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By H. H. Uhlig

In our study of the mechanism of and the prevention of corrosion in stainless steels, it was considered of fundamental importance to obtain knowledge of the surface structure of such alloys. If corrosion resistance is due to a self-healing oxide layer, which like a paint film protects the underlying metal, it would be obviously relevant were the effort made to make the film less permeable and more adherent; for example, the surface might be expected to respond to an anodizing process, which is found successful in increasing the film thickness and corrosion resistance of aluminum. However, if passivity and corrosion resistance of stainless steels are due to another cause, the attack of the problem would follow another path. One of the most effective techniques for studying passivity and corrosion tendency is the measurement of the electrochemical potential. Not only can one determine by potential measurements whether a metal is active or passive, but also one can determine the degree of passivity and rate of transformation of passivity with time. Chemical media that build up or destroy passivity when in contact with the steel can also be classified by potential measurements. Something can be learned, too, of the effect of alloy additions such as molybdenum to 18-8, known to decrease corrosion of the alloy in chloride solutions. A study of alloys in previous investigations has sometimes included data on the electrochemical potentials. Tammann and Sotterl measured the electrochenlical potentials of alloys of iron-molybdenum and iron-chromium and reperted the critical concentration of molybdenum or chromium at which passivity initiates. Strauss2 made similar measurements for the iron-chromium system. The electrochemical potential3 has also been used to indicate carbide precipitated 18-8. In 18-8, heat-treated to precipitate carbide, active metal exists at the region of the grain boundaries, contrasted with passive metal within the grains, the active metal accounting for a resultant active potential. Several

Jan 1, 1940

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975

By Walter Crafts, W. D. Forging, John J. Egan

Although many elements reduce the tendency to porosity in steel castings, manganese, silicon, aluminum, calcium, titanium and zirconium appear to be most generally suitable for the purpose. The manganese and silicon contents are usually maintained in a fairly constant range. Silicon-killed castings often are made to be sound with little or no addition of the stronger degasifiers. In many cases, however, it is more practical to utilize the stronger degasifying elements, aluminum, calcium, titanium and zirconium. Since they greatly modify the composition, shape, and distribution of the nonmetallic inclusions, and thereby the ductility, the strong deoxidizers must be used in such a way as to form the least harmful types of inclusions. As the reasons for failure always to obtain good results have not been obvious, an effort has been made to determine the mechanism of solidification of steels deoxidized to produce certain types of inclusions. Diagrams representsing the mechanism of their formation have been constructed from the appearance of the nonmetallic constituents and have not only illustrated the limiting features of specific deoxidizing treatments with respect to inclusion formation and ductility, but have also indicated a relation between inclusions and resistance to hot tearing. Three different types of deoxidation treatment have been used for obtaining sound castings with relatively high ductility. The first method is to make and cast the steel under such conditions that deoxidation with silicon and a small addition of a strong deoxidizer assures soundness. The effective addition that will promote soundness without causing the formation of intergranular inclusions varies with the furnace practice and composition, but may be limitled to about 0.025 per cent Al, Zr or Ti. Up to 8.10 per cent Ca and 0.15 per cent V are also used for this purpose. The inclusions in these steels are characteristically glassy silicates and round or irregular sulphides. As pointed out by Sims and Lillieqvist,1 the formation of fine intergranular inclusions, which are detrimental to ductility, limits the amount of strong deoxidizers that may be added.

Jan 1, 1940

By John J. Egan, W. D. Forging, Walter Crafts

Although many elements reduce the tendency to porosity in steel castings, manganese, silicon, aluminum, calcium, titanium and zirconium appear to be most generally suitable for the purpose. The manganese and silicon contents are usually maintained in a fairly constant range. Silicon-killed castings often are made to be sound with little or no addition of the stronger degasifiers. In many cases, however, it is more practical to utilize the stronger degasifying elements, aluminum, calcium, titanium and zirconium. Since they greatly modify the composition, shape, and distribution of the nonmetallic inclusions, and thereby the ductility, the strong deoxidizers must be used in such a way as to form the least harmful types of inclusions. As the reasons for failure always to obtain good results have not been obvious, an effort has been made to determine the mechanism of solidification of steels deoxidized to produce certain types of inclusions. Diagrams representsing the mechanism of their formation have been constructed from the appearance of the nonmetallic constituents and have not only illustrated the limiting features of specific deoxidizing treatments with respect to inclusion formation and ductility, but have also indicated a relation between inclusions and resistance to hot tearing. Three different types of deoxidation treatment have been used for obtaining sound castings with relatively high ductility. The first method is to make and cast the steel under such conditions that deoxidation with silicon and a small addition of a strong deoxidizer assures soundness. The effective addition that will promote soundness without causing the formation of intergranular inclusions varies with the furnace practice and composition, but may be limitled to about 0.025 per cent Al, Zr or Ti. Up to 8.10 per cent Ca and 0.15 per cent V are also used for this purpose. The inclusions in these steels are characteristically glassy silicates and round or irregular sulphides. As pointed out by Sims and Lillieqvist,1 the formation of fine intergranular inclusions, which are detrimental to ductility, limits the amount of strong deoxidizers that may be added.

Jan 1, 1940

By J. E. Pavlick, W. W. Mullins, H. W. Paxton

The growth of nitrogen-austenite during nitriding of large-gvained ferrite between 650" and 800°C has been studied as a functimz oJ time and nitrogen potential of the atmosphere for a variety of alloying elements dissolved in the ferrite. Whereas no preferential grain boundary penetration by aistenite takes place in zone-refined iron, the addition of aboit I zot pct oj' V, Ti, Cr. Si, or A1 produces significant protrusion of austenite down former 0-0 boundaries. This group of elernents also produces ragged y-0 interfaces in the a grains which advance more slozuly than those in zone-refined iron. 1 zut pct of Ni, Co, Mn, or Mo dissolved in ferrite leads to essentially smooth 7-a interfaces, which advance at rates very sinzilar to those in zone-refined iron. The reasons for this effect are not clear. Two possible limiting hypotheses, not necessarily exclusive, are discussed. One involves p.referentia1 grain bozindary diffusion of nitrogen. the other the production of a zone of ferrite, stpersatcirated with respect to nitrogen, from which austenite precipitates helerogeneozisly on the a-a gyain boundaries. In many phase transformations which occur by nu-cleation and diffusion-controlled growth, information on the parameters which control the rates of nuclea-tion and of growth is frequently not quantititative. The present work describes a continuation of efforts to obtain quantitative data on growth rates in systems where thermodynamic and kinetic factors are known independently, and thus where comparison with models of the growth process is possible. The work has been conducted on iron-base systems for two reasons. Firstly, there are several interesting transformations in this system, many of which are of practical importance. Secondly, the information on phase diagrams, activities, and diffusion coefficients is more complete in this system than in any other. These data are still inadequate to check all the effects of alloying elements, but at worst it is possible to make estimates and thus examine order-of-magni-tude agreement with proposed models. It will be necessary to do this in the present work. The problem studied was the growth of nitrogen-austenite in from the surface of large-grained columnar crystals of alloyed ferrite exposed to an NHs/Hz atmosphere. Earlier work by Grozier et al.' had suggested that growth of austenite may occur preferentially along grain boundaries of alloyed ferrite, whereas zone-refined (ZR) iron shows no such effect, Fig. 1. Growth of nitrogen-austenite into single crystals of zone-refined ferrite is planar provided sufficient nu-cleation sites for austenite are present, and is controlled by volume diffusion of nitrogen through the

Jan 1, 1967

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968

By G. L. Oldright, F. S. Wartman, H. E. Keyes

The economic manufacture of sulfuric acid by the ordinary chamber process usually involves production on a large scale and a plant that is costly to construct. The nature of sulfuric acid makes it costly to transport any great distance. For these reasons, the metallurgist has not found it feasible, at times, to beneficiate ores amenable to leaching, and a need exists for a local process that will produce acid cheaply on a small or large scale. To leach ores containing residual sulfides, an oxidizer, such as ferric sulfate, is needed in solution. Precipitation with scrap iron is one of the cheapest methods of removing some metals from solution, giving a plant of low first cost and supplying a source of cheap ferrous sulfate. The other ingredient needed for the process is SO2 roaster gas, the addition of which, as described below, will give both ferric sulfate and sulfuric acid. Where roaster gas is a waste or obnoxious product, the expense for materials is still further lessened. The use of ferric sulfate and sulfuric acid as a solvent lends itself well to the utilization of scrap iron as a precipitant, and the stages of the process fit in well together as an economic whole. Applications The hydrometallurgist usually thinks of ferric sulfate as a partial solvent for some of the sulfides of copper alone, as most work has been done on this metal. The processes of Hannay and Christensen, for leaching unroasted galena with ferric chloride made by anodic oxidation, show the added solvent action given by "ic" salts when added to brine solutions. It was found by R. D. Bradford (in some work to be published soon by the University of Utah) that, by the addition of a ferric salt to a brine solution, the silver as well as the lead in an unroasted semi-oxidized ore could be largely dissolved. The "ic" salt in the case of silver has evidently the same effect as the case of cupric sulfate when

Jan 1, 1926

By L. M. Higgins

Dust or fume control systems are devices for capturing contaminants at their source and preventing their discharge to atmosphere. The Primary Components Of Any Dust Control System Include: An enclosure around any potential dust source such as conveyor belt transfer, crusher, screening machine, bin loading and loadout. Ductwork including hood takeoffs (transitions) to convey the collected dust laden air away from the source of dust generation to a convenient location. A dust collector for separation of particulate matter from the air stream prior to its discharge to the atmosphere. A prime mover generally a fan, to draw air into an enclosure and to overcome resistance to flow in the ductwork, dust collector and stack.

Jan 1, 1978

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

Hydrogen forms a beta-stabilized system with titanium, with a beta eutectoid at about 300°C and 44 atomic pct H2. &apos;The solid solubility of hydrogen in alpha decreases from about 8 to about 0.1 atomic pct from 300°C to room temperature. Hydrogen has little effect on tensile properties, but decreases notch-bar toughness to a large degree. This latter effect appears to be the result of increased notch sensitivity. PRIOR to this investigation, only a small amount of information was available on the effect of hydrogen on the mechanical properties of titanium. The effects of the other interstitially soluble elements, carbon, oxygen, and nitrogen, had received detailed study. Jaffee and Campbell1 indicated that hydrogen up to 1 atomic pct did not affect tensile properties deleteriously. Pitler&apos; indicated that 1 atomic pct H, in titanium reduced the impact strength appreciably, but his alloys contained appreciable amounts of oxygen, and it was difficult to attribute the embrittlement entirely to hydrogen. The high temperature portion of the equilibrium diagram for the Ti-H system was established by McQuillan," and his data generally corresponded with the results of Kirschfeld and Sieverts," Gibb and Kruschwitz," Bevington, Martin, and Mathews," and other investigators. The lower concentration limit of the hydride phase varied considerably among investigators, and Gibb and Kruschwitz9 ad shown that small amounts of contaminants in either titanium or hydrogen caused considerable variation in this lower limit. In view of this pronounced effect of contaminants, the extrapolated value of McQuillan&apos;s, about 48 atomic pct at the 325°C eutectoid, appeared the most reasonable. McQuillan&apos;s lowest experimental value was 54 atomic pct at a temperature of 450 °C. The density of titanium had been shown to decrease with increasing hydrogen content, but discrepancies were noted among the various investigations. The best values indicated that the density was decreased from 4.56 grams per cc at 0.27 atomic pctl to 3.84 grams per cc at 61.3 atomic pct? This investigation was conducted to determine the effects of hydrogen on a titanium, both in high purity and commercially pure metals, and on high purity a titanium alloys. Material and Fabrication The literature indicated that impurities in either the hydrogen or the titanium must be kept to a minimum. For this reason, the initial studies were made with high purity iodide-refined titanium. The vendor&apos;s analysis of the iodide titanium and the hydrogen content of the as-fabricated Y4 in. diameter rods are shown in Table I. Two 1 lb ingots were prepared by arc melting under argon in a water-cooled crucible, using a water,cooled tungsten electrode. This equipment has been described.&apos; As-cast Brine11 hardness numbers of 88 and 58 for these ingots were low enough to insure that the high purity of the metal was maintained during arc melting. The ingots were hot forged to % in. diameter rods at 800°C, cleaned by grit blasting, and then cold swaged to Yz in. diameter rods. The rod was then air annealed at 725 "C, ground to remove scale, and cold swaged to Y4 in. diameter (75 pct reduction in area). The material was then annealed for 1 hr in argon at 800°C to develop an equiaxed a grain size of about 0.05 mm. Micro tensile specimens and microimpact specimens were machined from this rod prior to treatment in the Sieverts-type absorption apparatus. Two lots of commercially pure RC-55 titanium were also used in this investigation to determine the effects of hydrogen and the normal impurities on mechanical properties. The commercially pure RC-55 alloy was obtained in the form of % in. diameter rod. The analysis of this material is also given in Table I. The % in. diameter rods were hot swaged

Jan 1, 1955

To the Members It has been, and is the endeavor of the A. I. M. E. to serve each and every member. One of the means of letting the membership know what is going on in the mining; metallurgical and chemical fields, and by far the most important, has been our monthly Bulletin. To publish this costs money, and to partly defray the costs, it was decided to accept such advertising as could be secured. The A. I. M. E. is the only one of the American National engineering societies whose dues are as low as $10 per year, and it actually spends more upon the Bulletin and Transactions than the sun total it receives for clues. Hence the need of advertising revenues. We are planning even greater improvements for your Bulletin-improvements that will help you in your work. It will mean a better publication, with more information than ever before. To successfully carry out our plans, we must have your co-operation. We are not asking you for financial, but for your moral support. With that we shall accomplish a great deal. What we ask of you, brother member, is to give evidence to those patronizing our advertising pages, that you not only read the editorial pages, but the advertising section as well, and that you have in mind the welfare of your Institute by consulting the advertising pages when in the market for equipment. Do you realize that if you mention your Bulletin when writing advertisers or purchasing supplies, that not only would your publication secure more advertising, but better satisfy present advertisers. We have reason to know that our advertisers secure business as a result of our publication, but they demand some evidence that you see their advertisement. Unfortunately, our members do not as a rule mention where they saw the advertisement, and as a consequence advertisers have no means of knowing whether their investment in the Bulletin is paying. The A. I. M. E. Bulletin can be made the best advertising medium in the mining, metallurgical and chemical fields, simply by each member doing his bit. It is very little to ask of you, and the returns to the mining industry will be enormous.

Jan 9, 1915

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas&apos; which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy&apos;s law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy&apos;s law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas&apos; which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy&apos;s law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy&apos;s law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain&apos; and magnesia.&apos; Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann&apos;" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que&apos;s data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may&apos; exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948

By J. Weertman

An explanation is advanced for the recent results of Barrett and Sherby on the high-temperature creep of fee metals. Their measurements indicate that metals with a low stacking fault energy creep at a much slower rate than metals with a high stacking fault energy. The explanation is based on the assumption that the rate of core diffusion is much smaller in partial dislocations than in perfect dislocations. An experiment is suggested to test this assumption. The explanation also requires that the jog density is small on widely split dislocations. SHERBY and Barrett1,2 recently established an important result in the field of high-temperature steady-state creep. They have shown that fee metals whose dislocations split into partial dislocations separated by a wide stacking-fault ribbon creep at a much slower rate than fee metals whose dislocations are not split appreciably. The creep rates in the two cases may differ by a factor as high as 6000. (For the purpose of comparison, the test temperature of each metal was chosen so that its rate of self-diffusion was equal to a standard value. Similarly the stress levels were such that the ratio of the stress to an appropriate elastic modulus was the same for each metal. In all cases the stresses were sufficiently low that the steady-state creep rate was proportional to the stress raised to a power.) It is the purpose of the present paper to attempt an explanation of this interesting and significant result of Sherby and Barrett. The activation energies of high-temperature creep of the metals tested by Sherby and Barrett (aluminum, nickel, copper, and silver) were equal to their self-diffusion activation energies. Hence it appears reasonable to assume that this type of creep is controlled by a dislocation-climb process, which in turn is controlled by the diffusion of vacancies to or from dislocation lines. (It will be assumed that the diffusion of interstitial atoms is unimportant in the climb process. The analysis could be repeated for the case in which interstitial atoms are important.) In prior papers374 I have treated dislocation climb by using the assumptions that core diffusion is extremely fast down a dislocation and that a dislocation always maintains an appropriate vacancy concentration in its immediate vicinity. In this

Jan 1, 1965

By A. F. Meston

Centrifugal force has been used for centuries for separating liquids but machines for doing this are a comparatively recent development. The use of these machines is being extended into many industries but this paper is confined to their use in the oil industry. The centrifugal machine is found at the well where "cut oil" is dehydrated for acceptance by pipe lines; and in the refinery and byproduct plant. In fact, wherever finely divided suspended particles should be removed from an oil, there is a possible use for a centrifugal machine, if the particles have, or can be made to have, a specific gravity different from that of the oil. Centrifugal machines are also used for cleaning fuel and lubricating oils and dehydrating transformer oils. Applications and Results When oil comes from the well mixed with water, it is spoken of as cut oil. Settling often does not remove sufficient water for the oil to be accepted by pipe lines, thus necessitating chemical or other treatment. Centrifuging alone, or following chemical treatment, effectively prepares such oil for pipe lines, as is shown by the following data: WateR, Etc. Wat~R. Etc. Temperature, Oil to Pipe Line, aT StUt at Finish Degrees F. Bel. Per HouR PIE Cent. PEECent Oklahoma lease.... 160 10 10 0.25 Kansas lease....... 125 4 20 0.25 to 2 On the Oklahoma lease, the machine was cleaned of solid material once in 12 hr. At first, it was thought that chemical treatment was necessary to start separation and 1 qt. of prepared compound was added to each 100 bbl. of the cut oil before centrifuging. Later it was found that

Jan 1, 1924

By N. J. Themelis, P. Spira

The efficiency of the reverberatory furnace operation in producing. slags of 1020 copper content depends on the mixing and flow conditions in the bath. Radioactize-tmcer tests have indicated the jkaction of bath volume engaged inflow and the mixing conditions in the bath. The factors controlling the flow pattern of slag have been classified as laminar transfer flow, natrsral convection, and flou, due to the rapid addition or removal of slag.. Similarity criteria for model studies have been developed. The pyrometallurgical processing of copper begins with the smelting of either flotation concentrates, or direct-smelting ores which have been partially roasted to calcines. These materials are generally smelted in a reverberatory furnace, Fig. 1, and separate into two liquid phases, a sulfide matte and an iron silicate slag. he matte is tapped and subsequently reduced to metallic copper in a converter, while the reverberatory slag is usually discarded without any further treatment. Molten slag from the converting operation is returned intermittently to the reverberatory in order to recover its high copper content (1 to 3 pct Cu). The reverberatory furnace is about 115 ft long by 30 ft wide. In general, the solid charge is fed at intervals through openings along the sides of the roof and forms sloping banks from which the molten materials trickle down into the bath; the charge banks extend over a length of about 70 ft from the firing wall. The depth of the slag and matte layers varies from smelter to smelter; in the Noranda furnaces, the slag depth is 24 to 30 in., while the depth of matte at the taphole is about 20 in. Apart from smelting, the functions of the reverberatory are to recover most of the copper content in the converter slag by physical and chemical interaction with the furnace bath, and to provide adequate time for optimum separation between matte and slag. The efficiency of these operations depends on the mixing and flow conditions in the bath and is reflected on the copper losses in the slag. In the present study, the reverberatory furnace is considered as an open-channel chemical reactor and the driving forces for material transport through the bath are examined by means of flow and mathematical models. FLOW CONDITIONS IN THE REVERBERATORY FURNACE To facilitate the study of mixing conditions in continuous-flow reactors, two idealized patterns of flow have been accepted by workers in this field.&apos; The term "backmix" flow is used to describe complete and instantaneous mixing in the reactor (perfect mixing); all particles have the same chance of leaving the system, independently of their time of entrance, and the fluid is uniform in composition throughout the vessel. On the other hand, "plug" flow, or "piston" flow, assumes that a fluid element moves through the reactor without overtaking or mixing with fluid entering at an earlier or later time. In addition to the two idealized patterns of flow, "deadwater" flow accounts for that portion of the fluid which is moving so slowly that it may be assumed to be stagnant. According to the definition by evensppiel,&apos; the cut-off point between active and stagnant fluid may be taken as material which stays in the vessel for a period twice the mean residence time. The flow patterns in real vessels may be approximated by a combination of the above flows. Thus, the vessel is assumed to consist of interconnected flow regions with various modes of flow existing between them. The flow pattern may be determined directly from the flow paths of fluid through the essel. -However, the difficulty of obtaining and interpreting such information has led to the alternate approach of determining the residence time distribution of fluid elements by means of stimulus-response studies. The stimulus is provided by introducing a tracer in the inlet stream and the response by the record of the change in tracer concentration in the exit stream from the reactor. Such tests have been conducted in glass tank furnaces using either chemical7"9 or radioactive tracers1&apos;-&apos;&apos; and, in one case, experiments have been reported for a metallurgical furnace.&apos;"

Jan 1, 1967

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS,4 BRADLEY STOUGHTON.

Jan 9, 1913

STANDING COMMITTEES. Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. KARL EILERS, JOHN H. JANEWAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL .EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman 1 JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALEX. C. HUMPHREYS, 4 BRADLEY STOUGHTON.

Jan 12, 1913

By P. F. Gnirk, J. B. Cheatham

An experimental investigation has been made to study the effects of tooth angle and confining pressure on the force required for indentation of dry rock samples under confining pressure. In these experiments static single-tooth indentations were made on two standstones, a limestone, a schist and a slate under confining pressures of 5,000 to 15,000 psi. Sharp wedge-shaped teeth with included angles ranging from 30°to 105°were used. In all cases the force-displarenzent curves are approxinlately linear for rocks tested under confining pressure, as contrmted with the discontinuous curves obtained for silnilar rocks at atmospheric conditions. Photonzicrographs of thin sections through the craters indicate very little evidence of chip formation during indentation. In general the experimental data lie between calculated values for perfectly rough and perfectly smooth tooth-rock interfaces. INTRODUCTION The variables associated with ctrilling at depth are numerous and, in many instances, are not easity isolated and controlled. Also, many of these variables are interdependent; however, if the variables which are sufficiently independent of each other are held constant and are appropriately introduced, the dependent variables can be more easily studied and evaluated. It is the purpose of the present investigation to study experimentally the simplest case of bit tooth-rock interaction. In essence, the experiments have involved the static loading of sharp wedge-shaped tools on the surfaces of effectively semi-infinite dry rock samples subjected to confining pressures. During this investigation the following quantities have been maintained constant: 1. Pore pressure: atmospheric (i.e., the rock is dry). 2. permeability: although the rocks may be permeable, they are "jacketed" in such a manner that the fluid is not permitted to flow through them. 3. Temperature: 75F. 4. Rate of loading: essentially static (approximately 0.002 in./second). 5. Bit tooth: a sharp wedge-shaped tooth loaded normal to the rock surface. 6. Rock surface: smooth and flat. 7. Drilling fluid: hydraulic oil. In addition to the above conditions, the rock surface was free of a layer of cuttings. There was no indexing to previously indented surfaces, and the influence of corners of the borehole was neglected because the rock samples were effectively semi-infinite. The following quantities have been varied, and the resulting effects have been studied: 1. Rock a) Type (e.g., limestone, sandstone, etc.). b) Mechanical properties ) Necessarily dependent c) Porosity on type of rock. 2. Bit tooth (included angle of wedge-shaped tooth). 3. Depth of penetration. 4. cobfining pressure. On the basis of laboratory experiments which have shown that many rocks exhibit ductile behavior at confining pressures corresponding to depths usually reached during drilling,&apos;.&apos; a theory has previously been advanced which predicts the force required for penetration by a single sharp wedge tooth into a ductile* material.&apos; The material is assumed to be isotropic, homogeneous and rigidly plastic (no elastic deformation) and to obey the Coubomb yield criterion (Figs. 1 and 2). Equations governing the force required for penelration are given for two extreme cases:** 1. A smooth, perfectly lubricated tooth-rock interface (fridionless boundary), in which the solution gives a minimum value for the penetrating force: in which F = force of the tooth, b = length of tooth edge,