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By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By Roy W. Moore

The Tom Reed Extension and Big Jim mines of United Eastern Mining Co. are situated in the Oatman district, Mohave County, Ariz., about 28 miles southwest of Kingman, the nearest railway point. Articles descriptive of the mine surface plant, mill construction, and plant operations have been written by Otto Wartenweiler,' the designing engineer; Wheeler 0. North12 when he was assistant general manager for the company, and Earle M. Bagley, mill superintendent.3 The last article covers average costs for the full time the mill was operated. The geology of the mines is described by F. L. Ransome 4 of the United States Geological Survey. Production was started in January, 1917, and the known orebodies were exhausted in May, 1925, showing a life of seven years and five months. On account of the comparatively short life and the fact that stoping operations were confined to two orebodies, little experimenting was done with mining methods. The two orebodies were in what is generally called the Tom Reed-United Eastern vein, which occupies a fault fissure having a normal displacement of several hundred feet. Seven or eight very productive ore shoots were mined along this vein in a distance of 1 1/2 miles, the two worked by the United Eastern being 1 mile apart. The maximum dimensions of the Tom Reed Extension ore shoot were: height, 750 ft.; length, 950 ft.; thickness, 48 ft. The vein structure varied from a solid quartz-calcite filling to a series of parallel stringers separated by andesite. From this body, 511,976 tons of ore were mined. (Fig. 1.) The maximum dimensions of the Big Jim orebody were: height, 450 ft.; length, 850 ft., thickness, 35 ft. Its structure was similar to that of the Tom Reed Extension but larger sections of the vein were made up

Jan 1, 1928

By Warnie Flint

PERSONAL INJURY ACCIDENTS According to statistics compiled by the National Safety Council, US Bureau of Mines, American Medical Association, and other agencies, accidental injuries cause more deaths than all the leading diseases. NO one is immune to an accident. Probably the best way to describe an accident is to say that it is an unexpected happening. The automobile driver is not expecting a terrifying crash, the electrician does not expect to be electrocuted, nor is the coal miner expecting the roof to fall on him. All personal injuries will not result in death. There is a multitude of victims who arc living proof of what accidents can mean to an individual-victims who are blind, paralytic, missing arms, legs, etc. In most instances the earning power of these individuals is gone, and they arc utterly dependent upon family or welfare. For many years there seemed to be an attitude that prevailed in industrial America that accidents were inevitable, and that so many fatalities and injuries should be expected. This, of course, was utter nonsense. Since the birth of such organizations as The National Safety Council, American Society of Safety Engineers, and the US Bureau of Mines, much progress has been made in reducing accidents. The enactment of compensation laws greatly contributed to the progress that has been made. Does this mean that all accidents can be prevented? Unfortunately, it does not. Human psychology indicates that men will work unsafely or perform unsafe acts for the following reasons : 1) Lack of Knowledge or skill. 2) Conflicting motivations, such as: (a) to be more conformable, (b) to save time or effort, (c) to be accepted by a group. 3) Physical or mental condition. Nearly everyone desires his own safety, hut not all individuals are willing to do what they know to do to insure their own safety.

Jan 1, 1981

By J. A. Herbst, G. E. Agar

The effect of fluid viscosity on the classification of solids in a liquid-solid cyclone was investigated. The separation size was found to be proportional to Additionally, it was found that the prediction of flow rate through a cyclone is dependent on a Reynolds criterion. Above a critical value, the flow can be predicted by a simple equation, whereas, below this value a variable orifice coefficient must be introduced. INTRODUCTION The solid-liquid cyclone is widely used as a device for classification, thickening, and heavy media separations. The more important variables and how they affect the performance of a cyclone are known and have been the subject of several investigations.' In general, these studies have paid little attention to the viscosity and those which have, introduced it through Stokes settling considerations. Systems which contain appreciable amounts of swelling clays exhibit viscosities much greater than water, and in these systems the viscosity term becomes important in determining the separation size. The work described here was done to determine in a Newtonian system the dependence of separation size on viscosity. BACKGROUND The separation size for a cyclone classifier has been related to the parameters of the cyclone by an equation of the form: where a is probably between 1.3 and 1.5, ß is between 0.50 and 0.57, and 6 has a theoretical value of 0.5. where y has a value between 1.8 and 2.0. Although these relationships are empirical, equations that differ only in the exponents have been derived from theoretical considerations. Those interested in the origin of these equations are referred to some of the original work.6,7 MATERIALS AND PROCEDURE The laboratory apparatus used in this study is pictured diagramatically in Fig. 1. Feed slurry was pumped from an agitated 15-gallon plastic tank by a centrifugal pump driven by 3/4 hp motor. The static pressure of the feedstream and thus the pressure drop through the cyclone was measured on a gage located as close to inlet of the cyclone as possible. When samples were not being taken, overflow and

Jan 1, 1967

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10'6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By C. G. Dunn, W. W. Martin

Various X ray diffraction techniques have been developed for determining orientations of crystals. Transmission and back-reflection Laue methods1,2,3 in particular have been found to be very useful. In many applications, however, a need still exists for a simplification of the details of analysis so that orientations can be determined more rapidly, and operators with little or no training in crystallography can be easily instructed in the necessary procedures. Filling this need in part is a system of analysis that has been in use for several years in the Metals Section of the Laboratory, General Electric Co., Pittsfield, Mass. This method is an extension of the one of Majima and Togino,4 which uses fifty-five indexed standard transmission Lauemams to cover the entire range of crystal orientations. Greater rapidity in determining the orientation of a crystal is achieved by using a slightly larger set of standard Lauegrams and by systematizing the steps followed. This system of analysis in its present form constitutes the subject matter of the present paper. Although the method uses transmission X ray Laue patterns, many of the operations are applicable to the analysis of back-reflection Lauegrams. Very briefly the method is based on the fact that Bragg and azimuthal angles for two or more identified Laue diffraction spots completely determine the orientation of a crystal, and standard Laue photographs of the Majima and Togino type provide a ready means for identifying Laue spots. After a preliminary analysis, which consists of identifying the pattern in terms of one of the standard patterns, a correctly marked Lauegram is selected to carry out the final analysis. From measured Bragg and azimuthal angles, the normals (poles) of the reflecting planes for the selected Laue spots are located on a stereographic projection and the orient.at.ion of the crystal determined (in terms of the positions of cube poles for example) by a few additional operations on a \I1ulff net. The actual procedure followed will be illustrated in detail after a brief treatment or X ray problems connected with orientation determinations and a discussion of useful principles and techniques. X Ray and Plotting Problems RELATIVE ADVANTAGES OF BACK-REFLECTION AND TRANSMISSION LAUE DIFFRACTION METHODS In the back-reflection Laue method it is easy to make a direct measurement of the tilt of a zone of Laue spots. Specimen thickness also is generally no problem. In the case of thin specimens, however, the time of exposure is less for the transmission Laue method. For example, with silicon ferrite this advantage holds up to a thickness of 0.6 mm if tungsten radiation at 40 kv peak voltage is used. Furthermore, the transmission photograph represents the entire thickness of the crystal whereas the back-reflection picture represents only a surface layer (a thickness of less than 0.05 mm for silicon ferrite), the deeper layers supplying a negligible amount to the diffraction pattern. If a crystal is distorted, the transmission Laue pattern gives more information particularly with regard to the orientation of the crystal and the overall amount of spread in orientation. Finally a 3 1/4 X 4 in. film suffices for transmission photograms; a 4 X 5 in. or 5 X 7 in. film with a central hole is needed for back-reflection patterns Not only is the manipulation of film easier because of the size of film, but

Jan 1, 1950

By R. G. Davies, R. H. Richman

Several techniques, X-ray diffraction, transmission electron microscopy, conventional, metallography, and mechanical property measurements are combined to investigate decomposition in the suPersaturated solid solution Fe-27 at. pct Be. The following sequence of structures for aging temperatures below 400°C is established: massive short-range order, pseudo-FeBe (L2o) order, Fe3Be (DU3) order, sinusoidal modulation of composition, general or continuous precipitation, and discontinuous or cellular precipitation. In addition to this sequence itself, several features of the individual stages are noteworthy; for example, when coherent modulations occur, their development is parallel to (100) everywhere in the specimen apparently without incubation, and both the wavelength and the composition amplitude of the modulations increase with aging time. Two types of discontinuous reaction are observed, depending upon the aging temperature. At low temperatures (<550°C) the boundary-nucleated variety of discontinuous precipitate predominates; but at higher temperatures (>600°C) the crystallographic variety occurs instead. Hardness and flow-stress measurements clearly reflect the quoted structure sequence. Some qualitative aspects of the structure changes and of the relationship between mechanical properties and structure are discussed. BERYLLIUM in solid solution markedly strengthens iron.&apos;" A recent study demonstrated that not only were supersaturated single crystals of Fe-27 at. pct Be very strong, but they deformed primarily by mechanical twinning.3 Such behavior, coupled with the decrease in solid solubility of beryllium in a Fe from about 33 at. pct at 1165°C to about 10 at. pct at 500°C4 as shown in Fig. 1, leads naturally to questions about property changes with aging in this system. In 1929 roll,1 and later Seljesater and Rogers,5 reported that useful increases in strength could be obtained by aging quenched Fe-Be alloys, but it was not until quite recently that any of the details of precipitation in these alloys were studied. Richman6 observed that both an Fe3Be superlattice (with a DO3 crystal structure the same as Fe3A1, illustrated in Fig. 2) and a modulated structure preceded the appearance of a discrete second phase in the 20 at. pct Be composition. Here, a modulated structure refers to a periodic composition fluctuation within one crystal, while its lattice remains coherent. Subsequent work on a Fe-Be alloys by Heubner7 and von Heimendahl and Heubner8 confirmed the existence of the modulated structure, although only an FeBe (L20) ordered structure was detected (also shown in Fig. 2). Both Rich-man and Heubner corroborated the large increases in hardness during aging reported earlier, but other mechanical properties were not examined. Since modulated systems are encountered relatively infrequently, the influence of coherent modulation upon mechanical properties is not well-known. With the accumulation of information about age-hardening systems, it has become clear that many precipitation reactions cannot always be described by the concept of heterogeneous nucleation at some lattice discontinuity followed by diffusional growth. Rather, complex sequences involving prior "preparation" of the matrix are quite common; that is, a transition structure occurs in the parent phase, instead of in some "nucleus" form. Delineation of such subtle sequences appears to be a worthwhile step toward the understanding of solid-state precipitation. Since not many structural progressions of comparable nature have been reported, the objectives of the present survey are to identify and elucidate the various

Jan 1, 1967

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.&apos; The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.&apos; There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.&apos; The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By John Mark Patek

Knowledge of the relative floatability of silicate minerals is increasing in importance as flotation is being applied to the concentration of nonsulfides. Many silicates are in themselves commercial products amenable to concentration by flotation. Moreover, the selective flotation of other nonsulfide minerals, such as cassiterite, depends largely upon the floatability of associated gangue silicates. Differences in floatability existing between the various silicates have not- been sufficiently appreciated; for example, the feldspars that differ greatly in floatability have generally been merely treated as "feldspar." It was the purpose of the work described in this paper to determine by experiment the differences in floatability between silicates; to investigate the causes for such differences, and to discover a means of predetermining approximate floatability without the necessity of experimentation. Determining Floatability The relative floatability of 20 silicates so selected as to represent all of the more common silicate types1 was obtained by flotation tests enumerated in Table 1. The mineral to be floated was crushed dry on a steel plate, and screened repeatedly during crushing through an 80-mesh screen in order to produce a sand with all grains as close to 80 mesh as possible. The sand was placed in dilute (6N) hydrochloric acid until free of soluble foreign material, and then washed with tap water about ten times in order to remove both acid and fines. The resultant product, which averaged 82 per cent plus 200 mesh, was floated in 50-gram charges in a 50-gram Denver celluloid flotation machine with 0.008 gram of terpineol, and from 0.01 to 0.05 gram of oleic acid in a solution acidified with sulfuric acid. The degree of separation of one mineral from another was determined by counting under a nlicroscope the grains of each mineral, both in the concentrate and in the tailings, and comparing their relative abundance in each. Unless the comparison showed a decided difference in amount,

Jan 1, 1935

By R. C. Hepworth

Heaving in roads built on the Mancos Shale is a serious problem in east-central Utah. Heaves are expressed as local bumps, general rises and severe cracking of the pavement. The heaves usually occur in shale road cuts and generally show a seasonal cycle, which reaches a maximum development in the winter. The presence of certain salts, absorption of moisture and physical properties of the subgrade materials were considered, in Utah, to be the main factors in the heaving mechanism. Work done on similar problems elsewhere and studies conducted by the author indicate that the latter two factors are the most important. Results of this investigation indicate that heaving areas are associated with slaking shale or expansive clays, with and without salts present. Laboratory studies show that the initial moisture content of remolded samples and the desiccation history of un- disturbed samples have a major effect on swelling. Swell tests on compacted samples at various temperatures indicate that water has more influence on swell than temperature, except for samples containing sodium sulphate, which swelled with decreasing temperature. Chloride salts inhibited swelling. Tests on shale cores indicate that the stability of slaking shale can be preserved by maintaining its original moisture content. It is concluded that shales and expansive clays, when exposed in road cuts, become desiccated and are subject to expansion when moisture is subsequently available. The seasonal cycle of heaving may possibly be explained by the annual moisture excess and deficiency. To minimize the problem, freshly exposed shale should be kept wet, and the thickness of the subbase and base courses should be increased. The Utah State Department of Highways has been plagued for many years with a distressed condition that develops in roads constructed on the Mancos Shale. Locally these distressed areas are known as heaves, frost boils and alkali boils. These names refer to the surface expression, time of year

Jan 1, 1965

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

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3&apos;4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By R. C. Craze

During the past 20 years. research and development in the study of reservoir behavior have dealt principally with flow of oil through sandstones. Many reservoir studies of sand fields have proved valuable in promoting recovery efficiency. This paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone reservoir studies to the study of limestone reservoir performance. The characteristics of limestone porous systems, porosity-permeability relationships, distribution and occurrence of oil, and characteristics of flow through such systems are discussed. Recognition is made of the similarities or differences which these factors exhibit in limestone and sandstone systems. Comparisons between operating data for typical limestone and sand reservoirs are presented. It is indicated that the distribution and movement of fluids in and through porous limestones follow the same fundamental principles underlying such processes in sandstones. This fundamental similarity may readily be discernible in the performance of many limestone reservoirs. The volumetric balance and unsteady state radial flow equation, the fluid displacement equation, use of electrical analogue devices, and other analytical techniques to study the behavior of limestone fields appear fundamentally applicable, but do require thorough understanding of the properties of the formation, of the fluids, their behavior during flow, and adequate production operating data. Need for more complete coring and comprehensive examination of core properties is stressed. The results of "active oil" studies, and of flow and interference tests are presented. Well spacing, well completion, and efficient rates of production in limestone reservoirs are briefly discussed. INTRODUCTION Limestone and dolomite reservoirs constitute the largest source of supply of crude oil in the world. an estimated 60 per cent of present production coming from carbonate reservoirs. In many large geologic provinces such as Mexico. the Middle East, and more recently Canada, almost all the oil is found in this type of rock. In the United States, all of the major oil-producing areas except California and Pennsylvania contain oil-bearing carbonate formations. The discovery in recent years of large oil reserves in the Silurian, Devonian, and Ordo-vician formations in West Texas, in addition to the large reserves in the Permian, has accentuated the interest of operators, geologists, and engineers in limestone formations and in the many problems associated with understanding the performance of these reservoirs. The rapid increase in discovery of oil in limestone formations and the present-day position of prominence held by these fields in the production and reserve picture in all parts of the world emphasize the horizons opened to the reservoir technologist in the field of geological and production research. Pertinent to an interpretation of the behavior of limestone reservoirs are the methods of analysis which may be utilized and a possession of full knowledge of the many factors which influence the analytical procedures. During the past 20 years a well-developed science of reservoir engineering has been built upon the research of many workers who studied the fundamental nature of oil reservoirs, characteristics of the porous media, properties and behavior of the contained fluids, and the mechanics of flow. Application of these studies to production practice has resulted in greater recoveries and more efficient field operation. The major portion of this evolutionary process has been founded upon studies of sand fields. The applicability of these more thoroughly developed techniques for studying sand fields to the study of the behavior of limestone fields becomes a factor of technical and practical significance. In the light of the technological background available to the reservoir analyst, this paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone studies to the study of limestone reservoir performance. LIMESTONE RESERVOIR CHARACTERISTICS The characteristics of limestone and sandstone reservoirs are similar in many respects and they both may occur under similar structural conditions. Fundamentally, the distribution and movement of fluids in and through the porous limestone media follow the same basic principles which dictate such processes in sandstones. Herein lies a fundamental similarity, which may readily be discernible in the performance of many limestone reservoirs. In some limestone fields, as in many sand fields, widely varying formation properties and distribution may reveal themselves in deviations in the performance of the reservoir, in the behavior of wells, and in fluid flow through the rock, and make difficult the delineation of reservoir behavior. Only by reservoir studies, core analyses, and coordinated laboratory and field experimentation can the effects of the many influencing factors upon the nature of limestone production be determined. FORMATION CHARACTERISTICS The chief difference between limestone and sandstone, aside from their chemical compositions, is the difference in the geometry and origin of the porous systems in the two kinds of rock. In sandstone the porous system results entirely from the openings among individual sand grains which occur during deposition. The geometry of the openings between the sand

Jan 1, 1950

By Dennis J. McCarthy

TAX TREATMENT OF EXPLORATION AND DEVELOPMENT EXPENSES Exploration Expenditures General Principles. Exploration expenditures are expenses incurred within the United States or the Outer Continental Shelf for the purpose of ascertaining the existence, location, extent or quality of any deposit of ore or other mineral. Section 617 of the Internal Revenue Code permits a taxpayer to elect to deduct these expenditures currently. In default of election, exploration expenditures must be capitalized and included in the basis of the mineral property for purposes of determining cost depletion. Entitlement to Deduction. In order to qualify for current deduction, exploration expenditures must be incurred prior to the commencement of the development stage, i.e., when mineral deposits are shown to exist in sufficient quantity and quality to reasonably justify commercial exploitation. Generally, expenditures for geological and geophysical investigations, reconnaissance, surveying, testpitting, trenching, drilling, driving of exploration tunnels and adits and similar types of work constitute exploration expenditures if incurred prior to the commencement of development. However, expenditures to further delineate the extent and location of an existing commercially marketable deposit are not exploration expenditures. Exploration expenditures may be incurred from within a producing mine to ascertain the existence of what appears to be a different ore deposit. Expenditures for property which is subject to an allowance for depreciation are not deductible under §617. However, depreciation properly allowable on assets used in exploration is an exploration expenditure. Election to Deduct Exploration Expenditures. The election to deduct exploration expenditures is made by deducting these expenditures in the return for the first taxable year for which such treatment is desired. The election applies to all properties of the taxpayer. Once the election is made all exploration expenditures, in the year of election and thereafter, must be deducted, unless the election is revoked with the prior consent of the Commissioner. The Tax Equity and Fiscal Responsibility Act of 1982 (TEFRA) made substantial changes in the treatment of exploration expenditures. For exploration expenses incurred after 1982 and before 1984 by a corporation, the amount currently deductible is limited to 85% of the expenditure. The remaining 15% must be capitalized and recovered over a five-year period. Although exploration costs capitalized under this provision are not part of the basis of the property for cost depletion purposes, investment credit may be claimed with respect to these expenditures. Further changes have been added by the Tax Reform Act of 1984 with respect to expenditures made after 1984. The Act reduces the amount of otherwise currently deductible costs from 85% to 80%. Additionally, it limits the availability of the investment credit for capitalized mineral exploration costs to deposits located in the United States. TEFRA also allows individuals a special method of recovery under which exploration expenditures may, at the election of the taxpayer, be amortized ratably over a 10-year period beginning with the year in which the costs are paid or incurred. If taxpayer does not use this method, the excess of the exploration expenditures actually deducted over the amount that would have been deducted if 10 year amortization had been elected is an item of tax preference subject to the alternative minimum tax.

Jan 1, 1985

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A&apos; exp(-AT). In these equations, a and b are constants which depend on temperature, A&apos; is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By C. A. Siebert, O. S. Duffendack, A. W. Herbenar

IN metallurgical problems involving the study of equilibrium in binary systems, the ,existence of an additional vapor phase, due to the presence of a volatile component in the alloy, has often been neglected. This is well indicated by the modified form of the phase rule, usually accepted in condensed systems in which pressure is not considered as a degree of freedom. In many cases the vapor pressure of the volatile component is exceedingly small and for all purposes can be considered negligible, in which case this form of the phase rule is applicable. However, alloys containing Hg, Cd, Zn, or Mg, tend to show very marked equilibrium vapor pressure, even in the solid state, and therefore present cases where the modified form of the phase rule no longer holds true. A quantitative determination of the vapor pressure of zinc in alpha brasses is not only of practical interest because of the loss of zinc in the processing of these alloys, but also of theoretical interest in that such measurements provide a means of applying the principles of theoretical physics and physical chemistry to problems of applied metallurgy. A number of investigators have reported vapor pressure measurements of zinc in alpha brasses. Hargreaves1 made extensive measurements which were used by Birchenall and Mehl² and Guttman³ for the determination of activity coefficients of zinc in alpha brasses. Hargreaves1 used a differentially heated quartz tube and measured the condensation temperature at one end corresponding to the temperature of the heated brass at the other end. Birchenall and Cheng outlined the condensation method of obtaining vapor pressure of zinc and Cd over some of their silver alloys." The primary object of the present investigation was to increase the range and accuracy of the vapor pressure data for the alpha brasses. Preparation of Alloys: Six alloys were prepared from Bunkerhill zinc and O.F.H.C. copper, both of 99.99 pct purity. The cast ingots were annealed for 24 hr at 550°C, scalped, cold rolled 40 pct and annealed for 50 hr at 550°C. The annealed bars were then surface ground and degasified for 30 min at approximately 550°C in an induction heated vacuum furnace. The surface of the bars was removed before milling the bars into relatively fine chips for chemical analysis and samples for the equilibrium cell. The analyses of the six alloys are given in table I. Experimental Method: The vapor pressure of zinc over the various alloys at a number of temperatures was determined from absorption spectra data. The spark source was produced by means of a high tension discharge between two electrodes of pure zinc. The design of the absorption vessel is shown in fig. 1. The vessel was constructed of transparent quartz which transmits the whole of the visible spectrum and the ultraviolet down to a wave length of 2000 A. The thickness of the vapor space was set at 0.8 mm so as to permit a relatively wide range of measurements without altering the vapor space, and thereby necessitating recalibration of the vessel. The furnace used for heating the absorption vessel consisted of a split wound furnace as shown in fig. 2. The spectrograph used in obtaining the transmitted zinc spectra was a double prism type especially designed for a region of 2500-3500 A. A step diaphragm used in conjunction with a tungsten filament provided the necessary intensity patterns required for calibration of the photographic plates.

Jan 1, 1951

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane&apos; by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane&apos; by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949