made of the surface self-diffusion coefficients of metals. Nickerson and arker' measured the diffusion of silver over the surface of poly crystalline wires and estimated that the activation energy was 10.3 kcal per mole. Winegard and chalmers2 carried out measurements on both polycrystalline and single crystal surfaces but did not report a value of the activation energy. They found, however, that at temperatures between 250" and 400°C the diffusion coefficients were on the order of lo-' sq cm per sec and that there was an acceleration of the migration of silver on the polycrystalline sample when a change of surface shape occurred. Winegard and Chalmers used an autoradiographic technique, hereafter designated ARG, and Nickerson and Parker used a surface scanning geiger counter in order to determine the diffusion profiles. More recently, Hackerman and simpson3 measured the surface self-diffusion coefficient of copper at a single temperature (750°C), and the value of the diffusivity (- 10-5 sq cm per sec) is in agreement with that given by jostein from his thermal grooving measurements. This paper reports the results of an investigation of the surface self-diffusion coefficients of silver over a large temperature range and describes the adaptation of autoradiographic (ARG) techniques for the determination of diffusion profiles obtained from a radioactive point source. EXPERIMENTAL PROCEDURE The experimental procedure is a modification of the method employed by Hackerman and simpson3 in their measurements on copper. A brief description of their technique is as follows: A radioactive needle which sinters to the surface during the diffusion an- neal serves as the source of diffusing atoms. After the diffusion run the needle is removed and the surface is scanned with a shielded counting arrangement. The diffusion profiles reported in this paper were obtained by a modification of the above procedure which employs a precision ARG technique. Previous investigations in this laboratory and elsewhere51B have shown that under carefully controlled developing conditions and by the use of calibration sources a linear relation exists between the concentration of the isotope and the photographic density for values below unity. The use of ARG under these conditions has advantages over the counter scanning method in that cumbersome shielding and requirements for great mechanical precision of the scanner are eliminated. Also the ARG gives a complete picture of the surface which is advantageous in studies of anisotropic diffusion. A recording microdensitometer having a 0.1 p wide slit was employed. At low temperatures the disturbing effects of subsurface radiations are negligible. The diffusion anneals are carried out in the cell shown in Fig. 1. The needle is formed by grinding down a 1.0 mm rod of high-purity silver until a tip of 0.2 mm radius or smaller is formed. This tip is plated withA"' which becomes the source of the diffusing atoms that are detected by ARG. The needle carrier and the crystal holder, Fig. 1 are constructed of quartz and ports are provided in the holder pedestal which allow free vapor circulation ((2.0 oz) and the carrier apron fits snugly over the crystal holder cap, insuring that the needle does not move and scratch the surface. Temperatures are provided by a stabilized tubular furnace which can be quickly positioned around the cell, thus bringing the crystal up to temperature in a time that is short compared to the diffusing times. The diffusion anneals range from 2 hr for the high-temperature samples to about 25 hr for those at the lowest temperature. The possibility of vapor transport of the radioactive metal as a contributing factor in the diffusion profile was investigated in two ways. One method was to suspend the needle directly over a dummy sample, raise the temperature, for periods of time equal to the diffusion times, and then take an auto-radiograph of the surface. Negligible radioactivity appeared. In the second method a thin slot in the crystal face on one side of the source provided a "cong path" for surface diffusion. If evaporation was the primary source of surface atoms the region of radioactivity around the source would be symmetrical. This was not the case. The profile dipped abruptly at the edge of the slot but on the other side of the source the usual diffusion profile appeared.

Jan 1, 1963

By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By Robert Lowrie

Nine intermetallic compounds were tested in tension at various temperatures. Seven exhibited extensive plastic deformation at elevated temperatures. Correlations of tensile strength and elongation are attempted with melting (decomposition) temperature, valence electron configurations of the component elements, heat of formation, crystal structure, density, and volume decrease accompanying compound formation. A LTHOUGH intermetallic compounds have been -tX known for many years, the study of their mechanical properties, particularly in tension, is just beginning. The problem has been unattractive because of the well-known, erratic behavior of brittle materials tested in tension. The strong influence of surface or internal flaws as stress raisers in non-ductile materials and the effect of eccentricity of loading in superimposing bending stresses on the state of tension in the specimen are extremely difficult to mitigate and impossible to completely eliminate. Thus, tensile properties determined for brittle materials, such as intermetallic compounds at temperatures low in comparison to their melting points, are at best only general guides to the values to be expected in an ideal test of a perfect specimen of the material. It is, nevertheless, surprising that apparently no attempt was made to follow up the pioneer work of Tammann and Dahl1 in this field. Working with crude apparatus, these investigators succeeded in showing unequivocally that at temperatures sufficiently close to their melting points (from 75" to 400°C for the compounds tested) intermetallic compounds did exhibit plasticity. This was indicated by the appearance of slip lines on the surface of the specimen. No observations of strength were made in these tests, which were of a compressive or indentation type. Rossi2 in 1932 attempted to study the physical and mechanical properties of single crystals of a group of intermetallic compounds. However, he was able to prepare only one material, Cu2Z8,, in the form of large, defect-free, single crystals. Thus, he was able to report only the relative fragility of the compounds at room temperature. He reported one compound, Ag,Zn,, to be somewhat plastic at room temperature and Cu,Si to be friable, the latter in agreement with results reported herein. Although test results are available only in classified literature, it has also been announced that MoSi, possesses some ductility at elevated temperatures." In 1948 and 1949 Savitskii and Savitskii and Baron -ublished their work on the hot extrusion of Mg-Zn, Al-Mg, and Cu-Zn compounds. Under the favorable state of stress existing for this process MgZn, MgZn,, MgZn,, ß (Al-Mg), ? (Al-Mg) and 0 (Cu-Zn) could be reduced by amounts up to 90 pct at elevated temperatures. These authors also report that hardnesses of Mg-Zn compounds decrease from room temperature values of about 300 kg per sq mm to 30 to 50 kg per sq mm at 325°C. They found that alloys consisting solely of one Mg-Zn compound were most resistant to softening on heating, mixtures of a compound and eutectic less resistant, and mixtures of two compounds least resistant. The more rapid softening of mixtures of

Jan 1, 1953

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:'-' 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

By J. P. Nielsen

When two grains in a polycrystalline specimen meet at a point in the course of grain-boundary movements, and the new boundary created at the point is one of relatively low specific free energy, a nonequilibrium boundary condition occurs. The nonequilibrium is enhanced if the other grain boundaries involved at the point of meeting are relatively high in specific free energy. The nonequilibrium results in a correction by growth of the complex grain (two subgrains) to a large size, sufficient in many cases for it to become a self-propagating unit, i.e., a recrystallization grain. This mechanism, herein called "geometrical coalescence," is proposed as a logical origin for recrystallization nuclei, particularly for secondary recrystallization. RECENT publications1-' indicate that considerable progress has been made toward a complete understanding of the three microstructural processes in metals: recovery, recrystallization, and grain growth. However, a major problem persists, namely, the origin of recrystallization nuclei. It is generally accepted that once a recrystallization nucleus, a secondary recrystallization nucleus particularly, has reached a certain size, it will continue to grow at the expense of its neighbors, simply as a consequence of grain-boundary free-energy considerations. What has remained obscure, however, is the mechanism whereby such a nucleus comes into being and grows to the self-propagating size. Recrystallization Nucleation in a Two-Dimensional Grain-Boundary System In the left portion of Fig. 1 is shown schematically the meeting of grains 1 and 4 on disappearance of boundary 2-3, i.e., the boundary that existed between grains 2 and 3, as might happen in the course of normal grain-boundary migration. If, by chance —and the probability is not necessarily small— grains 1 and 4 are close together in their mutual orientations, or in some other special way mutually oriented so that the new common boundary has relatively a very low specific free energy (hereinafter referred to by s), then the grain boundary arrangement as depicted in the figure is highly unstable. This is particularly so if boundaries 1-3, 3-4, 4-2, and 2-1 are high in their s values. Assuming, for the sake of argument, that boundary 1-4 has a s equal to zero, and the s's of all the other boundaries present are equal to each other and constant, then the boundary arrangement on the right in Fig. 1 will be

Jan 1, 1955

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,' and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By Bernhard Blumenthal

A melting process was developed by which high purity electrolytic uranium crystals can be converted into sound ingots without serious contamination. Careful preparation of the crystals, melting in a high vacuum, and directional solidification led to a metal of better than 99.993 wt pct purity. The metallographic examination showed a substantially clean metal with only residual amounts of a second phase which responded to heat treatment. The density of high purity uranium is 19.05 g per cu cm. FOR the study of the fundamental properties of uranium and its alloys, a base metal of high purity is needed, and an investigation was started at Argonne several years ago to examine various methods of preparing high purity uranium. Early success was achieved by the fused salt electrolysis process in preparing high purity metal in crystal form,' and the problem became that of melting the crystals into ingots without contamination. The electrolytic crystals contained a few ppm of heavy metals, less than 15 ppm C, and large quantities of potassium and lithium in the form of trapped fused salt electrolyte. On melting in vacuo in magnesia or urania crucibles, the metal picked up considerable quantities of carbon and some iron, copper, and silicon but lost most of the potassium and lithium. It was not metallographically clean, and much research work was necessary to determine the optimum melting conditions for minimum contamination. This work has resulted in the development of a melting procedure by which sound ingots can be prepared with only a limited contamination by carbon. In the section entitled "Melting of the Electrolytic Metal," the equipment and processes that have been developed for melting the electrolytic crystals are described in detail. The "Metallography" section is devoted to the metallography of high purity uranium, and the section "Density of High Purity Uranium" contains the first property measurement on high purity uranium—a density determination. Melting of the Electrolytic Metal Apparatus—Melting and Vacuum Equipment: Uranium may be melted in either resistance or induction-type electric furnaces. Resistance heating was found to be preferable to induction heating for melting down the electrolytic crystals, for several reasons: Although induction heating permits fast heating, this advantage cannot be utilized when crucibles with limited thermal shock resistance are used. Temperature control of induction-heated melts is poor, and the stirring effect increases the rate of contamination of the melt from the crucible, slag, or the furnace atmosphere; liquation and controlled solidification are difficult to carry out. Because of these objections, resistance heating was chosen. A 10 kw Globar resistance furnace of low heat capacity permitted uniform heating of a uranium charge to its melting point in 45 min. The furnace was insulated with a removable aluminum shield so that, after melting and removal of the shield, the furnace could be quickly cooled to room temperature. The furnace was equipped with an apparatus for directional solidification; see Fig. la. The crucible was suspended in the center of the furnace; and when the melting was complete, the crucible was slowly lowered into the cold end of the furnace tube. Solidification took place upward from the bottom; and when the rate of lowering was small, a sound ingot free from sink holes and shrinkage cavities was produced. To remove the large quantities of gas contained in the electrolytic crystals, melting in a high vacuum is mandatory. While, from the standpoint of contamination, melting in a highly purified argon atmosphere appeared feasible, lithium and potassium removal proved less efficient under such conditions. Also, a vacuum-melted ingot has a cleaner surface than one melted in an inert atmosphere. The vacuum system must be of very high pumping speed and leak tight so that a vacuum of less than 2x10-7 mm Hg is attainable when the system is pumped down cold. The system must have a high pumping speed, so that the pressure maximum which may rise to 1x10-4 mm during heating can be quickly reduced

Jan 1, 1956