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By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By P. Rama Rao, D. H. Sastry, T. R. Anantharaman

Deformation (a) and twin (a') stacking-fault densities in cold - wor ked filings of fcc silver alloys containing 2, 4, and 6 wt pct Sb have been estimated from Debye-Scherrer peak shifts and asymmetries, respectively. Evidence has been obtained for a possible strain-induced transformation in a two-phase alloy containing 9.0 zut pct Sb. Using Fourier analysis of X-ray line profiles, the effective particle sizes and root mean square strains have been determined for the three fcc alloys in the cold-worked condition. The values of the compound fault probability 0.5a + a') evaluated from peak shifts and asymmetries are in reasonable apeement with those derived from peak broadening. COLD work of fcc metals may produce both deformation and twin (also called growth) stacking faults, which can be detected and quantitatively estimated by X-ray diffraction techniques.' In addition to peak broadening, deformation faults produce a shift in peak positions and twin faults an asymmetry of the Debye-Scherrer reflections. Besides stacking faults, a reduction in the size of coherently diffracting domains and distortion within these also broaden the powder reflections of deformed fcc metals and alloys. Fourier analysis' of peak shapes provides quantitative infor- mation about the effective domain sizes, lattice strains, and also the compound fault probability (1.5a + a'), where a and a' represent deformation-and growth-fault density, respectively. The Paterson method2 for determination of a from peak shifts, the warren3 or wagner4 method for evaluation of a' from peak asymmetries, and the Fourier analysis for quantitative estimates of all the contributory causes of peak broadening have, in the course of the last decade, been extensively applied to obtain data for a number of deformed fcc metals and alloys. One of the useful results of earlier measurements of a in several solid solutions is a correlation between a and the solute valence as well as electron concentration per atom (p) in alloy systems based on a particular solvent. The work of Smallman and westmacott5 on Cu-Zn, Cu-A1, and Cu-Sn, of Foley, Cahn, and ~aynor' on Cu-Si and Cu-Ge, and of Rama Rao and Anantharaman7 on Cu-Si and Cu-Sb has revealed a common trend in the increase of a with p and also a with valency of the solute. Cahn and Davies' and Ad-ler and wagnerg have observed similar trends for silver alloys containing cadmium, indium, and tin. Data on a for silver alloys with a pentavalent solute element are not, however, available. It is primarily to fill this need that the present investigation on Ag-Sb alloys was undertaken. Utilizing the Patersonand Warren methods, values of a and a', respectively, have been determined in three silver alloys containing 2, 4, and 6 wt pct Sb. By Fourier analysis of the broadening of Debye-Scherrer peaks, effective particle sizes, lattice strains, and the compound fault probability (1.5a +a') have also been evaluated.

Jan 1, 1967

By K. R. Waugh, Barbara S. Brown, D. W. James

AN electronic data-processing system is described which permits rapid, accurate, low-cost processing of strain-dependent damping data utilizing equipment normally available within the service facilities of most large laboratories. On analyzing the record of a stress-dependent damping test, the operator usually measures the double amplitudes at several points on the decay curve. The logarithmic decrement is then calculated for decay between consecutive amplitudes. These values of 6 are plotted against the corresponding maximum surface shear stress, T, which is proportional to the average of the two amplitudes between which is calculated: where d is the specimen diameter. The period of the vibration is not necessarily constant during decay; thus, each cycle must be counted. A decay curve may extend to, perhaps, 1000 cycles, and at least two curves are always obtained for each specimen or set of conditions. It can, therefore, be seen that manual analysis of decay curves is both tedious and costly in terms of man-hours. Furthermore, the resolution of the record is often such that accurate measurement of amplitude is extremely dif-

Jan 1, 1969

By J. J. Fischer

COMPOSITES containing cold-drawn, high-strength steel wires have shown promise for normal and slightly elevated temperature applications, particularly where strength-to-weight ratios or corrosion resistance are important.'-3 Although tensile strengths up to 500,000 psi may be obtained by cold drawing these wires, processing the composite at elevated temperatures will result in a rapid decrease of the wires' strength. In wrought maraging steels, high-strength levels can be obtained by aging at 900' . Because these alloys do not rely on heavy cold working to achieve their strength, and because they do not overage readily, they are of potential interest for use in composites. In view of this, the tensile strengths of composites containing The total heat effect thus represents the heat of formation, AHf of the compound at 273' . Since the heat of solution of tin in the tin solvent bath is zero, AHz = 3( - H273)Sn and Hf is given by: For LaSn3, AH3 had a measured value of 11,285 i 380 cal per g-atom while for La2Sn, the corresponding value was 33,658 870 cal per g-atom. Using the measured data for the compounds and pure lanthanum, a value of -15,150 200 cal per g-atom was calculated for the heat of formation of LaSn, at 273°K, while Hf for La2Sn3 was found to be -28,090 400 cal per g-i&om. The authors would like to acknowledge the financial support of the Army Research Office, Durham, North Carolina. under contract No. DA-31-124-ARO-D-384.

Jan 1, 1969

By Robert E. Reed-Hill, Edward R. Buchanan

A recent paper by Adams and vreeland30 describes dislocation density changes in zinc as a function of shear strain. The dislocation density was determined with the aid of an etching technique previously described by Brandt, Adams, and Vreeland.31 However, comparison of dislocation densities obtained by electron microscopy and this etching technique are not in good agreement, as will be shown below. Several zinc crystals of 99.999 pct purity were grown in air using a modified Bridgman technique.' These were annealed in air a 400°C for 1 hr and

Jan 1, 1969

By S. Shapiro, G. Krauss

We will reply to Dr. Pitsch's discussion by 1) presenting in greater detail the single surface trace analysis which we performed on the reversed austenite plates in a single parent plate of martensite of known orientation, 2) relating the results of our analysis to the conclusions which Dr. Pitsch makes on the basis of our data, and 3) examining the validity of our selection of twenty-nine individual traces from the over 200 austenite plates which were observed in a surface of this single martensite plate. Fig. 7 shows a standard (001) projection of the martensite plate from which the austenite-martensite interface traces were taken. The traces are plotted on the projection as the small solid circles, and the great circles corresponding to the loci of plane normals which could contain each trace or could intersect the surface plane along the measured directions are also plotted. It can be seen that these great circles intersect at a point which corresponds to the normal of the surface plane on which the traces were observed. Also rate which occurred only at particularly low heating rates, see Figs. 1 and 3 in the paper.2 Since in this case the interpretation of Jana and Wayman is plausible and since we have no alternative to this interpretation, we would like to state only that the existence of a diffusion-controlled reversal at low temperatures seems to be not yet proved beyond any doubt. The author wishes to thank Professor G. Krauss for making available his manuscript prior to publication. It is also a pleasure to acknowledge the lively written discussions, which the author has had with Professors G. Krauss and C. M. Wayman prior to this communication. The financial support of the Deutsche For-schungsgemeinschaft for the work on which this communication is based is also gratefully acknowledged. plotted within small dotted circles which represent a i3 deg scatter in each of the twenty-four unit stereo-graphic triangles are our A and B poles7 and the pole P determined by Kessler and itsch.' The data presented in Fig. 7 permit a direct association of the measured traces and the various proposed habit plane poles for the reversed austenite plates in the martensite crystal. If the sample measurements do in fact

Jan 1, 1969

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3'7

Jan 1, 1969

By N. R. Pillai, T. R. Anantharaman

THE striking alterations in the constitution and structure of cast A1-Si alloys brought about by addition of small quantities of some elements, particularly sodium, have been extensively investigated. Many theories' have also been propounded to explain this so-called lLmodification" process, but their main concern has been more to throw light on the action of sodium than to arrive at general criteria underlying this interesting as well as intriguing phenomenon. Such theories have generally dealt with one or more, but not all, factors that seem to have a direct or indirect influence on the cast structure of A1-Si alloys, e.g.., formation of ternary eutectic, removal of oxides, hydroxides, and so forth, by fluxing, morphological changes in silicon, and inhibition of growth of silicon grains through colloidal action, compound formation, preferential adsorption, or reduction of surface tension. Kim and Heine2 were the first to study the modification of A1-Si alloys in a systematic as well as comprehensive manner and to list the important characteristics of a satisfactory modifier. According to them, an important property of the modifying element is its capacity to form a stable compound with silicon in the appropriate temperature range. Other subsidiary requirements are that the element should get adequately dispersed in the melt at the inoculating temperature and also must not form stable compounds with aluminum. The alkali elements, with the exception of lithium, fulfill these requirements most satisfactorily and have been shown to be successful modifiers by these workers. Sodium is the most effective of these and seems to be in a class by itself for various reasons noted by earlier investigators.37 None of the other elements tried by Kim and Heine, viz., Mg, Ca, Cd, Zn, In, Pb, P, As, Bi, S, and Se, showed any significant modifying action. We wish to report here briefly on substantial modifications in cast eutectic A1-Si alloys brought about by some V group elements, which do not comply with the Kim-Heine requirements. Aluminum and silicon used in the present work were indigenous and had purities of 99.8 and 99.5 pct, re-

Jan 1, 1969

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By C. Y. Cheng

THE purpose of this note is to show that the dislocation mechanism controlling the creep of Fe-4 pet Si alloy1 may equally account for the behavior of a-Fe2 over the same temperature range. A recent study of the creep behavior of a-Fe has been made by Ishida et al.2 Their results were in agreement with the mechanism of nonconservative motion of jogged screw dislocations over the entire range of temperatures investigated, from 480° to 1045°K. However, the observed creep rate was much higher than that which could be accounted for by the above model unless the authors assumed that pipe diffusion became significant below 775°K. More recently, Cheng et al.1 inves-gated the creep of Fe-4 pet Si alloy over about the same temperature range and found that the results could be correlated fairly well with a dislocation climb mechanism as represented by Eq. [l]. Proceeding as shown previously,1 if creep is controlled by a single climb mechanism, at intermediate stresses, the shear creep rate, y, can be represented by where n and K are material constants {K is independent of the temperature but dependent on the structure, that is, K decreases during the primary stage and reaches a steady-state value over the secondary stage of creep), t is the applied shear stress, G is the shear modulus, gc is the free energy of activation for creep (usually equal to that for self-diffusion, gd), and RT has the usual meaning. By solving for y, the apparent activation energy for creep, Q which can be determined experimentally, is given by where hc is the enthalpy of activation for creep which usually is also equal to that for self-diffusion, h^. By using Eq. [2], the data in Fig. 2 of Ref. 2 can be re-plotted as shown in Fig. 1. By comparing the two figures, it is seen that the slight increase in the apparent activation for creep over Region II, as noted in Fig. 2 of Ref. 2, is due to the influence of temperature on the shear modulus rather than of the stress on the

Jan 1, 1969

By Wolfgang Pitsch

INVESTIGATIONS on the above topic have recently been published by Shapiro and Kraussl and Jana and wayman in this journal and by Kessler and Pitsch.- Parts of the results in these papers are in good agreement with each other but there are also some results which are substantially different. The main points of these differences shall be briefly discussed in this communication. Shapiro and Krauss' measured single-surface traces of the habit planes of reversed austenite plates formed within the martensite crystals and deduced from these measurements two distinct habit planes A = (0.174; 0.309; 0.935) and B = (0.375; 0.545; 0.749) within 3 deg. Kessler and pitsch4 found instead by two-surface analysis7 one habit plane n = {0.23; 0.62: 0.75) with a real scatter of 6 deg. The latter observation of a single habit plane apart from a certain scatter is in agreement with most of the investigations of martensite transformations. The differences between these two results are so great that they cannot be explained by experimental error. The purpose of this communication is to show that the A- and B-poles of Shapiro and Krauss are due to an erroneous interpretation of a single-surface trace analysis. The difficulties in the interpretation of such single-surface trace analyses are due to the high symmetry of cubic lattices, from which it follows that there are in general twenty-four equivalent possibilities of plotting a single-surface trace in a pole figure. All these possibilities must be taken into account, when putting different traces from different plates together in order to construct the habit plane. Alternatively the poles of all the traces may be plotted in a unit triangle. This is done in Fig. 1 with twenty-nine traces of different reversed austenite plates, all of this were measured by Shapiro and Krauss in the same plane of a single martensite ther traces taken from Fig. 13 in the Shapiro and Krauss paper' which were determined by electron diffraction. The traces in Figs. 1 and 2 have to be compared with the habits A, B, and n which are under discussion. Therefore the great circles of the poles A, B, and n are plotted in Figs. 3, 4, and 5 together with a 3-deg scatter region for poles A, B and a 6-deg scatter region for pole n. Comparing Figs. 1 and 2 with Figs. 3, 4, and 5 one finds the statements which

Jan 1, 1969

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By N. A. D. Parlee, I. D. Shah

THIS communication reports the results of some work done on the effect of gold, palladium, and platinum on the liquid-gas-solid equilibrium in the Ag-O system,1,2 see Fig. 1. Recently several investigators3, 4, 5 have reported the effects of gold, palladium, platinum, and copper on the solubility of oxygen in liquid silver. This communication represents only a portion of the work done here on the solubility of oxygen in liquid silver and liquid Ag-Au, Ag-Pd, and Ag-Pt alloyss—the greater part having already been reprted. The apparatus, materials, and procedures used were similar to those of earlier work.' l The main precautions observed in obtaining these freezing points at constant temperature and PO2 = 1 atm were as follows: 1) The points were approached very slowly from higher temperatures. 2) In the very near vicinity of the L-G-S equilibrium point precautions were taken to see that the melt was in equilibrium with oxygen at one atm. Equilibrium was considered to have been attained when no more absorption of oxygen was observed in the last 15 min at a fixed temperature. 3) In the case of these alloys, the freezing point of the melt at 1 atm of oxygen and the equilibrium amount of oxygen absorbed by the liquid "infinitesimally" above this point were determined by lowering the temperature in very, very small steps, equilibrating at

Jan 1, 1969

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By K. J. Anusavice, R. T. DeHoff, H. Oikawa, J. J. Pinajian

STUDIES of nickel self-diffusion and impurity diffusion in pure metals and alloys have, for the past two decades, employed predominantly the nickel radio-However, because of the low energy of the emitted particle, careful and time-consuming techniques must be used to obtain reproducible measurements. In our studies of nickel diffusion into copper, we have recently used Ni66 [Td1/2: 55 hr; : 0.20 Mev (100 pet)] which decays to it much more suitable as a tracer because of the presence of the high-energy y radiation from the cu66 daughter. Although the half-life of Ni66 is appreciably shorter than that of Ni63, the useful working lifetime of a small quantity, " 10 mc, is about 1 month. preparation bf Ni66. he Nis6 radioisotope was produced at Oak Ridge National Laboratory by means of a double (n,y) reaction:

Jan 1, 1969

By P. K. Strangway, H. U. Ross

Briquets consisting of pure artificial magnetite, pure artificial hematite, and mixtures of the two were reduced by hydrogen in a loss-in-weight furnace at temperatures in the range 500° to 1000° . The rate of reduction of the pure hematite briquets increased continuously with increased temperature. In contrast, the pure nmgnetite briquets exhibited a pronounced rate ninimutn at about 700°C. Metallographic studies of partially reduced briquets rerlealed that, at this temperature, the he.matite samples reduced in a topo-chemical manner while the magnetite ones reduced uniformly throughout, and after partial reduction their cross sections contained a mixture of iron and unreacted wustite grains. No iron shells could be detected on the surfices of any of these uwstite grains. X-ray diffraction investigations indicated that these grains had a rzinimum lattice parameter when they had been formed at the rate rninimum temperature. Also, it was found that an activation energy of 41,000 cal per mole zoas required for reduction when only these wustite grains were present. Thus, it is suggested that the overall reduction rate of the rnagnetile su?nples at temperatures in the range influenced by the rate nzinirnum phenomenon was limited by the rate qf iron ion diffusion in the unreacted wustite grains. THE rate minimum phenomenon, which has often been observed when reducing iron oxides at a temperature of about 700°C, is one of the most interesting, yet unresolved, problems in the field of reduction kinetics. Basic principles of chemical kinetics and 'In some instance, a second rate minimum has been observed at about 900°C. Since most investigators are in agreement that this minimum is directly related to the transformation from a to y iron (which takes place at 911°C) and since it was not encountered during the present reduction tests, it will not be referred to in this vaver. fundamental laws of diffusion all agree that, as the temperature is increased, the rate of reduction should also increase. However, with certain ores, it has been found that their reduction rate actually decreases with an increase in temperature up to some value X where a minimum reduction rate is reached. With further temperature increases beyond X the rate becomes more rapid again. Temperature X is usually referred to as the "rate minimum temperature", while the overall type of behavior constitutes the "rate minimum phenomenon". This phenomenon has been reported by numerous investigators. They have found rate minima during the reduction of both artifiial' and natural374 magnetites and artificia15j6 and natural5" hematites. Rate minima have been observed when reducing high-purity material2 or low-grade ores,3'4 when studying particles in the micronsize range5 or relatively large agglomerates,g10 and during reduction with either hydrogen7 or carbon monoxide.11"2 Previously, this phenomenon has been attributed to many factors; these include sintering and recrystallization of the iron formed during reduction374 changes in microporosity of the ore upon redction,"" formation of dense iron shells around retained wustite grains,11716 and chem-isorption,17 to name only a few. However, most investigators who have reported a rate minimum merely speculated as to what seemed to influence it and they did not examine the fundamental causes. Consequently, the present experimental study was initiated in order to evaluate the basic factors which could be associated with this phenomenon. MATERIALS AND METHODS The experimental techniques, followed during this investigation, are similar to those which have been described previously.18 The chemically pure magnetic powder was prepared by partially reducing Fisher reagent-grade hematite with a gaseous mixture of carbon monoxide and carbon dioxide in a rotating-drum furnace. Three-quarter-inch diam cylindrical briquets which weighed about 12 g were formed from this magnetite powder and pure hematite powder. All of the briquets were sintered while they were slowly raised through the 1200°C hot zone of a vertical tube furnace. An argon stream was continually flushed through this furnace in order to prevent oxidation of the magnetite briquets, while in the case of the pure hematite briquets sintering was carried out in air. The sintered hematite briquets had a density of 5.06 g per cu cm while the density of the sintered magnetite briquets was 4.27 g per cu cm. The sintered briquets were reduced by purified hydrogen in a loss-in-weight furnace at temperatures in the range 500" to 1000°C. In all instances, the critical reducing gas velocity was exceeded and, in order to ensure that the results were reproducible, duplicate briquets of each type were reduced under each set of experimental conditions. A continuous record of the weight loss during reduction was obtained with the aid of a Statham transducer. The present experimental setup was capable of detecting a change in weight as small as 10 mg. Since a weight loss of over 2 g usually occurred during each reduction test, an accuracy of better than 0.5 pct of the total weight loss could be achieved. RESULTS AND DISCUSSION Reducibility Tests. In the first set of experiments, pure hematite and pure magnetite briquets were used.

Jan 1, 1969

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969