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By Shun-ichi Satoh

Studies by many authorities have proved that nitrogen exerts an injurious influence upon iron and steel, but in the casehardening of steel by carbon, nitrogen has the advantage of accelerating the process of cementation. Its influence upon special steels is quite remarkable; it can produce the hardest layer ever known in metallurgical products—a fact hit upon by A. Fry and studied and ascertained by L. Guillet. As there have been very few investigations on the influence of nitrogen on special steels, the writer has listed important articles dealing with this problem and has conducted experiments on nitrification. He also has tested the influence of nickel upon the penetration of nitrogen in electric-arc welding. Nitrogen Process for Surface Hardening In 1919, Siegmonl conducted an experiment known as "Versticken" by treating steel with ammonia gas and found that the steel thus treated has the properties of resisting corrosion. In 1922, L. E. Benson3 nitro-genized iron and steel by sodium nitrate. Fry3-"studied the nitrogen process for surface hardening and published the results of his studies in 1923, 1924 and 1926. Guillet tested special steels containing various elements with the current of ammonia at 500' to 510' C.10, 11, 12, and determined the hardness of some of them at various temperatures.13 He also conducted corrosion tests14 in 1927. Fry15 stated that tinplat-ing could prevent nitrogen from penetrating into steel in the course of nitrification. In 1927, Guillet 65 described the historical notes of the nitrification; and many applications of nitrification were published in the Kruppsche Monatshefte.51, 59, 62, 63, 64-74~75 H. K. Herschman66 conducted the wear test of the nitrified steel. Gunnar Hägg investigated

Jan 1, 1930

US 4,181,588 - Direct extraction of lead from lead sulflde ore. Ore is leached with a solution of ferric chloride and sodium chloride. The leach liquor is filtered to remove sulfur and gangue, then cooled in a crystallizer to precipitate lead chloride The slurry from the crystallizer is subjected to electrolysis to deposit lead chloride on the cathode plate. Solution from the electrolysis cell is used in the leaching step. M.M. Wong and F.P. Haver, assigned to US Secretary of the Interior Jan 1, 1980. 6 pp. (204-115). Filed: 1-4-79 (1,026).

Jan 1, 1982

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.' Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

OIL FLOTATION DISCUSSED BY SOUTHERN CALIFORNIA SECTION . A meeting of the Section was held in the home of R. H. Norton, 335 W. 27th Street, on Mar. 10, thirty-two members and five guests being present. Vice-chairman Staunton opened the meeting with a description of an experiment he made with oil flotation, and then introduced the guest and speaker of the evening, L. C. Penhoel, of the South-western Engineering Co., who gave a very interesting and informal talk on the subject of Flotation. During the talk, as points were raised, there was a general discussion, in which valuable information was brought out. A number of examples of successful competitive, results by cyanidation and flotation in large milling plants in this country and Mexico were cited and discussed. The latter part of the meeting was devoted to a discussion of the bill introduced in the California State Senate, to license and register engineers. Mr. Ernest Strout gave a most favorable opinion of the principal of licensing mining engineers from his extensive experience in the working out of such a law on the Rand. All members who spoke were opposed to this bill as drafted but felt that the subject was of too great importance to the profession to attempt to amend the present bill in the week or two that remains, and that the passage of a bill that was so crude and inefficient for the achievement of the results desired, would harm the engineering profession. After the meeting adjourned a short time was spent in social intercourse, during which light refreshments were served. The appreciation and thanks of the Section is extended to Mr. and Mrs. R. H. Norton for their hospitality. ALVIN B. CARPENTER, Secretary-Treasurer.

Jan 5, 1919

H. G. Haemers (Ghent University, Belgium)—The authors claimed "the results of their work indicate that the metals can be arranged in a sulfation series similar in its application for selective sulfation tot the electromotive series for displacement of metals from solution". The series as stated in decreasing order for tendency of SO3 give up, is the same as that stated by free energy diagrams. Indeed, the degree of stability of a sulfate is measured by the free energy of sulfate formation out of the corresponding metal oxide and SO3. The more negative the value of the free energy (-DG) the greater the stability of the sulfate. As a second consequence this statement results in a relative aptitude for capture of SO3 by each metal oxide when brought in contact with the sulfate of other metals. Let M1 and M1 be the two metals, and — DG1 and — DG2 their free energy values at temperature T. Both sulfates are stable at temperature T if - DG1 < O and — DG2 < O. In case where — DG1 < — DG2 the stability of M1SO4 is greater than that of M2SO4, and when M1O (oxide of

Jan 1, 1958

By M. P. E. Desvaux, P. Charsley

OLIP-line observations on copper alloys, using the electron microscope, have been made by a number of workers,13 but this work has been confined to a brass. In a CuAl alloys Koppenaal4 and Koppenaal and Fine5 have made observations with the optical microscope and by the use of interferometry. They found that the observed slip step heights inside the Liiders bands accounted for only 42 pet of the total macroscopic strain. The suggestion was put forward that optically unresolvable slip in other parts of the specimen accounted for a major part of the macroscopic strain. This is surprising since it is known from other workers that slip in a brass is inhomogeneous; i.e., large amounts of slip occur on individual {lll) closelys paced than being shared by a large number of closely spaced planes. Furthermore, a brass and a CuAl alloys with high concentration of aluminum exhibit similar deformation characteristics and slip-line patterns. Prior to investigations into the behavior of copper and a CuAl alloys under reversed stresses in tension and compression, some preliminary experiments have yielded results which the authors think resolve this discrepancy, and throw some further light on the behavior of a CuAl in tension. An experiment was carried out on a 10 at. pet CuAl single crystal, of gage length 7.5 cm, diameter 3.1 mm, and orientation shown in Fig. 3 (inset), for the purpose of resolving the above discrepancy. The specimen gage length was electropolished for 10 min in a 50:50 orthophosphoric acid (SG=1.75)-distilled water system, with 2 v across the cell and a current density of 0.5 amp per sq cm. The cathode was made of copper. After a tensile strain of 0.067 ± 0.001, intense slip was observed over a length 2 cm of the gage length whilst the rest of the specimen was relatively undeformed. In the lightly deformed region, slip bands of mean width 20 /x were spaced about 1 mm apart on average. The transition from the heavily slipped region (usually called a Liiders band) to the lightly deformed region was gradual, the slip-band density increasing as the "Liiders band" was approached. In the latter, the slip bands became so close together that, to the naked eye, the specimen appeared to be continously slipped, and the typical microtopography of this region is shown in Fig. 1. Twelve electron micrographs were taken at random from replicas of the Liiders-band region, and the widths of the slip lines were measured. The slip lines account for an over-all tensile deformation of 7.0 ± 0.7 pet, after allowing for the lengths of the un-slipped regions, which is in good agreement with the macroscopic strain. The distribution of slip-line widths was also measured and is shown in Fig. 3. Since Koppenaal could not resolve slip lines with height less than 540A (limit of resolution represented by dashed line), then it was deduced that he could have measured only about 50 pet of the deformation within the &apos;Liiders Band&apos;. It is concluded, contrary to the suggestion of Koppenaal,5 that virtually all the macroscopic strain is accommodated within the "Luders band" and that there is no need to invoke fine slip distributed uniformly over the gage length.

Jan 1, 1967

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal etfect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24s-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to inter-crystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot he accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. Review of Previous Work In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknalll demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K • io"^ (i) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-~/m (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver.rich copper alloyZ and of duralumin.3

Jan 1, 1946

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal etfect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24s-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to inter-crystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot he accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. Review of Previous Work In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknalll demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K • io"^ (i) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-~/m (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver.rich copper alloyZ and of duralumin.3

Jan 1, 1946

By M. A. Quader, D. Kuhlmann-Wilsdorf, R. A. Dodd

STACKING fault tetrahedra were first observed in quenched and aged pure gold by Silcox and Hirsch1 and identified as defects originating in the collapse of vacancy discs on {111} planes. It was supposed that sessile loops are the first product of the collapse, and that by a dislocation dissociation/glide sequence these are converted into tetrahedra. Although the tetrahedra can be mechanistically accounted for in this way, recent investigations indicate that their growth occurs by the absorption of individual vacancies on small nuclei involving perhaps as few as six vacancies.2-7 Besides stacking fault tetrahedra, triangular and crystallographic shaped Frank loops, although fewer in number, have always been observed in quenched and aged gold.19798 It is not known definitely whether these loops form from collapsed tetrahedra. The fact that the Frank loops are usually larger than the accompanying tetrahedra might indicate that the loops grow independently by absorbing vacancies, but this does not rule out the possibility of the collapse of tetrahedra into loops under all circumstances. Silcox and Hirsch1 have actually observed under the electron microscope tetrahedra collapsing into loops, probably due to stresses set up by the heating of the specimen by the electron beam. The energy residing in the stacking faults of a tetrahedron is proportional to the square of the edge length, while the energy of a triangular perfect dislocation loop depends on its edge length, L, as const L ln(L/ro). Therefore, beyond some critical size tetrahedra must become unstable with respect to collapse into triangular loops.1,3,8-11 However, it seems that in the absence of strong stresses tetrahedra usually decay by the

Jan 1, 1969

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

THE first session of the Institute was held in the hall of the Washington University, Wednesday evening, May 27th, President Raymond in the chair. After the address of welcome by Hon. Thomas Allen, and the reply of Mr. Raymond, the following names were presented for election as members and associates, duly indorsed by the Council. They were unanimously elected : *Henry Booth, - New York City. *Charles H. Morgan, - Worcester, Mass. *Howard Painter, - West Chester, Pa. *Dr. M. J. Goodfellow, - Eberhardt, White Pine Co., Nevada *Otto Wittelshach, - Eureka, Nevada. *John T. Williams, - New York City. †Charles A. Young, - Philadelphia. *Charles E. Stafford, - Boston, Mass. *Arnold Hague, - Orange, N. J. *Richard Pearcé, - Black Hawk, Colorado. *W. R. Maffet, - Wilkes-Barre, Pa. *Prof. George A. Koenig, - University of Pa., Philadelphia *Prof. R. Nutting, Jr., - Indianapolis, Indiana. *Edwin Mickley, - Hockendauqua, Pa. *G. C. Broadhead, - St. Louis, Mo. *Dr. Adolph Schmidt, - St. Louis, Mo. *Alexander Leonhard, - St. Louis, Mo. *Edward D. Meier, - St. Louis, Mo. *John W. Meier, - St. Louis, Mo. *Prof. Forrest Shepherd, - St. Louis, Mo. *Edward Walsh, - Pilot Knob, Mo. *George Riggs, - St. Louis, Mo. †Col. Chas. B. Parsons, - Cadet, Mo. † W. A. Scott, - Mine La Motte, Mo. *Prof. Paul Schweitzer, - Columbia, Mo. *William E. Guy, - St. Louis, Mo. †William Harris, - St. Louis, Mo. *Henry Black, - Pittsburgh, Pa. †W. Noyes, - New York City. *W. Lorenz, - Philadelphia. †E. A. Whetmore, - New York City. * Members. †Associates.

Jan 1, 1875

By W. W. Stephen, J. P. Walsted, W. J. Kroll

FOR the production of carbides, various furnace types are available, especially those using arc, resistance, and high-frequency heating. Selection of a specific means of heating depends primarily on the material to be treated and the physical properties of the carbide produced. In the present case, zirconium carbide had to be prepared on an industrial scale as a raw material for the production of anhydrous zirconium chloride. Considering that a rather expensive pure oxide was to be used, the arc-furnace treatment recommended for zircon sands in a previous publication&apos; was ruled out because of the considerable volatilization and dust losses caused by the blast of the arc. For this reason, either high-frequency or resistance heating seemed to offer more promise. Since there was not enough capacity of the former available, resistance heating was chosen. It was first thought that the Acheson silicon carbide furnace would be suitable for the present purpose, but the voltage in such a furnace, in which the current passes through the batch, varies from 220 to 75 v from the start to the end of a run. This variation is so great that a special tap transformer would have been required. Trouble was also expected by local melting of the carbide. Pure zirconium carbide melts at about 3527°C, but the melting point is brought down to 2427°C, according to Agte,2 when an excess of 6 pct C is present in the carbide. This we found confirmed by experiments in a high-frequency furnace. Excess carbon is needed in the batch to obtain a complete reduction. Fusion of the charge would cause great difficulties in an Acheson-type furnace because of the good electrical conductivity of the carbide as compared with that of the loose batch. Also, fused carbide is much more difficult to chlorinate than the spongy product that can be made in the radiation furnace described below. It was apparent that, to obtain a good-qual-ity zirconium carbide, the heat input would have to be well-controlled. The hairpin-resistor principle seemed to offer possibilities in this regard, and a furnace of this type was therefore developed. The advantages of the hairpin-resistor radiation principle have been discussed in previous publications, and a split-tube graphite-resistor furnace," now increasingly used in various laboratories, as well as a centrifugal quartz melting furnace4 of this type, has demonstrated the usefulness of this heating method. The hairpin-heater element has the following definite advantages over a straight resistor of the type used, for instance, by Georges:5 Its resistance is four times greater; it can expand freely; it is sturdier because of the larger diameter, and it has a larger radiation surface; there are no hot contacts that might wear out or overheat; only one clamp is used which permits assembling all electrical leads at one side of the furnace, making the other sides easily accessible to the operator. The shorter element and its larger diameter permit greater concentration of heat. The furnace developed is shown in fig. 1. The box (I), made of 2 1/2-in. graphite plates, has inside dimensions of 23x17x16 in. It contains the briquet-ted batch (2). The box is embedded in lampblack (3) up to the cover plate. The cover plate contains an opening for the gas escape (4) and for the observation hole (5), which permits measuring the temperature with an optical pyrometer. The cover plate is embedded in charcoal (6). The lampblack is contained in the insulating brick lining (7), held in the 1/4-in. sheet steel box (8). The graphite box is set on two rows of triangular graphite bars (9). The hairpin-heater element (10), the dimensions of which are given below the main drawing, extends horizontally in the graphite chamber and radiates freely on the batch. A graphite tube (11) keeps the lampblack from falling into the slot. The split electrode, which in reality is turned 90" against the drawing, is so arranged that the slot is vertical. The water-cooled packing gland (12) is insulated by an airgap from the heater element. A thin pipe (13)

Jan 1, 1951

By T. S. Lundy, J. I. Federer

A graphical method has been developed and tested for separating the effects of grain boundary and lattice diffusion in polycrystalline materials. The method is based on the assumptions that for unidirectional diffusion from a plane source of radioactive material, the penetration of activity far into the specimen from the source is due solely to grain-boundary effects, and 2) pure grain-boundary penetration is described by a linear plot of log activity vs the perpendicular distance x from the source. The former is based on the fact that at any temperature the grain-boundary diffusion coefficient is always very large relative to the lattice diffusion coefficient; and the latter is based on the derivation of Fisher.1 Using these criteria along with appropriate penetration data (in this case, data for the diffusion of Cb95 in pressed and sintered UO2) one first plots the data as log activity vs x2 and as log activity vs x, as shown by curves 1 and 2, respectively, in Fig. 1. A tangent line to curve 2 for large x (curve 3) is then transferred to the x2 plot as curve 4. The subtraction of curve 4 from curve 1 yields curve 5 which represents only lattice diffusion and may therefore be related to the diffusion coefficient by using the appropriate solution to Fick&apos;s second law. It should be noted that the method has inherent inaccuracies for small and large values of x2 and only the subtraction at intermediate values can be used. For the illustrated specimen the calculated diffusion coefficient is 3.4 X 10-11 sq cm per sec at1445°C while data using a single crystal of UO2 at the same temperature yielded a value of 2.9 x 10-11 sq cm per sec.2 The same method of subtracting grain-boundary diffusion effects to obtain lattice diffusion coefficients has been successfully used to determine self-diffusion coefficients of Th230 in polycrystalline thoria.

Jan 1, 1962

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into &apos;&apos;high", &apos;&apos;medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4&apos;6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~&apos; for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By Sylvan Z. Beer

Aluminum phosphide was synthesized and grown in solution of excess aluminum using a modified two-temperature technique. An inversion in the density difference between ALP and molten aluminum takes place at about 1100°. Dispersed nuclei can act as sources for further crystal growth in a manner resembling ripening. Advantage was taken of this phenomenon by introducing a stirring motion into the molten liquid. This was done with a split-phase 10-kH2 rotating magnetic field produced by four horizontal coils placed symmetrically about the furnace at the level of the molten metal. The method also prevents the formation of a surface film which would impede the reaction. By this technique vastly improved yields were obtained and flat crystals 5 by 5 by 0.5 mm were grown at lower temperatures and at greater rates than heretofore. THE family of III-V intermetallic compounds has received much attention since the prediction of their semiconducting properties in the early 1950s. Of the family, A1P has perhaps the highest band gap of those compounds normally possessing the zinc-blende structure. But it has been least studied because it is difficult to handle and grow. The handling difficulties have been dealt with elsewhere and it is sufficient to say here that, by various techniques, many of the difficulties can be overcome.&apos; The difficulties encountered in crystal growth can be related to the refractory nature of A1P and in turn to its high band gap. Because of the anticipated high melting point of the material and the accompanying high phosphorus vapor pressure, the reported work on synthesis and growth was done by epitaxial synthesis-growth via chlorine2 and iodine3 transport and from solution of excess aluminum by the two-temperature technique.4&apos;5 The transport-grown crystals take on the dimensions of the substrate but do not grow easily in thickness. In the usual two-temperature technique as applied on the synthesis of Alp, the temperature of the molten aluminum is kept at 1000° to 1250°C while the phosphorus is maintained at 1 to 20 atm. A thin film of aluminum phosphide and oxide form immediately, impeding the reaction and affecting the yield. Attempts to grow the Alp from such solutions by the methods used to grow Gap and InP from excess gallium and indium have not been successful. As discussed in the preceding paper,5 the yield can be greatly increased

Jan 1, 1969

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author&apos;s reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By J. O. Brittain, N. R. Adsit

A number of zinc bicrystal specimens with the grain boundary loaded in simple shear were plustically deformed in creep in a vacuum at 200°C and under an argon atmosphere at 350°C. The results indicated that the amount of grain boundary sliding at a given time was controlled by the slip in the grains and was proportional to the resolved shear stress on the slip plane. Curves of grain boundary sliding vs time were found to be cyclic with no regular periodicity. ALTHOUGH grain boundary sliding (G.B.S.) has been investigated in a number of different types of tests on various materials there is substantial disagreement on the interpretation of the various observations. Gifkins1 has presented a comprehensive review of the subject of G.B.S. and fracture. He reports that the activation energy for high-temperature creep is equal to that for volume self-diffusion and that pure metals show less tendency towards intercrystalline fracture than alloys. Pure metals show appreciably greater grain boundary migration than alloys, and both grain boundary migration and grain boundary sliding follow the same general trend in time as plastic deformation during creep.&apos; While there have been a number of different mechanisms proposed to account for G.B.S., none of the models explains all the results. Since zinc has only one prominent slip system, it was hoped that experiments on G.B.S. in zinc bicrystals might enable us to separate the effect of grain boundary angle and the effect of matrix slip and thereby resolve at least one part of this complex phenomenon. EXPERIMENTAL PROCEDURE Bicrystals of pure zinc (99.99 pct) were grown by a Bridgeman technique in a furnace having a gradient of 20°C per in. The bicrystals were seeded to a desired orientation and grown in a split graphite mold which was 3/4 by 5/8 by 8 in. The mold was enclosed in a Pyrex tube and the tube was evacuated and then filled with a small amount of argon before it was placed in the furnace. The growth rates were 1/2 to I in. per hr for the bicrystals and 1/2 to 3 in. per hr for the single-crystal seeds. The longitudinal V notches served to hold the grain boundary in position during the growth process. A schematic rep- resentation of a specimen which had been cut with a jewelers saw from the bicrystals is shown in Fig. 1. All specimens of a series were cut from the same crystal, some of which were 7 in. in length. After specimen preparation the boundary was approximately 5/16 in. long and the V notches had a radius of 1/16 in. The boundaries were straight at a magnification of X100 with the exception of a few which had a gradual radius of curvature of greater than 3.2 in.-1. Laue back-reflection photograms were taken on the specimens to check the orientation of grains in the bicrystals. The method of relating the orientation of the two lattices is shown in Fig. 1, where 0 is the angle between normal to the boundary and the trace of the basal plane, is the angle in the boundary between the trace of the basal plane and a line parallel to the V notch, and x is the angle in the basal plane between the Burgers vector and the perpendicular to the grain boundary. After mechanical polishing the specimens were chemically polished.2 Subsequent to the polishing operation the specimens were encapsuled under a vacuum of better than 25 annealed at 340°C for 1 hr to remove the effects of this handling, and again chemically polished. Finally, fiduciary marks were scribed on the specimen using a micromanipulator. Creep tests, which were conducted in a modified Bausch apparatusS with the boundary loaded in simple shear, were run at a constant load (since the boundary area remained essentially constant this is approximately constant grain boundary stress). The temperature was controlled to ±1/4°C as measured on a semiprecision potentiometer with a calibrated thermocouple. The specimens were tested in a vacuum of better than 0.5 at 200°C and in purified argon at a pressure of 1/2 atm at 350°C. The op-

Jan 1, 1965

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Jan 1, 1961

By B. K. Larkin, H. K. van Poollen, H. C. Bixel

A detailed treatment is given of the transient pressure behavior of a well located near a linear discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility, and porosity are uniform, but may be different from those on the other side of the discontinuity. These results generalize previously published works which assumed the permeability ratio for media on different sides of the discontinuity was zero, one, or infinity. One application of this material would be to facilitate detection of facies changes or fluid-fluid contacts by transient testing. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables examined includes dimensionless time from 0.1 to 100, rnohility ratio from 0.001 to 1000 and specific compressibility ratio from 0.001 to 1000. For dimensionless tinze less than 0.4, the pressure behavior is essentially that of a well in an infinite reservoir. Thus, reservoir properties near the well may be estimated in the usual manner. Using an overlay technique to match an experimental curve with one of the theoretical curves, it is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time , at which a match occurs into the equation where is the diffusivity near the well, and may be estimated from data taken at early time. Because of both the complexity of the solutions and limited computer facilities, well interference problems were not examined extensively. However, it was found that well interference may be masked by the discontinuity in some cases. By superposition of the results of constant rate fluid production, the problenz of pressure buildup may be treated. Such results show that for early shut-in times correct values for the transnzissibility are obtained from conventional semilog plotting. However, erroneous values of the static reservoir pressure are obtained unless data at large shut-in times are taken. INTRODUCTION Transient well testing has yielded estimates of such reservoir parameters as static reservoir pressure, permeability. porosity, and well bore effects. In most tests, it was assumed that the reservoirs were homogeneous and iso-tropic. Anisotropic media&apos; and radial discontinuities were considered.&apos;.&apos; Various studies have been made on multiple-layer reservoirs." &apos; Linear discontinuities have been described for problems of one-dimensional flow.&apos; In the present paper, a mathematical treatment is given for a well located near a linear discontinuity in an otherwise infinite medium (see Fig. 1). An actual reservoir analogy would be a well in a relatively thin reservoir near a fluid-fluid contact, or a well located in a reservoir exhibiting a sudden change in rock and formation characteristics, such as thickness, porosity, or permeability. A sudden change in porosity or permeability may be caused by clay fill or other types of facies changes. Sudden thickness changes niay be the result of such geological formations as buried shore lines and channel deposits. In otherwise uniform formations, a linear discontinuity may be caused by fluid-fluid interfaces such as oil-water contacts. 3s-oil contacts, or gas-water contacts.