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By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By A. B. Parsons

Jan 1, 1971

By E. J. Bonet, P. B. Crawford

It is fairly common practice to reinject water into the aquifer near the oil-water interface in water-drive reservoirs. There have been many studies of aquifer behavior without reinjection,l-5 but apparently no analytical studies have been made to indicate performance when injection wells are present in the aquifer. The diffusivity equation may be used to describe the pressure behavior in an aquifer. When sources are present it can be written as A general solution of Eq. 1 may be obtained as the sum of two solutions. One is a general solution of the homogeneous equation, obtained by dropping the source term in Eq. 1 and still satisfying the required boundary conditions. Another is a general solution of Eq. 1 satisfying homogeneous boundary conditions.1° The first solution, which corresponds to the aquifer without reinjection, has been given quantitative and qualitative treatment in the literature.l-5,8,9 The latter solution will be treated here. Solutions with variable injection rates are obtained by superimposing solutions with constant rates, so we have considered only the latter. Five cases have been treated here: 1. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The pressure along the line x = 0 is maintained at zero pressure. (See Fig. 1.) Equations showing the pressure distribution, rates, velocity and cumulative influx have been developed. Certain numerical results are shown. 2. A linear aquifer of finite width and extent. Water is injected into the aquifer at point xo, yo at constant rate. The rate of production along the oil-water water contact is maintained constant. Equations showing the pressure distribution inside the aquifer are presented. 3. A linear aquifer of finite width and extent. Constant pressures are maintained at opposite ends of the aquifer. Water is injected at constant rates at point xo, yo. Equations showing the pressure distribution are shown. 4. A linear aquifer of finite width and infinite extent. The pressure is maintained constant at the oil-water contact. Water is injected at a constant rate at point xo, YO. 5. A linear aquifer of finite width and finite extent. The pressure at the oil-water contact is maintained constant. Water is injected at constant rate per unit length along a line x,. The Linear Aquifer The linear closed aquifer, performing at constant terminal pressure was selected as the first case to be analyzed. The development of the equations is based on uniform injection per unit of thickness, and gravity effects are neglected. In practical application this condition is probably most closely achieved when the

Jan 1, 1970

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson's material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,' however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965

The following is an incomplete list of members and guests who. called at Institute headquarters during the period Dec. 10, 1917 to Jan. 10, , 1918: A. A. Arluck, Camp Merritt, N. J. W. Spencer Hutchinson, Boston, Mass. C. L. Bruns, Santiago de Cuba. William F. Jahn, New York, N. Y. Henry C. Carr, New York, N. Y. C. H. James, Tucson, Ariz. L. J. Charles, Santa Fe, N. M. Charles Janin, San Francisco, Cal. W. A. Deane, Waxhaw, N. C. Joseph T. Kupferstein, Shreveport, Pa. P. St. John Dixon, Rio de Janeiro, Brazil. Richard Lamb, New York, N. Y. M. C. Drake, Marquette, Mich. Walter R. Malm, San Francisco, Cal. F. W. Draper, Petrograd, Russia. W. H. Nash, Buffalo, N. Y. Paul W. Gaebelein, Boise, Idaho. Edmund Newton, Minneapolis, Minn. H. F. E. Gamm, Rutherford, N. J. Guy C. Riddell, Port Pirie, South Australia. C. A. Grabill, El Paso, Tex. Williams A. Simkins, San Francisco, Cal. William H. Hampton, New York, N. Y. Henry B. Smith, Northampton, Mass. R. M. Henderson, Brackenridge, Colo. H. E. Smith, Chicago, Ill. Geo. B. Holderer, Northpines, Ont., H: C. Spaulding, Washington, D. C. Canada. Y. Wakabayashi, Tokyo, Japan. H. H. Howry, Camp Upton. N. Y. A. P. Watt, Mine La Motte, Mo. L. Douglas Anderson", superintendent of the Midvale, Utah, smeltery of the United States Smelting Co., has been appointed manager of smelteries for the company at Salt Lake City, Utah.

Jan 2, 1918

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

By J. Gurland

A method of measuring the degree of contact between grains of 1 phase in multiphase alloys is derived. It is shown that the number and the areas of contacts between grains can be determined by metallographic analysis. Relations between the area of contact, the dihedral angle, and the mean free path of spherical grains are developed. It is often desirable to interpret the mechanical behavior of alloys in terms of structural features observed under the microscope. A quantitative description of microstructures of multi-phase alloys requires consideration of geometrical and topological factors such as the amount, size, and shape of grains and the continuity of the constituent phases. The number and dimensions of grains may be metallographically determined by applying the methods described by Smith and Guttman1 and by Fullman2 in their papers on the measurement of particle size and internal boundaries in opaque bodies. The present work intends to show that the same methods can be used to evaluate some of the parameters of phase continuity; namely, contiguity, number of contacts, and areas of contact of grains of 1 phase. Application of these concepts may be found in such problems as the calculation of electrical conductivity of 2-phase alloys, or the evaluation of the length of fracture path through grains of a brittle phase more or less dispersed in a matrix. I. DEFINITION The following definitions and derivations are based on 2-phase alloys, of which the units of the microstructure are grains. Contiguity is defined as the average fraction of surface area shared by 1 grain of a phase with all neighboring grains of the same phase. In a 2-phase alloy of constituents A and B, the contiguity of phase B is given by: where Cb is the contiguity of phase B aBß is the average area of contact between a grain of phase B and adjacent grains of phase B, aAB is the average area of contact between a grain of phase B and adjacent grains of phase A. The contiguity is a measure of the average degree of contact between grains of phase B in the 2-phase mixture. The ratio varies from 0 to 1 as the distribution of phase B changes from a completely dispersed to a fully agglomerated structure. Smith and Guttman1 have shown that the relative areas of 2 kinds of interfaces in a volume are directly proportional to the number of interfaces of each type intersected by a random line. The lines can be drawn on metallographically prepared surfaces as long as these are random sections through the sample. The contiguity ratio of phase B then becomes: Cb = 2NBB/NAB + 2N BB [2] where: NBB is the number of interfaces between grains of phase B intersected per unit length of random line. Nab is the number of interfaces between grains of phase B and grains of phase A intersected per unit length of random line. The factor 2 arises in Eq. [2] because each interface B-B is associated with 2 grains of B-phase, whereas the interface A-B involves only 1 grain of B-phase. The calculations of contiguity do not require any assumption as to volume fraction, particle size, or particle shape. Fullman2 gives an expression for the determination of the mean free path between particles. The mean free path PB between grains of phase A, i.e., through grains or agglomerates of phase B, may be found from the relationship: PB =2fB/NAB [3] where fB is the volume fraction of phase B. The calculation of the mean free path is independent of grain shape and grain size distribution. The calculation of the number of contacts and of contact area requires assumptions of grain shape, grain size, and contact shape. In the case of uni-

Jan 1, 1959

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

President-Mrs Andrew E Beer, Richardson Ave, Sea Cliff, L I, N Y First Vice-President-Mrs Lyman H Hart, 6-F Essex House, Garth Woods Apts, Scarsdale, N Y Second Vice-President-Mrs John R C Mann, 90 Edgemont Road, Scarsdale, N Y Third Vice-President-Mrs Edward P Chapman, Jr, 2632 Vista Larga Dr N E, Albuquerque, N M Fourth Vice-President-Mrs R A Cattell, 7717 14th St, N W Washington 12, D C

Jan 1, 1959

By AIME AIME

ATER the preliminary registration at which approximately 380 members and guests were registered, the 138th meeting of the Institute was opened in the Concert Room of the Palace Hotel. E. A. Hersam, chairman of the San Francisco Section, voiced a brief welcome and introduced F. W. Bradley, president of the Institute, who presided over the remainder of the morning session. After expressing the welcome of the Institute to the members and guests, he read a telegram from Secretary H. Foster Bain, extending the best wishes of the eastern staff and members for a successful meeting. He next introduced Theodore J. Hoover, dean of the School of Engineering, Stanford University, who read an address by the Secretary of the Interior, Ray Lyman Wilbur, briefly outlining California's part in the mining industry and giving the welcome of California to this meeting of the Institute.

Jan 1, 1929

By F. Claisse, R. Angers

Self-diffusion in iron has been measured during rapid a-r transformations using a variant of the Kryukou and Zhukhovitskii diffusion method. The study was performed by thermally cycling iron foils (1 to 6 cpm) through the transformation (=910°C). Some foils have been subjected to over 1000 cycles and some have spent more than 15 pct of their total diffusion time in the process of transformation. The experimental results show that the a-r transformation has no measurable effect on self-diffusion in iron. The study is completed by a quantitative analysis of mechanisms which can affect the diffusion rate during the transformation. The analysis confirms the experimental results. SINCE diffusion is an important factor in many solid-state transformations, it is of interest to study how it is affected by the stresses generated during these transformations. Clinard and Sherby1'2 were the first to make a study along these lines. They measured diffusion coefficients in Fe-FeCoV couples subjected to slow thermal cycling (1.5 cph) through the a-r transformation range. They found an enhancement of diffusion by a factor of about two. The purpose of the present paper is to report measurements of the self-diffusion coefficient of iron during much more rapid thermal cyclings (1 to 6 cpm) through the a-r transformation (-910°C). These more rapid cyclings produce higher strain rates during the transformation and should emphasize any possible influence of transformation upon diffusion. EXPERIMENTAL Iron foils, 25 to 35 µ thick, were cold-rolled from 99.92 pct pure iron and annealed in pure helium for 2 hr at 870°C; the resulting grain diameter was about 150 µ. Specimens 0.5 by 8 cm were cut from the foils and I7e55 was vapor deposited on one of their surfaces. A 38 gage alumel-chrome1 thermocouple was spot welded in the middle of one of the specimen long edges, Fig. 1. Two 38 gage chrome1 wires were also spot welded along the same edge on each side of the thermocouple; they were placed 2.5 cm apart and used for electrical resistance measurements. In order to prevent twisting and crumpling, the specimens were pinched between two quartz plates 0.1 by 1 by 7 cm and the assembly was close fitted into a 1 cm ID quartz tube. Four holes were drilled through the tube to let the 38 gage wires out: these were connected to the recording equipment by means of extension wires. 20-gage nickel wires fixed at both ends of the specimens were used to thermally cycle the foils by Joule heating. The above described device was placed in a 2.7 cm ID quartz tube which in turn was placed in a tubular furnace. Either a pure helium atmosphere or circulating hydrogen was used during the experiments. Specimens were subjected to thermal cycles between a minimum temperature To and a maximum temperature Tm at rates ranging from 1 to 6 cpm. This was obtained by maintaining the furnace at a constant temperature near the minimum temperature To and periodically passing an electric current through the specimen. Cooling was achieved by heat losses to the surroundings. The forms and periods of cycles were varied from one specimen to another; however, each specimen was subjected to one type of cycle only. The temperature and electrical resistance variations of the specimens were recorded as a function of time. The temperature curves were used for diffusion calculations while the electrical resistance curves were used to monitor the transformation and to determine its starting point and its approximate duration. Diffusion was measured by the method developed by Kryukov and zhukhovitskii3 and modified by Angers and Claisse.4,5 In this method a metallic foil is coated on one side with a radioactive isotope and the activity is measured periodically on both sides during the diffusion anneal. The following equation then holds: where: I1 Activity on the surface on which the deposit is made. I, Activity on the opposite surface. t Diffusion time. B Constant. D Diffusion coefficient. d Foil thickness including the deposit. G(t) A function of time; it is a second order correction term which is given graphically in Refs. 4 and 5. The diffusion coefficient D is found by plotting ln[(Il - I2)/(I1 + I,)] -G(t) against t; the resulting slope m leads to an accurate calculation of D through Eq. [2]. The effect of the a-r transformation on diffusion is expressed by the ratio DT/DU where:

Jan 1, 1970

By K. Kobayashi, K. Ueda, K. Yamaguchi

Lead concentrates from Kuroko (black ore) mines, which contain 4-7% Cu, 55% Pb, 3-777, Zn, and 0.5-0.9% As, are pretreated by a hydrometallurgical process before electric furnace smelting with other lead resources from Kuroko. The hydrometallurgical pretreatment involves sulfuric acid leaching in the first stage and ferric leaching in the second stage. This paper describes the short history of lead recovery from Kuroko and the performance of laboratory tests and pilot plant and commercial operations.

Jan 1, 1985

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York LOUIS D. HUNTOON, Chairman. ARTHUR S. DWIGHT, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. E. MALTBY SHIPP. Treasurer. GEORGE F. KUNZ, W. De L. BENEDICT. Boston ROBERT H. RICHARDS, Chairman. ALBERT SAUVEUR, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE. HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer. P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY. S. H. RICHARDSON.

Jan 5, 1914

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York LOUIS D. HUNTOON, Chairman. ARTHUR S. DWIGHT, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. E. MALTBY SHIPP, Treasurer. GEORGE F. KUNZ. W. DE L. BENEDICT. Boston ROBERT H. RICHARDS, Chairman. ALBERT SAUVEUR, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. 0. Drawer 2154, Spokane, Wash. R. S. McCAFFERY, S. H. RICHARDSON.

Jan 4, 1914

By N. J. Grant, K. M. Zwilsky, J. T. Blucher

DISPERSION strengthening has been studied in a number of metal-metal oxide systems. To date those pure metals available as fine particles (less than about 5 p) have received most of the attention whereas solid solution alloys, generally unavailable as fine powders, have not been examined in detail. The present work was undertaken as a preliminary study to evaluate combined effects of solid solution and dispersion strengthening. The technique used was that of dry mixing of elemental powders with the oxide, followed by a diffusion treatment to obtain the solid solution. The average particle size of the powders used was: Ni, 3.2 p (1nco B); Mo, 1.3 p (Fansteel Metallurgical Corp.); and y alumina, 0.027 \i (G. L. Cabot, Inc.). The particle size of the metal powders was determined by Fisher subsieve measurements while the size of the alumina was calculated from a surface area determination. Prior diffusion studies on small compacts pressed from mixtures of nickel and molybdenum powders with and without 7.5 vol pct A1203 indicated that diffusion was complete after sintering for 100 hr at 1800" , or 50 hr at 2250", or 20 hr at 2550° F. The progress of diffusion was followed by microstructural examination and micro-hardness measurements. Two observations made during the diffusion experiments were: 1) That diffusion proceeded faster in the presence of alumina, confirming similar findings by Seith and Loepman on "SAP'';4 2) That diffusion at temperatures above 1800°F resulted in coarsening of the alumina in agreement with results of other authors reporting on the growth of alumina in nickel above 1800"F. Similar experiments in the Ni-Cr system using 6 and 20 p Cr powders of 0.7 and 0.025 pct 0, respectively, did not result in significant solid solution formation even after long time exposures at 2550° F. It must be concluded that chromium oxide films around individual particles interfere with normal diffusion. A nickel alloy containing 5 wt pct Mo and 7.5 vol pct alumina was fabricated by dry mixing of powders, isostatically compacting at 30,000 psi, diffusing for 120 hr in dry hydrogen at 1800" F, and extruding at 1950"~ with a 30 to 1 reduction of area ratio. The resulting structure, presented in Fig. 1

Jan 1, 1963

EXECUTIVE COMMITTEES OF LOCAL SECTIONS New York LOUIS D. HUNTOON, Chairman. ARTHUR S. DWIGHT, Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. E. MALTBY SHIPP. Treasurer. GEORGE F. KUNZ, W. DE L. BENEDICT. Boston ROBERT H. RICHARDS, Chairman. ALBERT SAUVEUR, Vice-Chairman. AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. TIMOTHY W. SPRAGUE, HENRY A. WENTWORTH. Columbia F. A. THOMSON, Chairman. GEORGE W. RODDEWIG, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. R. S. McCAFFERY. S. H. RICHARDSON.

Jan 3, 1914

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959