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Jan 1, 1907

By D. Hanson

Fox most of their practical applications metals are required to with-stand stresses of appreciable magnitude: indeed, it is because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances-or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By M. Gensamer

THE PURPOSE OF THIS PAPER is to lay a foundation of elementary theory that might be useful in the discussions which it is hoped will be evoked during this Symposium. It is not my purpose to try to expound the details of the most complete theories as that would be impossible in the time at our disposal and, even if time were available, would probably be of less usefulness than a discussion of the principles underlying the advanced theoretical treatment. I shall try to discuss the fundamental bases for these advanced theories. There exists at the present time very much less need for a detailed description of complete theory than existed when this Symposium was being organized. The reason for this is that a series of papers by L. R. Underwood has been appearing in the magazine Sheet Metal Industries. It is understood that this series will he published soon in the form of a book. Dr. Underwood's articles are complete, critical and well written and it would be hopeless to try to do better in less space. The need, then, is for a brief treatment of basic theory. The objective of any theory of plastic forming- is to enable one to calculate the force and power requirements for the process, and where the deformation is not uniform, to calculate the distribution of strains- In the formed object. We need as the basis for the calculation the relationship between stress and strain in the metal, particularly for the combination of stresses imposed by the forming process. We need to know the stress-strain curve for some simple state of stress, and we need in addition some theory

Jan 1, 1948

By R. L. Perrine

This paper shows how stability theory can be used to optimize solvent recovery of oil. Application of the theory leads to definition of the limiting conditions required for stable displacement to occur. One of these conditions is that the size of a solvent "slug" must at least equal a prescribed minimum. The criteria to be satisfied are miscibil-ity and stability. Stability implies that no viscous fingering will occur and that mixing will be caused only by a dispersion process. Miscibility implies that complete recovery will be obtained from the swept regions. Thus, for any specified set of reservoir conditions, an optimum use of solvent is defined. INTRODUCTION The early outlook for solvent flooding as a means to increase oil recovery was very favorable. Some laboratory results indicated that a "slug" containing perhaps 2 to 3 per cent of a hydrocarbon pore volume could be successful. However, other data suggested as much as 30 per cent would be required. The difference is of considerable economic importance. A theoretical explanation for these divergent results has been advanced by the author.1,2 Stability theory defines conditions for two distinct flow regimes. In stable displacement, solvent and oil become mixed by a dispersion process, and the solvent requirement is small. On the other hand, unstable displacement can degenerate into viscous fingering. The practical result is a considerable increase in the extent of mixing and, thus, in the solvent required. The present paper shows how to use stability theory to optimize solvent recovery of oil. Oil is usually considered to be displaced by a small amount, or a slug, of solvent. Gas in turn follows solvent. Any fingering will permit contact of nearly solvent-free gas and oil, leading to immiscibility and reduced recovery. Thus, our optimum is defined by two restrictions — stable flow and miscibility. Although an immiscible solvent process could prove more profitable than any miscible process, such processes lie outside the selected definition of an optimum. The usefulness of computations based on the present work will depend on the validity of the general theory. Because the important idealizations required tend to minimize the predicted solvent requirement, the results should state correctly the limiting conditions required. Therefore, theoretical calculations should have practical value. This paper first reviews several principles that result from stability theory. The following section describes use of these ideas in relatively simple systems which symmetry makes appear one-dimensional. Of particular importance is the step-by-step design of 3 stable minimum-solvent slug. The use of stability theory in cases of multi-dimensional displacement is discussed and, finally, suggestions are given for simplified practical application of the theoretical results. PRINCIPLES OF STABILITY THEORY The use of perturbation methods to derive stability conditions has been shown by the author.l The discussion is presented in terms of the fractional concentration of solvent in the single hydrocarbon phase. Quite generally, any disturbance can be represented as a Fourier series, of which only the least stable term need be considered. Denoting this term at time t = 0 by cn,

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,'" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

Jan 1, 1966

By C. R. Wohrman

A MELT of pure electrolytic iron with about 0.4 per cent. sulfur and 7 per cent. manganese was prepared in connection with a study of inclusions in iron. The alloy darkened rapidly when etched with a 10 per cent. alcoholic solution of nitric acid, and microscopic examination revealed the presence of a semimartensitic, semi-Widmanstättian structure (Figs. 1 and 2) closely resembling the structures found by Benedicks in his artificially prepared "meteoric iron." 1 The structures found by Benedicks were readily explained by the presence in his alloy of the two well known iron-nickel solid solutions, taenite and kamacite, and of their eutectoid (?) aggregate, plessite. By analogy, one would infer the existence of similar phases in the iron-manganese alloy just described, such as inference being strengthened by the similarity displayed in many ways by nickel and manganese in their effects on iron. IRON-MANGANESE ALLOTS ARE REGARDED AS HOMOGENEOUS Heterogeneity of iron-manganese alloys has not been recognized heretofore, judging from the data of standard metallographic books and those of original papers. In fact, iron and manganese are quite generally regarded as completely miscible in the solid state. Dr. Rosenhain,2 for example, writes: Alloys of group (a), of which those of gold-silver, iron-manganese, and copper-nickel are examples, when allowed to crystallize sufficiently slowly to attain their condition of final equilibrium, present a microstructure exactly similar to that of a pure metal-the homogeneous character of the molten solution is in that case so completely maintained that the microscope cannot detect the presence of any second constituent.

Jan 1, 1927

By Clyde E. Williams

MORE has been said about the iron and steel situation on the Pacific Coast than has been done .about it; but perhaps as much has been done as conditions have warranted. The production of finished steel in an amount sufficient to take care of the local demand for certain sizes and shapes is an established industry on the .coast. The amount .and the variety of products, so made, changes with the demand or them which is largely dependent upon the growth in population. An increasing demand will not always increase the quantity of steel produced locally because the cost of production may rise so -high as to let in steel from the outside. The reason for this is that all of the steel made in the West comes from steel scrap, the supply of which is .limited. From the standpoint of the metallurgist, it would. be desirable to subititute pig iron for some of ' the steel scrap, but this cannot be done profitably because the pig iron now available is too expensive. In other words, the large future demand for steel and pig iron on the Pacific Coast must be supplied by reduction of ores in the West, unless we are to be content with paying high transportation costs for material produced elsewhere. ."

Jan 1, 1924

By William E. Ford, Edward Salisbury Dana

1. Normal Class (25) Barite Type 2. Hemimorphic Class (26) Calamine Type 3. Sphenoidal Class (27) Epsomite Type Mathematical Relations of the Orthorhombic System Crystallographic Axes. - The orthmhombic system includes all the forms which are referred to three axes at right angles to each other, all of different lengths. 296 Any one of the three axes may be taken as the vertical axis, c. Of the two horizontal axes the longer is always taken as the b or macro-axis * and when orientated is parallel to the observer. The a or brachy-axis is the shorter of the two horizontal axes and is perpendicular to the observer. The length of the b axis is taken as unity and the lengths of the other axes are expressed in terms of it. The axial ratio for barite, for instance, is a : b : c = 0'815 : 10 : 131. Fig. 296 shows the crystallographic axes for barite.

Jan 1, 1922

By Bradley Stoughton

As a part of the systematic study of the alloys of iron under the auspices of the Engineering Foundation, and preliminary to the commencement of comprehensive work on this larger subject, the authors have undertaken an investigation of the available literature dealing: with the alloys of iron and silicon. The purpose is to collect all the data in English and foreign languages and present them in two mono-graphs, one of a more scientific and the second of a more industrially useful nature. Of course, a great deal of information upon the constitution of the iron-silicon alloys was found specificially upon the changes of phase in the equilibrium diagram and the different phases present, such as solid solution, chemical compounds (iron silicides), etc. While no extended research was contemplated in the particular study undertaken, nevertheless the data collected proved to be so contradictory in many respects that a simple study of some of the outstanding problems involved in the constitution and equilibrium diagram was undertaken Because research was not a primary object of the work, and also because of the extreme industrial importance of the silicon alloys between 0.80 and 14 per cent. silicon, and finally because of the unsatisfactory state of knowledge existing as to these alloys, the experimental investigation was limited entirely to alloys with less than 10 per cent. silicon.

Jan 1, 1930

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By N. Nemeth, L. L. Sirois

The role of the filter medium in continuous-vacuum filtration and the special circumstances which influence the resistance to flow through the porous cake and filter cloth are discussed. Due to negative pressure differential, gas bubbles evolve in the slurry, constrict passages in the filter cake and medium, and further restrict flow through the tortuous channels. Filtration is a liquid-solid separation process taking place at a porous medium under a pressure differential. The liquid passes through the medium; the solids are retained on the medium as a partially dewatered cake. Filtration is far from a simple process and has been described in terms ranging from "complex" to "subtle." Because of the many variables involved, no unified filtration theory has been developed, and the filtration process is still considered very much an art. In industrial filter design, basic relationships, whether derived for idealized conditions or developed empirically, are usually adapted to suit local conditions. In the mining industry where continuous-vacuum filtration is the main dewatering process, the physical state of the concentrates and the relatively low pressure differentials permit the assumption that the cakes are noncompressible, an assumption which leads to the use of theoretically sound rate equations. Notwithstanding this simplification, there are other problems, unique in the application of vacuum to dewatering, and until now completely ignored, which demand special attention. The basics of filtration involve the capture of solids on, while permitting the flow of liquid through, a porous layer of cake and cloth. Flow is determined by the structure of the solids which make up the cake and the particles permanently attached to the cloth. The problem of this structure, essentially one of solid geometry, has been considered insoluble by Hatscheckl as early as 1907 and by Freshwater as recently as 1967. Since cake structure is determined by the slurry parameters, that problem is far too large for inclusion in this study. For theoretical considerations, uniform buildup of the filter cake must be assumed; and for efficient practical operation, the resistance of the medium must be kept constant over long periods. The latter can be achieved by careful selection of the filter cloth, since the greatest part of the total filtration resistance will develop at the cake-cloth contact. This paper discusses the role of the filter medium in continuous vacuum filtration and the special circumstances which influence the resistance to flow through the porous cake and the filter cloth.

Jan 1, 1971

By D. M. James, J. C. Martin

The results are presented of a study of the application of analytical methods to the solution of two-phase flow into single wells. Approximate analytical expressions for the pressure distribution in two-phase flow are found ;;; a number of conditions. The results obtained from the analytical solutions me found to be in good agreement with results obtained by finite difference techniques using a high speed digital computer. Mathematical solutions for four sets of boundary conditions are presented. All of these solutions are composed of a short-term transient plus a steady or quasi-steady state. The rates of decay of the short-lived transients are analyzed. It is found that the durations of the short-term transients may be characterized by a parameter defined as the time constant which can be determined from simple relations. It is shown also that if the outer radius is much greater than the radius of the well. the short term transients decay at rates which are proportional to the square of the exterior radius, and the rates of decay are only slightly dependent upon the radius ratio. Numerical solutions based on finite difference techniques are presented for a number of conditions. The numerical solutions are in good agreement with the predictions based on the theoretical analysis for small and moderate drawdowns. Examples involving large drawdowns indicate that the nonlinearities in the equations of flow do not appreciably alter the longevity of the short-term transients. In all cases the time required for the short-tern transients to disappear is predicted satisfactorily. INTRODUCTION The mechanism by which oil and gas flow into a single well is of vital interest to the petroleum industry. The fundamental equations of two-phase flow which describe this mechanism are nonlinear partial differential equations. Numerical solutions of these equations describing pressure transients have been obtained with the aid of electronic computers. Although solutions obtained in this manner take into account a large number of effects, the reduction of this information to useful generalities is difficult. One method of obtaining generalities is the use of linearized approximations of the nonlinear equations. Since it is possible to obtain explicit solutions of the linearized equation, general properties of the role of pressure in the flow mechanism may be ascertained. Results obtained from this approach are limited to some extent by the linearizing assumptions. The severity of these limitations may be evaluated by comparing solutions of the linear equation with numerical solutions of the more exact nonlinear equations of two-phase flow. In the past considerable amount of work has been devoted to studying pressure build-up using the single-phase flow theory. Unfortunate1y, most prep sure build-up tests involve multiphase flow. A small amount of work has been done studying pressure build-up where the flow is two-phase. The encouraging results of these studies suggest that useful results may be found from additional studies of not only pressure build-up, but also the rapid transients associated with placing a well on production. This paper presents the basic theory of the pressure transients associated with placing a well on production and with closing it in. The paper is concerned chiefly with two-phase compressible flow; however, the results also apply to single-phase flow. The results are based on analytical solutions of the flow equations, and they are verified by numerical solutions using finite difference techniques. Much of the previous work on compressible flow into wells has been confined to single-phase flow. Some work has been done on compressible two-phase steady state flow, and solutions of the equations of flow have been found by finite difference techniques using high-speed computers. Muskat1 presents some rather general solutions to the equations of single-phase compressible flow into wells. Much work has been done on pressure build-up in wells (see, for example, Refs. 2-6). Almost all of the work on pressure build-up concerns single-phase flow with the exception of Ref. 5 and part of Ref. 2. Some work has been done on pressure fall-off in injection wells.718 Muskat9 presents the solution of the equations for radial steady state two-phase compressible flow. Handyl0 extends Muskat's solution to obtain

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By John M. Cummings, Warren. Harry V.

THE Geology Department of the University of British Columbia has undertaken the task of examining the ores from as many as possible of the gold mines of British Columbia. The object of this work is two- fold. First, it is known that detailed mineralographic studies are useful in attacking ore-dressing problems, and these studies are intended to be helpful to mill operators. Second, it is hoped that mineralogical and mineralographical studies will prove useful adjuncts to those of lithology and structure in throwing more light on problems related to the origin of the deposits. The paper shows that gold, for all practical purposes, is not present in an ore mineral in solid solution nor as a eutectic with any mineral; if the latter were true the gold particles would be distributed equally throughout that mineral. The gold occurs either as native gold or as a gold-silver telluride and is not distributed regularly through any mineral or minerals. The relationship between the gold or gold-bearing telluride and the associated minerals affords a means of classification that is not only simple but also appears to be directly related to the geological nature of the deposit, which may be summarized as follows: 1. Disseminated Gold Type.-Precious minerals in extremely small grains, which are distributed without regard to grain size, fractures or grain boundaries: (1) Hedley variety-gold in native form; (2) Surf Point variety-gold predominantly as telluride. 2. Veining Gold Type.-Precious minerals in grains of various sizes, which occur mainly along fractures and grain boundaries: (1) Cariboo gold quartz-goldin native form. (2) Waneta variety-gold as telluride. Application Te Ore Dressing These mineralographic studies have proved to be of value to mill operators, and future studies of a similar nature should prove increasingly useful because every year provides a further opportunity to correlate

Jan 1, 1937

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.' The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast' reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By M. Cross

INTRODUCTION The development of refining processes involving gas injection into liquid metals has seen the evolution of a variety of designs [I]. During the last few years or so the top, bottom and side blown processes have, essentially, been combined to produce a series of mixed gas blowing schemes (eg. the LBE [2,3] and LD-OB processes [4,5]). Although, a variety of mixed gas blowing processes have been carefully engineered and recorded operational experience now attests to their effectiveness, optimising their design and operational performance is another matter. Detailed process analysis of such operations is impeded by the complex nature of the physical and chemical processes involved: . fluid flow behaviour of the liquid metal and injected gases, . chemical reactions in the vessel, . mass and heat transfer within the fluid phases in the vessel, . influence of the geometry (eg. location of the tuyeres, etc.), . monitoring the operational performance. By and large, design and operating parameters evolve from a combination of laboratory scale experiments, pilot plant work and, of course, practical engineering experience. Conventionally, the gas-liquid system used to model the industrial process is air-water, for a number of valid reasons including – . visual demonstration plus geometric and (to some extent) dynamic similarity, . the fact that the system demonstrates, at least, qualitatively many of the complex features of gas injection - interaction between the gas and the liquid - the nature of the gas flow behaviour - qualitative indications of mass transfer rates Important experimental contributions to the understanding of gas liquid systems include the work of Brimacombe [6], Wraith [7], T.Robertson [8], D.Robertson [9], Guthrie [10] and Szekely [11] (these references provide starting points to identify the major published work in this area). Although air-water systems have been instrumental in providing a great deal of qualitative insight into the fluid flow behaviour of the processes, reliable quantitative predictions are more problematic. A number of workers (notably Brimacombe and colleagues [6, 12])have demonstrated that different gas-liquid systems can lead to wide variations in behaviour. Other limitations of physical modelling include the assumptions of isothermal flow, scale- up of turbulent flow behaviour and the inability to directly include the effects of chemical reactions. The above limitations in physical modelling, therefore, yield a natural role for mathematical modelling provided that it can be made comprehensive enough whilst remaining cost-effective. The major physical processes involved in gas injection systems may be summarised as . behaviour of the gas envelope structure in moving through the liquid metal . the global movement of the liquid metal . momentum interaction between the liquid metal and the injected gas . heat transfer and mass exchange via the chemical react ions. The behaviour of gas envelopes forming at a tuyere and then moving through the liquid has been investigated thoroughly by a large number of workers. Such models are generally based upon simple physic- al concepts derived from visual observation. An early model by Davidson and Schuler (DS), based upon a force balance between the liquid inertia and a combination of the bouyancy and momentum forces on the envelope, has proved to be a useful tool in predicting bubble volumes at detachment [13]. The DS model has been successfully modified in a number of ways [14-17] to cope with heat transfer and reactive transfer rates, etc. Furthermore, the basic ideas summarised above have also been confirmed on industrial converters by both Guthrie [I8] and Brimacombe [19]. Models have also been developed to predict the behaviour of the "chemical" component of some gas-liquid systems. However, one thing is clear; all gas-liquid reactive systems are governed by the degree to which effective mixing occurs. As such, the processes are dominated by the behaviour of the heat and mass exchange of the two phase fluid flow system. It is the pattern of movement of the turbulent liquid metal plus its interaction with the injected gas which must be predicted reliably, if sufficiently comprehensive comp-

Jan 1, 1984