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By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum, tungsten, and the binary alloys thereof were grown by electron-beam zone melting and tested in tension between 77° and 373°K. The ductile-to-brittle transition temperature increased sharply with solute concentration, for both tungsten-rich and tantalum-rich alloys; apparently, the maximum transition temperature exists near the 50 pet concentration. Twinning was observed to be a consequence of cleavage-crack propagation. Cleavage occurred on(100)planes, and extensive tearing and "river markings" were present. The onset of brittleness could not be associated with any change in deformation mode, the yield point phenomenon, or the large rise in yield stress with decreasing temperature. Cleavage was observed to initiate at either the specimen surface, or subgrain boundaries. The observation was made that the grain boundaries of Polycrystalline materials are probably even better as nucleation sites for fracture, and are responsible for brittleness at high temperatures and lower solute concentrations than those of the corresponding single crystals. TUNGSTEN and tantalum, the two high-melting neighbors in the third transition period of the periodic table, present striking contrasts. Although both are bee, tungsten has far higher elastic moduli, and the highest ductile-to-brittle transition (DBT) of all the pure metals.' Tantalum, however, is ductile at liquid helium temperatures. Large strain aging and yield point phenomena are observed in tantalum,2,3 but only to a lesser extent in tungsten.4 Tungsten work-hardens at a high rate,5 whereas this effect is negligible in tantalum.' Since the mutual solid solubility of these two metals is complete,7 and no ordering has yet been reported in the binary system, the possibility of depressing tungsten's DBT by tantalum additions was considered. Also, tungsten additions to tantalum could produce hard, high-melting alloys which might be ductile at room temperature. Such alloys offered excellent bases for complex alloy development, particularly with regard to the effect of rhenium on Group VI metals.8"10 In addition, there was the opportunity to examine flow and fracture modes in the vicinity of the DBT, with particular emphasis on the correlation between brittleness and fundamental deformation mechanisms. Myers11 has reported that recrystallized alloys with up to 10 pet W in tantalum are ductile at room temperature, but alloys with 20 pct W could not be swaged at temperatures as high as 500°C. The whole spectrum of Ta-W alloys has been surveyed by Braun, Sedlatschek, and Kiefferl2 using sintered powder compacts. In addition to some physical properties they reported a maximum hardness at about 50 at. pet W, dropping to much lower hardness levels for the pure components. They were able to cold work tantalum-base alloys with as much as 30 pet W and to warm work tungsten-base alloys with up to 20 pet Ta by procedures similar to those used for pure tungsten. EXPERIMENTAL In order to study deformation modes and to keep the impurity concentrations at a minimum, electron-beam zone melting was used to prepare single crystals of high purity. The electron-beam zone melting apparatus is similar to that described by Calverley, Davis, and ever" and incorporates a grid control rectifier to maintain control of emission current. Pure metals were refined by making three zone passes at 4 mm per min up the rod. Alloys were prepared by melting together wire of one constituent on a previously melted rod of the major constituent. Subsequently, two zone passes were made in opposite directions to level the composition after the manner suggested by pfann.14 Purification of the starting materials was accomplished by evaporation of the several impurities, and the degree to which this was accomplished is indicated in the chemical analyses of Table I. The uniformity of composition along a zone levelled rod was within the i 1 pet accuracy of the fluorescent X-ray technique used to determine composition. Crystallographic orientation of the

Jan 1, 1962

By T. G. Maepa

"The creation of mine excavations alters the stress distribution in the surrounding rock mass. In modern mining, resin-grouted rockbolts are used as a means of support in order to redistribute stresses and reestablish equilibrium in the rock mass. The success of resin-grouted rockbolting depends on the design of the system and the correct installation of the support units.The support design and rockbolt installation procedure at a platinum mine in the Bushveld Complex were investigated. A number of issues that resulted in poor installation were identified, including resin admixture, incorrect length and orientation of support holes, over- or under-spinning of the resin, and incorrect rockbolt tensioning. The support design used at the mine was reviewed and its limitations identified. A number of recommendations were made for optimizing the support design by reducing the diameter of the drill bit and reducing the length of the support holes. These changes will enable the mine to use different combinations of resin capsules. Implementation of the proposed changes will lead to a significant reduction in the cost of installation per support hole, as well as improve productivity and safety.IntroductionThe creation of any mine excavation disturbs the virgin state of stress in the Earth’s crust. This results in stress concentrations that interfere with the stability of the rock mass surrounding the excavation. It is essential to modify the internal behaviour of the rock mass surrounding excavations in order to reinforce the ground and stabilize excavations. Resin-grouted rockbolts are extensively used for this purpose. Esterhuizen (2014) stated that when effectively installed, the rockbolt exerts a clamping force and a bonding strength that keeps the rock mass together. This increases the cohesive strength of all discontinuities in the rock mass and enhances the stability of the excavation. Poorly designed and installed ground support is ineffective and constitutes a safety hazard. It is therefore crucial for every mine to ensure that any form of ground support is designed and installed correctly. This research evaluates the installation of resign-grouted rockbolts and identifies challenges and solutions for improved safety as observed at an operating hard rock mine. The support design used at the mine was reviewed and the design parameters optimized. The outcomes will enhance the efficiency of support and minimize the costs associated with the installation of resingrouted rockbolts."

Jan 1, 2017

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By B. M. Larsen

Attempting to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic" and "macroscopic," depending on whether the variations in concentration of solutes or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also untlerly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all sepregation effects. Undercooling and Nuclei Formation It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus temperature. In practical terms this means that the nuclei number illcreases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. Temperature Gradients and Heat Dissipation during Freezing Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period. Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1945

By R. G. Hawthorne

This report is concerned with fluid displacement in porous media, in those cases where viscous and gravitational forces control the displacement. Such a system would usually be found in a sand body of large physical dimensions such as an oil reservoir, although it is possible to create such a system in the laboratory. It is shown that the position of the fluid interface can be predicted by numerical calculations using a basic idea presented by Dietz. Fluid flow is considered in a vertical plane in a homogeneous, porous medium of sufficient thickness that the capillary transition zone is small in comparison with the total reservoir. A theory developed by Dietz' is used to make numerical calculations of the position of the fluid interface. The results for several conditions are compared with scaled model experiments. The results show that, for gas drive in a reservoir of steep dip, a relatively low flow rate can displace large volumes of oil before gas breakthrough. On the other hand, water injection at favorable mobility ratio and low dip may show best performance at high rates. Water tends to underride the oil and, given sufficient rime, will break through without much oil displacement. For certain conditions, which include relatively low flow rate, the interface is a straight line and its behavior is simple to calculate. At higher flow rates, the interface is unstable, and a numerical solution was programed for an automatic computer. In general, good agreement is shown between the fluid model and the computed results so long as gravitational forces have control. For a water drive at very unfavorable mobility ratio, many small water fingers appear. These viscous fingers are not controlled by the relatively small gravitational forces. When viscous fingering becomes the controlling factor, the mathematical model is oversimplified, and results do not check the fluid flow model. INTRODUCTION Present methods of reservoir analysis depend upon certain simplifying assumptions to obtain mathematical descriptions of practical use. Material-balance methods (Muskat2 or Tarner2) assume uniform fluid saturations in the entire reservoir, or in a few subdivisions of the reservoir. An unsteady-state flow calculation by West, er at considered pressure and saturation changes in flow to a well during solution gas drive, and neglected gravity effects. Results showed only a 4 per cent difference for ultimate oil recovery by the Muskat method, even though the case chosen for study was one in which unsteady-state effects should be high. The Buckley-Leverett5 method commonly assumes a one-dimensional flow system. It is applicable at high flow rates where viscous forces predominate over gravity forces. Simultaneous, parallel flow of the two fluids is assumed, and the concept of a fluid interface is not introduced. Permeabilities to each fluid for a given saturation must be known. The method is not applicable for a two-dimensional system where cross flow becomes possible. Less well known is the displacement equation derived by Dietz. This method is designed for two-dimensional flow systems and assumes a definable fluid interface within the porous medium. Dietz showed that, for a range of low flow rates, the interface would be stable. straight and at an angle of inclination which could be simply calculated. At a certain critical flow rate, the calculated interface tilt would equal the formation dip. For higher flow rates, a finger of displacing fluid would invade the displaced fluid. Dietz indicated that his method applied only to macroscopic reservoir behavior, while the Buckley-Leverett method applied to the small transition zone at the fluid interface. The examples worked out in this report are based on the fluid-displacement theory of Dietz. It is shown that the Dietz theory may be used to derive equations analogous to the Buckley-Leverett equations. In contrast to the Buckley-Leverett method, flow is considered in a plane rather than being limited to a line. Rather than a frontal advance, the movement of a fluid interface is followed. For flow rates substantially exceeding the critical rate and for high viscosity ratio, many fingers of invading fluid occur-—rather than the single finger assumed by Dietz. On the other hand, so long as some gravitational influence remains, the flow is not entirely parallel to the bedding planes as assumed by Buckley and Leverett; therefore, both methods fail to give an adequate descrip-

By William Hurst, A. F. van Everdingen

For several years the authors have felt the need for a source from which reservoir engineers could obtain fundamental theory and data on the flow of fluids through permeable media in the unsteady state. The data on the unsteady state flow are composed of solutions of the equation Two sets of solutions of this equation are developed, namely. for "the constant terminal pressure case" and "the constant terminal rate case." In the constant terminal pressure case the pressure at the terminal boundary is lowered by unity at zero time, kept constant thereafter, and the cumulative amount of fluid flowing across the boundary is computed, as a function of the time. In the constant terminal rate case a unit rate of production is made to flow across the terminal boundary (from time zero onward) and the ensuing pressure drop is computed as a function of the time. Considerable effort has been made to compile complete tables from which curves can be constructed for the constant terminal pressure and constant terminal rate cases, both for finite and infinite reservoirs. These curves can be employed to reproduce the effect of any pressure or rate history encountered in practice. Most of the information is obtained by the help of the Laplace transformations, which proved to be extremely helpful for analyzing the problems encountered in fluid flow. The application of this method simplifies the more tedious mathematical analyses employed in the past. With the help of Laplace transformations some original developments were obtained (and presented) which could not have been easily foreseen by the earlier methods. INTRODUCTION This paper represents a compilation of the work done over the past few years on the flow of fluid in porous media. It concerns itself primarily with the transient conditions prevailing in oil reservoirs during the time they are produced. The study is limited to conditions where the flow of fluid obeys the diffusivity equation. Multiple-phase fluid flow has not been considered. A previous publication by Hurst' shows that when the pressure history of a reservoir is known, this information can be used to calculate the water influx, an essential term in the material balance equation. An example is offered in the literature by Old² in the study of the Jones Sand, Schuler Field, Arkansas. The present paper contains extensive tabulated data (from which work curves can be constructed), which data are derived by a more rigorous treatment of the subject matter than available in an earlier publication.' The application of this information will enable those concerned with the analysis of the behavior of a reservoir to obtain quantitatively correct expressions for the amount of water that has flowed into the reservoirs, thereby satisfying all the terms that appear in the material balance equation. This work is likewise applicable to the flow of fluid to a well whenever the flow conditions are such that the diffusivity equation is obeyed. DIFFUSITY EQUATION The most commonly encountered flow system is radial flow toward the well bore or field. The volume of fluid which flows per unit of time through each unit area of sand is expressed by Darcy's equation as where K is the permeability, the viscosity and aP/ar the pressure gradient at the radial distance r. A material balance on a concentric element AB, expresses the net fluid traversing the surfaces A and B, which must equal the fluid lost from within the element. Thus, if the density of the fluid is expressed by p, then the weight of fluid per unit time and per unit sand thickness, flowing past Surface A, the surface nearest the well bore, is given as The weight of fluid flowing past Surface B, an infinitesimal distance 6r, removed from Surface A, is expressed as

Jan 1, 1949

By A. F. van Everdingen, William Hurst

For several years the authors have felt the need for a source from which reservoir engineers could obtain fundamental theory and data on the flow of fluids through permeable media in the unsteady state. The data on the unsteady state flow are composed of solutions of the equation Two sets of solutions of this equation are developed, namely. for "the constant terminal pressure case" and "the constant terminal rate case." In the constant terminal pressure case the pressure at the terminal boundary is lowered by unity at zero time, kept constant thereafter, and the cumulative amount of fluid flowing across the boundary is computed, as a function of the time. In the constant terminal rate case a unit rate of production is made to flow across the terminal boundary (from time zero onward) and the ensuing pressure drop is computed as a function of the time. Considerable effort has been made to compile complete tables from which curves can be constructed for the constant terminal pressure and constant terminal rate cases, both for finite and infinite reservoirs. These curves can be employed to reproduce the effect of any pressure or rate history encountered in practice. Most of the information is obtained by the help of the Laplace transformations, which proved to be extremely helpful for analyzing the problems encountered in fluid flow. The application of this method simplifies the more tedious mathematical analyses employed in the past. With the help of Laplace transformations some original developments were obtained (and presented) which could not have been easily foreseen by the earlier methods. INTRODUCTION This paper represents a compilation of the work done over the past few years on the flow of fluid in porous media. It concerns itself primarily with the transient conditions prevailing in oil reservoirs during the time they are produced. The study is limited to conditions where the flow of fluid obeys the diffusivity equation. Multiple-phase fluid flow has not been considered. A previous publication by Hurst' shows that when the pressure history of a reservoir is known, this information can be used to calculate the water influx, an essential term in the material balance equation. An example is offered in the literature by Old² in the study of the Jones Sand, Schuler Field, Arkansas. The present paper contains extensive tabulated data (from which work curves can be constructed), which data are derived by a more rigorous treatment of the subject matter than available in an earlier publication.' The application of this information will enable those concerned with the analysis of the behavior of a reservoir to obtain quantitatively correct expressions for the amount of water that has flowed into the reservoirs, thereby satisfying all the terms that appear in the material balance equation. This work is likewise applicable to the flow of fluid to a well whenever the flow conditions are such that the diffusivity equation is obeyed. DIFFUSITY EQUATION The most commonly encountered flow system is radial flow toward the well bore or field. The volume of fluid which flows per unit of time through each unit area of sand is expressed by Darcy's equation as where K is the permeability, the viscosity and aP/ar the pressure gradient at the radial distance r. A material balance on a concentric element AB, expresses the net fluid traversing the surfaces A and B, which must equal the fluid lost from within the element. Thus, if the density of the fluid is expressed by p, then the weight of fluid per unit time and per unit sand thickness, flowing past Surface A, the surface nearest the well bore, is given as The weight of fluid flowing past Surface B, an infinitesimal distance 6r, removed from Surface A, is expressed as

Jan 1, 1949

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

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 R. K. Rath

Adsorption, electrokinetic and flotation studies were carried out. The maximum density of adsorption of guar gum was obtained at pH 7.5 on sphalerite and at pH 11.5 on galena. Flotation recovery of sphalerite was reduced only marginally by the presence of guar gum in the pH range investigated, whereas recovery of galena was reduced to about 20% at pH 12. Differential flotation tests on binary mixtures indicated that 10 ppm of guar gum can depress galena and separate it from sphalerite at around pH 12.1. Co-precipitation tests confirmed the formation of a metal ion-guar gum complex in the bulk solution, suggesting that this is the precursor to adsorption. The adsorption isotherms for both minerals followed Langmuirian behaviour, but adsorption of guar gum on galena was significantly higher than on sphalerite and dissolution tests indicated that the concentration of Pb ions released from galena was an order of magnitude greater than that of Zn ions dissolved from sphalerite

Jun 21, 1905

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.&apos; The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,&apos; a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.&apos;-&apos; Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham&apos;" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill&apos;s solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.&apos; In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis&apos;&apos;

By O. C. Baptist

The Umiat oil field is in Naval Petroleum Reserve No. 4 between the Brooks Range and Arctic Ocean in far-northern Alaska. The Umiat anticline has been tested by 11 wells, six of which produced oil ; however, [lie productive capacity and recoverable reserves of the field are subject to considerable speculation because of unusual reservoir conditions and because several wells appear to have been .seriously damaged during drilling and completion. Oil is produced at depths of 275 to 1,100 ft; the depth to the bottom of the permanently frozen zone varies from about 800 to 1,100 ft, .so that most of the oil reserves are in the permafrost Reservoir pressures are estimated to range from 50 to 350 psi, increasing with depth, and the small amount of gas dissolved in the oil is the major source of energy for production. Laboratory tests were made on cores under simulated permafrost conditions to estimate oil recoverable by solution-gas expansion from low saturation pressures. The cores were also tested for clay content and susceptibility to productivity impaiment by swelling clays and increased water. content if exposed to fresh water. The results indicate that oil can be produced fronz reservoir rocks in the permafrost and that substantial amounts of oil can be produced from depletion-drive reservoirs by a pre.s.r~lrr drop of as little as 100 psi below the saturation pressure. Freezing of formation water reduces oil productivity much more than that due to increased oil viscosity: Failure of we1ls drilled with rtuter-base mud to produce is attributed to freezing of water in the urea immediately surrounding the wellbore. Swelling clays apparently contributed very little to the plugging of the wells. INTRODUCTION Naval Petroleum Reserve No. 4 lies between the Brooks Range and the Arctic Ocean in northern Alaska. The Umiat oil field is located in the southeastern part of the Reserve and is about 180 miles southeast of Point Barrow (the only permanent settlement in the Reserve and the primary supply point for drilling of the wells at Umiat). Eleven wells were drilled for the U. S. Department of the Navy, Office of Naval Petroleum and Oil Shale Reserves, between 1944 and 1953 to test the oil and gas possibilities of the Umiat anticline. Six of these wells produced oil in varying quantities and the best one pumped about 400 B/D.&apos; Estimates of recoverable oil range from 30 to 100 million bbl. The main oil-producing zones are two marine sandstone beds in the Grandstand formation of Cretaceous age: these are referred to as the upper and lower sands. Good oil shows were found throughout the sand settions in the first three wells drilled on the structure, but the highest rate of oil production obtained on any 01 the many tests was about 24 BOPD. These first wells were drilled with conventional rotary methods using water-base mud; later wells were drilled either with cablc tools using brine or rotary tools using oil or oil-base mud. These experiments were successful as is shown by comparing the oil production from Well No. 2 with that from No. 5. These two wells are only 200 ft apart and are located at about the same elevation on the structure. Well No. 2. drilled with a rotary rig using water-base mud, was abandoned as a dry hole after all formation tests were negative. Well No. 5. drilled with cable tools and reamed with a rotary using oil, pumped 400 BOPD which was the maximum capacity of the pump and less than the capacity of the well. These field results indicated that the producing sands were extremely "water sensitive" and it was assumed that the cause of this sensitivity was the presence of swelling clays in the sands. Because of the very unusual reservoir conditions and the difficulties encountered in completing oil wells in the permafrost. the Navy asked the U. S. Bureau of Mines to make laboratory studies under simulated permafrost conditions to assist them in estimating the production potential of the field and the recoverable reserves. These tests were designed to determine the cause of the plugging of wells in the permafrost and to test oil recovery from frozen sand by solution-gas expansion with the oil gas-saturated at very low pressures. EXPERIMENTAL METHODS AND PROCEDURES Samples Analyzed Core samples were analyzed that represent the lower sand in Umiat Well No. 7, the upper sand in No. 3. and both the upper and lower sands in No. 9. These sands should be productive in all of the wells because of their location on the structure. Core samples from

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By Phil Thwaites

"The mining industry uses many types of mineral and metallurgical plants to produce saleable product from ore mined. Plant design history has left current operations with a mixture of manual operation and various forms of automated process controls. Consequently, we typically see high variability in the continuous operations together with a shortfall in the attainment of full capacity, or higher utilization of consumables.At a level of best practice, “Operational Performance Excellence” focuses on process control, using automation and control systems to deliver process optimization. This more sophisticated delivery is a great deal more difficult than the first stage of equipment selection / installation. It includes the appropriate selection of the right instrumentation, control system, key process knowledge, individuals with a solid control engineering background/experience, and the essential backing/ support of the operations management team together leading to higher value delivery. Robust solutions can be realized, considerably minimizing process variation, thus leading to process optimization. This approach results in an easier, efficient and safer process while providing considerable returns for the plant owners.How variable are your processes, and do you maintain optimized process performance with dedicated resources, modern instrumentation, ‘best practice’ control systems and performance monitoring tools? In this lecture, these questions and their possible answers are discussed.357"

Jan 1, 2013

By F. V. Lenel

Two years ago in Chicago a seminar was held on the theory of sintering of pure metal powders. As an introduction to this seminar D,.. Rhines1 gave an excellent survey of the literature on this subject, His method of presentatioll was to summarize the experimental observations on sintering and from them to develop a composite theory of sintering in which he combined all the important contributions to the theory into one organic whole. In contrast to the mechanism of sintering of pure metal powders, which, of course, al\vays takes place in the solid phase, sintering j,, the presence of a liquid phase, cannot be treated as one unified mechanism, such as the sintering mechanism of pure metals. The reason is that there are really several mechanisms depending upon the type of alloy system which is sintered and the field of its con. stitutional diagram ill which the sintering takes place, Two mechanisms have heen investigated and will be reviewed in this paper. Ill the first lnechanism the liquid is presellt during the entire time while the compacts are at the sintering temperature, In other words they are sintered between the liquidus and the solidus of the alloy system and are ~e~erogelleous during the entire sintering cycle. The second mechallism applies to alloys in which the liquid phase is formed during the sintering process, but disappears before the sintering process is completed through diffusion and formation of a solid solution. These alloys are therefore homogeneous at the end of the sintering cycle. This second mechanism is more complicated because of the two stages of sintering, the liquid and the solid, as they may be called. It is therefore not surprising that the few detailed investigations of sintering in the presence of a liquid phase have been concerned with heterogeneous sintered alloys, namely the tungsten-nickel-sinter ing which is the so-called "heavy alloy," and the cemented carbides. The mechanism of sintering of these systems is characterized by the fact that theoretical or near theoretical density is attained during sintering, while simultaneously a distinct grain growth takes place through solution of the smallest grains of the solid phase in the liquid phase and reprecipitation on the larger grains. In the first part of the survey this sintering mechanism which is called for short the heavy alloy mechanism is treated in detail. In the second part Of the survey experimental observations for the sintering of homogeneous sintered alloys where the liquid phase disappears before the completion of sintering are discussed. Much less systematic work has been done on these alloys to which the conlmercially important Porous bronzes and the iron-nickel-aluminum permanent magnet alloys belong. Emphasis will be laid throughout this survey upon the microstructural and density changes during sintcring because the Sintering mechanism can usually be described directly by these changes. Other

Jan 1, 1949

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By D. Mraz

"In certain instances, rocks around underground excavations behave as a plastic mass. This paper offers several solutions to predicting the mode of plastic flow around cavities and designing mining pillars where plastic conditions exist.IntroductionWhen stresses around underground cavities exceed yield limits of the host rock, the material often behaves as a plastic mass. The best example of this phenomenon is the behaviour of salt rocks in deep salt and potash deposits (more than 500 m deep).However, many other soft rocks exhibit similar properties. For example, Jeremic(1) described certain types of coal yielding plastically under high pressure. Alder suggested that granulated rock behaves plastically.The object of this paper is to propose a de sign procedure for mining pillars exhibiting plastic flow due to the combination of rock properties and in-situ stresses.Prandtl(3) mathematically defined a concept of a generalized, perfectly plastic substance, not possessing the property of strain hardening (Fig. I). He had in mind, a solid with a quasi quasi-isotropic , polycrystalline structure having a well defined yield point, and he postulated that its material elements start and continue to deform plastically when the maximum shearing stress ""&apos;MAX"" reaches a sharp limit, dependent on the mean value of the sum of the major and minor principal stresses:"

Jan 1, 1984

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated&apos; single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-&apos; atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith&apos;s graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970