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By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

By J. G. Early, F. V. Lenel, G. S. Ansell

The isothermal shrinkage rates of copper-powder compacts were determined in the temperature range from 760o to 1060oC. The rates for compacts fabricated from a pure spherical copper powder were compared, on the one hand, with those fabricated from a spherical powder containing a dispersion of aluminum oxide in the copper matrix and, on the other hand, with those fabricated from a pure copper powder having irregularly shaped particles. The irregular copper-powder compacts shrank much faster than the spherical copper-powder compacts and these, in turn, shrank faster than dispersion -strengthened copper -powder compacts. The experiments were run under a small external load. By varying this load, the stress dependence of the isothermal shrinkage rate could be measured for compacts from spherical-copper powders. This stress dependence was found to be approximately proportional to the 4th (dispersion-strengthened alloys) or 4.5th (pure metals) power of the stress. It is concluded that the material-trans port mechanism is due to dislocation climb rather than to Herring-Naharro creep. In this investigation the isothermal shrinkage rates of compacts made of copper powder with an average particle size of 70 g in the temperature range from 780o to 1060°C were studied. The aim of the investigation was to determine the mechanism of material transport responsible for the shrinkage of these compacts. Since the phenomenon observed in this investigation was shrinkage of compacts at high temperatures, it will be necessary to consider all the material-transport mechanisms possible in sintering. It is unlikely that evaporation and condensation, surface diffusion, or even volume diffusion of vacancies, in which surfaces of small radius of curvature are vacancy sources and those of larger radius of curvature vacancy sinks, will materially contribute to a sintering process involving shrinkage, i.e., one in which the centers of adjacent particles move towards each other. The two principal mechanisms which were considered were the so-called Nabarro-Herring mechanism and a plastic deformation mechanism by dislocation movement. Both of these mechanisms were originally conceived to explain creep, i.e., the plastic deformation of metals at elevated temperatures under a constant applied stress. The shrinking of metal-powder compacts which was studied in this investigation can be readily treated as a creep process. This means that the shrinkage rates observed are considered as creep rates under the influence of an applied stress. It is true that the stresses in sintering experiments are generally not constant but decrease continually with time, but, by considering creep rates or shrinkage rates over a relatively short time interval, the small changes in stress during this time interval can generally be neglected. Nabarro-Herring microcreep is a high-temperature deformation mechanism which is caused by a diffusional flow of vacancies from boundaries under a tensile stress towards those under a compres-sive stress. Herring1 has shown that in this type of microcreep the strain rate e is proportional to the applied stress and follows an equation of the form ma, aexp(-Q/RT) [l| where <j is applied stress, Q is the activation energy for self-diffusion, R is the gas constant, and T is the absolute temperature This type of creep can explain the shrinkage of a porous compact. The surface of the pores are subjected to the tensile stress of surface tension, while the grain boundaries are under a compressive stress also due to surface tension. Vacancies diffuse from the pore surface through the lattice to the grain boundaries, where they are eliminated. In order to maintain vacancy equilibrium at the pore surface the vacancies leaving the region of the pore surface are replenished from the volume of the pore, which means that the pores shrink.

Jan 1, 1964

By C. M. Heath, B. W. Gonser

Soft solders are used principally in the automotive, can-making, building construction and electrical industries, but their field of usefulness extends well beyond these principal users to a vast list of miscellaneous applications where metal joints are required. The most common soft solders and the only ones considered in this discussion are those composed of lead and tin, with or without various relatively small percentages of impurities or additions. A small amount of antimony is often purposely added. As an indication of the importance of these lead-tin solders, 8620 long tons of tin were consumed in 1934 in the United States for making new solder, and during most of 1935 from 900 to 1000 long tons often were used each month. In addition, many thousands of tons of secondary solder are recirculated annually. A great many factors influence the properties of joints made with soft solders. Fluxes and the fluxing procedure used to prepare the surfaces to be joined in order to give a true metal-to-metal contact are among the most important of these factors. The temperatures used, cleanliness of the work and general soldering technique have their effect, but when results are unsatisfactory they are usually attributed to the metallic solder itself and the raw materials from which it is made. Sometimes criticism of the solder is justified. The wrong composition may be chosen for a given job, impurities may be present that ruin certain desired qualities, or uniformity may be lacking. A solder may even be looked upon with suspicion because of its ancestry, regardless of its true composition and behavior. To clarify the effect of slight differences in composition as found in commercially refined solders, a comparison of properties of solders grouped according to their origin has been undertaken. This investigation seeks to give practical information on the properties of tin-lead solders produced from virgin metals, from commercially refined secondary solder, and from an electrolytically refined crude

Jan 1, 1936

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1&apos;2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900&apos; C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1&apos; and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By Simon H. Ash

The coal-mining districts of Washington are mainly west of the Cascade Mountains; Fig. 1. The mines are on the foot hills of the slope, the lignite fields of Lewis and Thurston counties extending into the valleys west of the mountains. An exception is the Roslyn field, a small but important area on the eastern slope. If western Washington is divided into three areas from north to south, the bituminous coal fields and most of the active operations will be found largely in the middle area. The southern portion contains lignites over a large area. In the northern portion, mining is practically restricted to one mine, the Bellingham, which is working a subbituminous coal seam near the city of Bellingham. The degree of alteration that the coal of a particular field has undergone may be gaged roughly by the position of the field with reference to the Cascade Mountains. The lignites of Tenino, Tono, Mendota, and Castle Rock, on the railway line connecting Seattle and Portland, occur in a region of low relief, in which the Eocene coal measures have suffered only minor disturbances. Subbituminous coals occur in the foot hills, as at Renton, Newcastle, and Bellingham. Coalg high in fixed carbon are found nearer the mountains, where the measures have been sharply tilted and folded, as at Black Diamond and Carbonado. The two typical anthracite fields are located still higher, in the rugged mountains where outcrops appear both in deep gorges and on ridges at elevations approaching 5000 ft. At Carbonado is found the only semianthracitc seam worked on a commercial basis. The occurrence of this seam in a region of bituminous coal is due to the nearness of an igneous sill, which has changed its character from bituminous to semianthracite. Purpose of Paper On account of the various faults and dips and the varying nature of the wall rock, many difficulties are encountered in mining and winning the coal. The paper gives some of the methods used in mining and, in some detail, the conditions that affect the efficiency of these methods.

Jan 1, 1925

By J. Clayton Nichols

The principal mines of this region are 7 miles SE. from Gusa, and about 4 miles in a direct line from the seacoast. Gusa is a small town on the north coast of Mindanao, 4 miles east from Cagayan, the capital of the province of Misamis. The mines are reached by steep, narrow trails over ridges varying in altitude from 1100 to 1600 feet above sealevel. The whole region is covered with a thick growth of tall grass, except a few spots on the sides of some of the hills, where there are patches of timber and jungle.

Jan 1, 1902

By S. W. Poole, J. A. Rosa

The object of this investigation was to determine the distribution of chemical elements within a large, killed alloy-steel ingot, by sulphur printing and quantitative chemical analysis. With regard to segregation in steel ingots, the factors of melting practice, pouring temperatures, mold design, etc., and the mechanics of solidification and its attendant functions, have been the subject of intensive study over a period of years by many investigators. Notable among these is the Sub-committee of the No. 5 Committee of the British Iron and Steel Institute. For an exposition of the many problems awaiting the researcher on the heterogeneity of steel ingots, the methods of attacking these problems, together with some of the answers, the reader is referred to the nine reports and numerous papers of that committee and its membership. Steelmaking Data Melt.—The heat was made in a 70-ton direct arc-type basic electric furnace. Furnace charge consisted of nickel-chromium-molybdenum steel, most of it in the form of heavy mill scrap. All of the scrap was charged cold. The standard double-slag method was employed, the heat being finished under a strong carbide slag. Aluminum was used as the deoxidizing agent. Tapping tempera- ture, as observed with an optical pyrometer, was 3000°F. Detail of Mold and Ingot Size.—Details of the ingot mold and the ingot itself are given in Fig. I. Teeming.—Teeming temperature of the subject ingot as observed with an optical pyrometer was 2830°F. The ingot was top-poured directly through a 1 1/2-in. nozzle and required 7 min., 44 sec. to fill up to the hot top. An additional 2 min., 30 sec. were required to fill the hot top. The ingot was stripped hot and charged with the remainder of the heat into an annealing furnace. There it was given the standard annealing cycle used for these ingots. Subsequent heat-treatments are described elsewhere in this paper. Sectioning and Preparation for Sulphur Printing Because of previous favorable experience in sectioning ingots up to 21 1/2 in. square with an oxyacetylene torch, it was decided to use this method to section the subject ingot. The ingot was preheated to 900°F. for 12 hr. It was then placed on a steel bed in a horizontal position so that the longitudinal axis was level and parallel to the track of the motor-driven torch carrier. Two cuts were made, one 2 in. above the longitudinal axis and the other 2 in. below. The time required to make each cut was approximately 75 min. The cutting operation is shown in Figs. 2 and 3. The 4-in. thick slab was mmediately charged into a furnace standing at 1200F.

Jan 1, 1945

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. ROBERT W. HUNT CHICAGO, ILL. (Term expires February, 1907.) VICE-PRESIDENTS OF THE COUNCIL. WILLIAM P. BLAKE TUCSON, ARIZ. THOMAS F. COLE DULUTH, MINN. IRVING A. STEARNS WILKES-BARRE, PA. (Term expires February, 1907.) HENRY AL HOWE NEW YORK, N. Y. J. B. GRANT DENVER, COLO. JAMES D. HAGUE NEW YORK, N. Y. (Term expires February, 1909.)

Jan 1, 1907

By W. S. Owen, A. R. Rosenfield

The measured changes in the yield stress of a poly crystalline Ta-O alloy after strain aging at 100°C have been separated into two components; the change inflow stress and the change in dislocation locking parameter. These two components vary independently indicating that at least two separate recovery processes take place during strain-aging. Variations in the locking parameter can be accounted for by segregation of oxygen atoms to dislocations, but variations inflow stress cannot be explained by current theories. STRAIN-AGING in Fe-C and Fe-N alloys has been studied extensively.&apos; The kinetics of the removal of the interstitial solute from solution appear to agree with the predictions of the cottrell-bilby2 model or a variation of it proposed by harper.3 Solute segregates to the dislocations under the influence of the elastic strain field of the dislocation and the rate of depletion of the solute can be measured by following the change in electrical resistivity4 or internal friction.5 On reloading a prestrained specimen, plastic flow starts at Fig. 1, but after aging the reloaded specimen yields discontinuously at a higher stress The aging index reflects the extent to which the yield has returned. Until recently it was usual to assume that ? is a result solely of the pinning of dislocations by the segregated solute atoms, that is, that op and oj coincide and the strain hardening curves AB and CD are continuous. Thomas

Jan 1, 1963

By J. R. Low

The brittle fracture of a Tic-lnconel cermet at room temperature is shown to occur primarily as a result of the cracking of the larger carbide particles (at a tensile strain of approximately 0.3 pct), followed by cracking of adjacent, smaller carbides and, finally, by the rupture of the lnconel matrix between cracked carbides (at a strain of-1.2 pct). No evidence was found for separation at the interface between carbide and matrix at any point in the fracture process. MATERIAL used in this study was a Tic-Inconel cermet prepared by infiltration (50 pct Tic, 50 pct Inconel: designated as TC66-I). A thin section of this material was brazed to a piece of low carbon steel and then mounted in lucite for metal-lographic preparation." After grinding, polishing, Deformation and fracture of the specimen was accomplished by bending the specimen as a simply supported, centrally loaded beam, in a bending fixture which could be placed in the stage of a microscope, with the tension side of the bend specimen under the microscope objective.? This method of deformation and observation has the advantage that the surface under examination is the most severely deformed portion of the specimen. The procedure followed was to deform the specimen a small amount, scan the surface at Xl OOO for any evidence of deformation or cracking, deform another small increment, scan the surface again, and so on until a

Jan 1, 1957

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts&apos; law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN&apos;S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts&apos; law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.&apos; The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."&apos; The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-&apos;* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

By W. R. Hibbard

It has been proposed1 on the basis of slip and flow that the ideal deformation texture of drawn wire for face-centered cubic metals is a (111) direction parallel to the wire axis. Under these considerations, an intermediate [loo] texture is permissible but should eventually change to the stable [Ill] orientation. This theory does not explain why copper and its alloys containing up to about 30 pct nickel, 5 pct zinc and 1 pct aluminum were found to have a double [Ill], [100] texture, while alloys with at least 8 pct zinc and 2 pct aluminum developed essentially a single [Ill] texture.1,2 It does suggest, however, that the [loo] component of the former alloys should disappear with additional deformation.3 Some evidence exists to support this suggestion. Howald4 reported that annealed copper wire previously drawn 93.8 pct and 98.5 pct developed a single [Ill] texture. Since, in wire, the drawn and annealed textures are similar, these wires probably had a single [Ill] deformation texture before annealing. In addition, although cold rolled polycrystalline copper and 80-20 brass were found to form different types of pole figures,5,6 single crystals of these metals when rolled from the stable (110) [112] orientation were found to produce essentially the same polo figure.7.8 It may be, therefore, that while the addition of solute elements changes the path by which the final texture is obtained, the final texture is not changed. Experimental Results The wires remaining from the previous investigation1 already drawn about 50 pct reduction in diameter were further drawn to 86 pct and then to 96.4 pct total reduction in diameter. The textures were determined after these stages by transmission X ray photograms taken with a copper K-alpha beam rotated 0 degrees toward the wire axis. It was found that the ratio of the [111].] and [100] intensities of the double texture in copper and its alloys containing 0.94 pct aluminum, 30.70 pct nickel, 2.61 pct zinc and 4.99 pct zinc increased from about 3:l for the 50 pct reduction to about 9:l for the 86 pct reduction. After 96.4 pct reduction, these wires exhibited essentially a single [lll] texture. Summary Thus, the drawn wire deformation texture of copper and its alpha solid solution alloys containing aluminum, nickel or zinc is essentially a single [Ill] texture as predicted by theoretical considerations of slip and flow.&apos; For copper and its alloys containing up to about 1 pct aluminum, 5 pct zinc and at least 30 pct nickel, an intermediate [loo] component is found after about 50 pct reduction in diameter, but disappears after about 95 pct reduction in diameter. For alpha solid solution alloys containing at least about 2 pct aluminum and 8 pct zinc the single [Ill] texture is developed considerably more easily and is found after about 50 pct reduction in diameter. No explanation of this compositional effect is apparent. Similar work is contemplated for cold rolled and cold compressed alloys. References 1. w. R. Hibbard, Jr. and M. K. Yen: Trans. AIME 175, 126. Metals Tech., Feb. 1948, TP 2334. 2. W. R. Hibbard, Jr. and D. E. Trout, 11: Trans. AIME 185, 620. Jnl. of Melals, Sept. 1949, TN 18. 3. W. R. Hibbard. Jr.: Disc. of R. M. Brick&apos;s paper on Deformation Textures, ASM Symp. on Cold Working of Metals, Oct. 1948. 4. T. S. Howald: Disc. of Ref. 1. Trans. AIME, 175, 126. Melals Tech. Aug. 1948, TP 2449. 5. R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675. 6. 0. Dahl and F. Pawlek: Zlsch. Melall. (1936) 28, 266. 7. C. S. Barrett and F. W. Steadman: Trans. AIME (1942) 147, 57. 8. J. E. Burke and C. S. Barrett: Trans. AIME 175, 106. Melals Tech., Feb. 1948. TP 2327.

Jan 1, 1950

By G. N. Maniar

G. W. Healy (union Carbide Metals Co.)-The author&apos;s paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author&apos;s recently published one1 on the CaO-FeO-Fezo3 system will be most helpful to others learning to apply Schuhmann&apos;s method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fe2O3 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By H. F. Yancey, M. R. Geer, C. L. Allyn, R. H. Eckhouse

W. M. Bertholf—This is an excellent report of a well-conducted investigation, of sufficient scope to provide generally useful information. Some years ago we had occasion to test the Humphreys spiral on the middling from our table plant. The conclusions reached in this investigation come as no surprise to us. In certain applications it is virtually impossible to improve on the spiral from the monetary returns point of view even though its "efficiency" may be low. We have noted that in all successful applications of the spiral the feed is "classified," hence we were somewhat disappointed in the showing the spiral made on the Poplar Ridge coal, the only one of the four which could really be considered the equivalent of a classified feed. As was noted in the paper, however, this coal contained a considerable amount of middle and high-gravity material, apparently more than enough to make up for the theoretical advantage of small particles in these categories. A comparison of particle size in the various specific gravity classes of the four coals is given in table XXV. Table XXV. Comparison of Particle Size in Various Specific Gravity Classes. (Unit size, 150 m to 0.105 mm) Black Eagle Clements Poplar Ridge Rosly,n 1.3 Float 7.47 10.60 8.68 9.66 1.3 x 1.4 7.89 7.96 7.58 8.20 1.4x1.6 7.24 8.36 5.58 6.85 1.6 x 1.8 7.98 8.31 3.42 7.33 Sink 1.8 7.85 7.13 5.09 7.41 Avg 7.69 10.08 7.15 8.38 This tabulation indicates that there was very little difference in the size of the various gravity fractions for three of the coals, Poplar Ridge varying the most. Examination of figs. 3, 6, 7, and 8 reveals a general similarity of behavior for all coals except Black Eagle. Would the authors care to speculate on the reasons for the difference in the distribution curve for the sink 1.60 material in the washed coal of fig. 3 as compared to the others? This difference is particularly noticeable in the 8xl4-mesh size. Was there a "shape effect"? J. D. Price and W. M. Bertholf—The performance data on three of the coals studied appear to be typical, but there are certain departures from the general pattern in the case of the Poplar Ridge coal which are large enough to deserve special consideration. For example: 1. Despite the high proportion of sink 1.60 material in the feed, it was not possible to make a corresponding proportion of high-ash reject. (See table XVI.) 2. Even though approximately 70 pct of the feed was 1.40 float with an ash content of 6.6 pct, and this

Jan 1, 1951

By R. H. Eckhouse, M. R. Geer, H. F. Yancey, C. L. Allyn

W. M. Bertholf—This is an excellent report of a well-conducted investigation, of sufficient scope to provide generally useful information. Some years ago we had occasion to test the Humphreys spiral on the middling from our table plant. The conclusions reached in this investigation come as no surprise to us. In certain applications it is virtually impossible to improve on the spiral from the monetary returns point of view even though its "efficiency" may be low. We have noted that in all successful applications of the spiral the feed is "classified," hence we were somewhat disappointed in the showing the spiral made on the Poplar Ridge coal, the only one of the four which could really be considered the equivalent of a classified feed. As was noted in the paper, however, this coal contained a considerable amount of middle and high-gravity material, apparently more than enough to make up for the theoretical advantage of small particles in these categories. A comparison of particle size in the various specific gravity classes of the four coals is given in table XXV. Table XXV. Comparison of Particle Size in Various Specific Gravity Classes. (Unit size, 150 m to 0.105 mm) Black Eagle Clements Poplar Ridge Rosly,n 1.3 Float 7.47 10.60 8.68 9.66 1.3 x 1.4 7.89 7.96 7.58 8.20 1.4x1.6 7.24 8.36 5.58 6.85 1.6 x 1.8 7.98 8.31 3.42 7.33 Sink 1.8 7.85 7.13 5.09 7.41 Avg 7.69 10.08 7.15 8.38 This tabulation indicates that there was very little difference in the size of the various gravity fractions for three of the coals, Poplar Ridge varying the most. Examination of figs. 3, 6, 7, and 8 reveals a general similarity of behavior for all coals except Black Eagle. Would the authors care to speculate on the reasons for the difference in the distribution curve for the sink 1.60 material in the washed coal of fig. 3 as compared to the others? This difference is particularly noticeable in the 8xl4-mesh size. Was there a "shape effect"? J. D. Price and W. M. Bertholf—The performance data on three of the coals studied appear to be typical, but there are certain departures from the general pattern in the case of the Poplar Ridge coal which are large enough to deserve special consideration. For example: 1. Despite the high proportion of sink 1.60 material in the feed, it was not possible to make a corresponding proportion of high-ash reject. (See table XVI.) 2. Even though approximately 70 pct of the feed was 1.40 float with an ash content of 6.6 pct, and this

Jan 1, 1951

By B. D. Cullity

INTRODUCTION THIS investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy-the thermoelectric efficiency-has been discussed by Telkes1 in a recent review of the subject. She gives the thermoelectric efficiency as: [ ] For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of properties. BISMUTH-SELENIUM ALLOYS Work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson,2 who gives the diagram reproduced in Fig I. There are two intermediate phases in this system, BiSe and Bi2Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedral crystal

Jan 1, 1948

By J. C. Borland, J. H. Rogerson

Jan 1, 1963

By H. A. Dierks

PENNSYLVANIA&apos;s anthracite region lies in the heart of the richest and most densely populated area of the U. S. Nearly 70 million people live within a radius of 500 miles, in which 130,000 manufacturing plants employ more than 8 million workers. The region comprises some 3000 sq miles and contains 484 sq miles of coal measures, which folding and erosion have divided into four separate and distinct fields, known as the Northern, Eastern Middle, Western Middle, and Southern.

Jan 10, 1957

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.&apos; Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951