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By C. J. Ramsburg

The construction and operation of by product coke-oven plants in America are essential to strong national defense and of the greatest importance to many widely diversified undertakings as well as to safety and health. Carbonization Process Coal used under a boiler or in a locomotive is consumed by combustion. Coal used in a by-product oven is distilled or carbonized, meaning that heat is applied to the coal, out of contact with air, causing a distillation that removes the volatile matter in the coal in the form of gas and vapor, leaving coke as a final product. From the gas and vapor distilled from the coal, many valuable substances can be secured, known as by-products. Hence the name "by-product oven." The simplest example of this principle can be shown by means of an ordinary clay pipe. If powdered coal is placed in the bowl of the pipe, the opening of the bowl is plugged with clay, and the bowl placed in a flame, the bowl will become hot, transferring the heat through the wall of the bowl to the coal within. When this coal attains a temperature of about 750°F., gas will begin to pour out of the pipe stem, and this gas may be lighted. A black liquid also will exude from the stem of the pipe, This is tar mixed with certain other products. What remains in the bowl after distillation is coke. A coke oven corresponds to the bowl of the pipe. A modern oven of the latest type is a refractory brick chamber approximately 42 ft. long and 14 ft. high, averaging 18 in. in width. The oven is filled with coal through closable charging holes in the oven top. Each end of the oven consists entirely of a self-sealing door, the removal of which permits the finished coke to be discharged by means of a power-operated pusher machine. The ovens are built in batteries, and the heating is effected by gas burned in vertical flues in the oven walls, each set of flues heating the walls of two adjacent ovens. Such ovens carbonize a charge of approximately 18 tons of coal in 18 hr., or have a daily throughput of 24 tons per oven, producing about 17 tons of coke. In times of need, the output may be increased by raising the temperature of flues, thus shortening the coking time. There is one great essential difference in principle between distillation in a clay pipe and in a coke oven. In the 18-in. oven, the distillation proceeds from two parallel walls held at a high temperature (over zooo°F.) and instead of all the coal being heated at once, the distillation is a progressive one creeping inward. The average travel of this heating is 35 in. per hour from each vertical wall, and as the volatile products are formed progressively they must push away from the interior toward the wall through the previously formed hot coke, then up the walls and Over the top of the coal charge, finally escaping through the outlet pipe. This results in a cracking of the components into many different and valuable substances not formed when the carbonizing temperature is low.

Jan 1, 1942

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By R. S. Shoemaker, D. L. Harris

PST investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation. The X-ray diffraction analysis of chemical compounds of crystalline form has proved of inestimable value for structure studies and rapid qualitative analytical purposes in a number of fields.' In some cases X-ray diffraction analysis has been found suitable for quantitative determinations. H. P. Klug2 found that quantitative procedures for quartz powders when mixed with calcium fluoride were reproducible within ±1.0 pct. Talvenheimo and White3 reported quantitative analyses of clay minerals to be accurate within 10 pct and also detected 1 pct of bentonite in 99 pct illite. In other investigations,'" powders of quartz and mica have been analyzed quantitatively with accuracies from 1 to 5 pct. A powder of tungsten carbide was analyzed similarly by Redmond7 and Rooksby8 reported the determination of small amounts (0.11 pct) of calcium oxide in magnesium oxide. In the most generally practiced use of X-ray diffraction, traces of the diffracted beam are recorded as lines on a film much as lines of elements are recorded on an optical spectrograph film. As with the spectrograph, the darkness of the lines denotes the amount of the constituent in the sample. If the film is replaced by a Geiger tube assembly and a graphic recorder or a scaling unit, the intensity of the diffracted beam can be registered as a peak on a chart or energy impulses per unit of time on the scaler. Several methods of quantitative measurement have been investigated and reported in literature. Klug2 used manual operation of the goniometer and a counting technique to determine the difference in counting rates at the diffracted angle and for the background. In another case3 the area under the recorded diffracted peak was the basis for the determination. In other instances the height of the recorded diffraction peak above background, measured while the goniometer was moving, has been the basis for the measurement. The sizes of particles most suitable for diffraction techniques are reported in the literature as follows: for tungsten carbide a maximum of 40 microns7 and for quartz a maximum of 5 microns.' Very fine sizes of crystals are known to cause a broadening of the diffused beams; hence some workers have set a lower limit of 0.1 micron for quantitative results. Guinier10 has indicated that broadening of the diffracted X-ray beam is not appreciable for crystallites larger than 0.02 to 0.03

Jan 1, 1956

By G. C. Wallick, W. R. Foster, J. G. Savins

A comprehensive review of the salient features of the differentiation method of rheological analysis in Poiseuille flow from its inception circa 1928 is presented. Here no initial assumptions regarding the nature of the function relating rheological parameters to observed kinematical and dynamical parameters are required in the data-analysis process. In contrast, the integration method involves interpreting flow properties in terms of a particular ideal model. It is shown that, although both methods represent modes of solution of the same integral equation, being relatively bias-free, the differentiation method offers a more discriminating procedure for rheological analysis. The application to problems involving plane Poiseuille flow is also described. INTRODUCTION In most instances, the approach to the problem of interpreting the rheological properties of various compositions as they are affected by changes in chemical or physical environment, assaying the characteristics of a particular constituent of a suspension, analyzing flow behavior in terms of interactions between components in a system, to cite but a few examples, has been in terms of what Hersey1 terms the integration method. Briefly, it consists of interpreting flow properties in terms of a particular ideal model. The usual practice of the integration method is to choose a model with a minimum number of parameters because, other things being equal, it is desirable to use the simplest model which will describe the behavior of a real material and yet be mathematically tractable for the requirements of data analysis. This expression is then substituted into an equation which relates observed kinematical and dynamical quantities, such as volume flux Q and pressure gradient ], and angular velocity and torque T, in a capillary and concentric cylinder apparatus, respectively. The rheological parameters appear on integrating, in an expression relating the pairs of observable quantities such as those just given. In many instances a particular model provides a good representation of rheological behavior over a reasonable range of compositional and environmental changes. Just as often, however, it is obvious that the interpretation of rheological changes by the integration method is not providing realistic information about changes in flow behavior. A more general method of interpreting rheological data for a given material is to make no initial assumptions regarding the nature of the function relating rheological parameters to observed kinematical and dynamical quantities, e.g., flow rate and pressure drop in capillary flow or angular velocity and torque in a rotational viscometer. This general method Hersey1 terms the differentia-ation method. Instead of integrating, one differentiates the integral equation with respect to one of the limits, i.e., one of the boundary conditions; the resulting expression contains the same observable quantities just given, their derivatives, and the rheological function evaluated at that boundary. By obtaining these derivatives from experimental data, graphically or by a computer routine, they can be substituted into the differential equation and a graphical form of the function derived. THEORY OF THE DIFFERENTIATION METHOD FOR POISEUILLE-TYPE FLOWS In this introductory paper, two flow cases which are important in viscometry are considered (one for the first time) from the differentiation method of analysis, flow in a cylindrical tube and flow between fixed parallel surfaces of infinite extent, the basic integral equations being formulated in a manner analogous to the way they originally appeared in the literature. In addition, the following ideal conditions will be assumed: (1) an absence of anomalous wall effects, (2) isotropic behavior everywhere, and (3) steady laminar flow conditions. Before proceeding it would seem appropriate to preface the analysis of these flow geometries with the comment that the basic philosophy of the differentiation method could be said to stem directly from the efforts of Herzog and weissenberg2 to indicate systematically the various ways of using

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By R. D. Lee

A simplification of the method of Hurst and McCarty for conducting potentiometric model studies by the single probe method is presented along with experimentally determined invasion patterns for certain idealized flow problems. The analytical solution for one class of these problems is given. Finally, a general description is given of a newly developed instrument which permits direct mapping of flow lines and determination of transit times in potentiometric-model studies. Introduction The object of this paper is to present: I. A simplification of the method of Hurst and McCarty for conducting poten-tiometric-model studies of oil and gas reservoirs by the single probe method. 2. Results of a series of studies of certain idealized flow problems and the general conclusions to be drawn therefrom. 3. A description of a new instrument, the Chronocartograph, which greatly reduces the labor and time required for conducting potentiometric-model studies. Certain general conclusions may be drawn as results of the investigation of the idealized flow problems. They are: I. Injection and extraction areas should be separated by as great a distance as conditions permit since, in general, the recovery prior to first breakthrough tends to vary as the square of this distance. 2. Little advantage is to be gained by use of more than eight injection wells or groups of injection wells for the case of circular productive limits. 3. Elongated shapes of productive limits are best exploited by injection on the extended major axis only, with a line of extraction wells lying on the major axis. 4. The use of peripheral injection wells for elongated shapes is permissible, if necessary, but requires extension of the line of extraction wells. The exploitation of an oil or gas field is effected either by the expansion of the gas and oil, or by their displacement by another fluid. Both methods may be used simultaneously. When the displacement of the oil or gas is the controlling factor there arises the problem of mapping the progress of the boundary between the fluid in place and the displacing fluid. This problem is of particular interest in the operation of a cycling project in a gas-condensate field, where the wet gas is produced from one or more wells, commonly called "extraction wells.'' This wet gas is taken into a processing plant where the condensate is removed. The remaining "dry" gas is injected back into the field through one or more wells, called "injection wells," both to conserve the gas for future use and also to maintain the pressure in the field. In an operation of this type it is essential to anticipate the manner in which the dry gas will spread through the field, because the ultimate recovery of the wet gas depends

Jan 1, 1948

By Arthur Gates

INTRODUCTION RITTINGER'S law of the energy expended in crushing is, as roughly stated by Professor Richards,1 that the work of crushing is proportional to the reduction in diameter; or, as I have more fully expressed it: "The work done in crushing is proportional to the surface exposed by the operation; or, better expressed for this purpose, the work done on a given mass of rock is proportional to the reciprocal of the diameter of the final product-assuming that all the mass has been reduced to one exact size, which is only theoretically possible.?2 Kick's law is stated by H. Stadler as follows:3 "The energy required for producing analogous changes of configuration of geometrically similar bodies of equal -technological state varies as the volumes or weights, of these bodies." In other words, the energy expended is porportional to the volume reduction, instead of the diameter reduction. That these two laws would give widely different results may be shown by a simple imaginary case. A ton of 16-in. cubes is broken to 1 -in. cubes at the first operation, and these are broken to 1/16 -in, cubes at a second operation. Since the first operation produces only one-sixteenth as much new surface as the second, the ratio of energy expended in the two operations would be by Rittinger's law as 1 to 16. By Kick's law, since the volume-reduction ratio is the same in both cases, the ratio of energy would be 1 to 1. This discrepancy is great enough to challenge a test by actual experiment, of which there has been, hitherto, but little compared with the amount of argument. The present paper is the record

Jan 9, 1915

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.' The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown' to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown' has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler' is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:'

Jan 1, 1970

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 G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By H. C. Lukens, E. V. Potter

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

By W. C. Coffin

Fire-brick stoves have become a necessary part of the modern coke blast-furnace equipment, and are also superseding the cast-iron pipe stoves in anthracite- and charcoal-furnaces. The brick stoves in general use are of either the Cowper or Whitwell type, or modifications of these bearing the names of those who invented the alterations from the original types rather than any real departure from then]. All these stoves have approximately the same valve-equipment and follow the same line of operation. The waste gas from the furnace enters at one port and burns in a single combustion-chamber, and the heated products are drawn through the various passe; in the brickwork to a stack of proper height to create the necessary draught. The last passes of these stoves receive a very small percentage of the heat from the gas, owing to their extreme distance from the combustion-chamber; and this chamber also suffers great deterioration in the attempt to force the heat into the farthest passes. At best, about 70 per cent. of the heat taken up is held in the combustion-chamher and the first down-pass of the Whitwell stoves. Mr. Hugh Kennedy, Manager of the Isabella Furnaces, Pittsburgh, Pa., who has had a large experience with the fire-brick hotblast stoves, was so strongly impressed with the fact that but about thirty per cent of the brick of the average stove were doing proper duty as heat-agents, that, after careful study and experiment, he had three 20- by 60-feet stoves constructed with a view of more uniformly heating all the brick. In these the general lines of the Whitwell stove are followed, with the blast-connections unaltered, but gas is introduced at the bottom of each pass, and outlets are provided at the top, so that the gases have a direct natural draught in each pass and the highest heats are obtained at the bottom instead of the top. The natural tendency being toward the reverse condition, the brickwork soon acquires an almost uniform temperature.

Jan 1, 1893

By E. V. Potter, H. C. Lukens

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

By M. C. Dow

Belt conveyors generally are conceded to be the most economical method yet devised for the transportation of large quantities of bulk materials within plants. Belts are coming into greater use for transportation over long distances and are replacing other forms of long-haul conveyance. It is not the intent of the writer to comment on the design of belt conveyors, but to offer some suggestions for improvement in the operation of conveying belts, based on many years experience with belts in several stone-crushing plants. It is the contention of this writer that opportunities for improvement not fully realized by most operators exist in many plants and that a study of the individual conveyors can result in lower unit belt costs. General Reliability It is the fool-proof nature and general reliability of the belt conveyor that is responsible for its neglect. Even when abused, a belt will carry large tonnages and last a long time, often outlasting the personnel responsible for its care. Some operators look upon the purchase of a new belt as an expensive outlay every so many years, rather than a constant and steady cost amounting in belt wear alone to several dollars every operating day. This belt wear for all conveyors in one stone-crushing plant known by the writer costs 1 /12 cents per ton or $12 to $15 per hour, based on the present cost of belt replacements. The fact that these replacement costs are double those of prewar quality emphasizes the necessity of improving the conditions that make belts wear out. Some of those conditions are the responsibility of the conveyor designer, and if a serious original error has been made, this handicap cannot be overcome by the operator. If the belt is too narrow, too steep, or too fast for good loading, the operator finds that he has an inherently expensive belt. The other factors that decrease the life of a belt are more or less under his control. The two factors of most importance are the loading conditions and the alignment. Most of the cover wear and carcass cutting occurs at the loading point and if the alignment is not good under all conditions, edge wear or damage may result, Fig I. Loading the Belt It is difficult to load a belt in an ideal manner; that is, to flow the material on the moving belt at a steady rate, without impact, without turbulence, and with a velocity equal to and in the same direction as the belt. An inclined belt is especially difficult to load and particularly when its speed is over 300 or 350 fpm. Inclined conveyors require longer skirt plates to prevent spillage until the load settles. It does not seem reasonable to expect an inclined the to carry the same load as a horizontal belt of the same width and speed, because of the difficulty in loading

Jan 1, 1948

By M. C. Dow

Belt conveyors generally are conceded to be the most economical method yet devised for the transportation of large quantities of bulk materials within plants. Belts are coming into greater use for transportation over long distances and are replacing other forms of long-haul conveyance. It is not the intent of the writer to comment on the design of belt conveyors, but to offer some suggestions for improvement in the operation of conveying belts, based on many years experience with belts in several stone-crushing plants. It is the contention of this writer that opportunities for improvement not fully realized by most operators exist in many plants and that a study of the individual conveyors can result in lower unit belt costs. General Reliability It is the fool-proof nature and general reliability of the belt conveyor that is responsible for its neglect. Even when abused, a belt will carry large tonnages and last a long time, often outlasting the personnel responsible for its care. Some operators look upon the purchase of a new belt as an expensive outlay every so many years, rather than a constant and steady cost amounting in belt wear alone to several dollars every operating day. This belt wear for all conveyors in one stone-crushing plant known by the writer costs 1 /12 cents per ton or $12 to $15 per hour, based on the present cost of belt replacements. The fact that these replacement costs are double those of prewar quality emphasizes the necessity of improving the conditions that make belts wear out. Some of those conditions are the responsibility of the conveyor designer, and if a serious original error has been made, this handicap cannot be overcome by the operator. If the belt is too narrow, too steep, or too fast for good loading, the operator finds that he has an inherently expensive belt. The other factors that decrease the life of a belt are more or less under his control. The two factors of most importance are the loading conditions and the alignment. Most of the cover wear and carcass cutting occurs at the loading point and if the alignment is not good under all conditions, edge wear or damage may result, Fig I. Loading the Belt It is difficult to load a belt in an ideal manner; that is, to flow the material on the moving belt at a steady rate, without impact, without turbulence, and with a velocity equal to and in the same direction as the belt. An inclined belt is especially difficult to load and particularly when its speed is over 300 or 350 fpm. Inclined conveyors require longer skirt plates to prevent spillage until the load settles. It does not seem reasonable to expect an inclined the to carry the same load as a horizontal belt of the same width and speed, because of the difficulty in loading

Jan 1, 1948

By C. W. Hoffman, W. R. Hinken

Probability sizing, a fairly recent development in the field of particle separation, is now under investigation to determine its value to the mining industry. The method employed is probability sizing through a vibrating network of decreasing screen openings. While probability sizing is not new, the possibility of using it for coarse, highly abrasive ores at high tonnage rates has only recently appeared to merit practical consideration. The advantages of probability sizing vs. conventional screening methods are: (1) reduced space requirements for a high capacity unit, (2) fewer moving parts, (3) more versatile product sizing selection, (4) reduced maintenance requirements, and (5) lower power consumption. Screening is a necessary part of virtually every crushing circuit. At some stage in the process, particle separation becomes a controlling factor in the operation. The basic type of screen in use today is the vibrating unit, which usually employs a mechanical vibrator of one type or another to obtain sizing and material transportation across the screen surface. The vibrating screen has its limitations and inherent problems. Operators must live with: (1) high maintenance — worn rods, screen cloth, spacers, cross members, chutes, etc., (2) low capacity in relation to floor space requirements, (3) extreme noise levels, (4) high power consumption, and (5) structural problems in the screens and supporting steelwork. All plant operators have become tolerant of these drawbacks through the years, and little innovation has been developed in screening. The vibrating screens in use today incorporate improved metals, more efficient power sources, better lubricants, and increased manufacturing skill, but the basic machine itself remains unchanged. Screening is a relatively small part of most plants' operating expenditures and gets relatively little attention from research and development. The HiProb sizer is a new approach to the problem of particle separation on a high tonnage basis. Developed by Dr. Fredrik Mogensen (president of Fred-rik Mogensen, A. B. of Djursholn, Sweden), this unit has found its primary acceptance in the sizing of wet or dry materials in the fine ranges. Climax has been working cooperatively with Mine and Smelter Supply Company, the United States licensee, on the adaptation of the sizer to obtain consistent recovery at a high tonnage rate on a — 3/8-in. separation. This was a new application for the sizer and opened up a whole new field of problems. Dr. Mogensen's machine utilizes the control of normal probability of falling particles and is designed to eliminate some of the undesirable features of vibrating screens mentioned earlier. The machine is light, compact, consumes less power than conventional screens and has a low noise level. PRINCIPLES Probability sizing is a process designed to allow solid particles to segregate with a high ratio of the materials reporting into their respective size fractions with a minimum amount of misplaced particles. Sizing is defined in this paper as segregation of dry solid particles into fractions of comparable sizes. Probability is usually estimated as the ratio of the number of ways an event might occur vs. the total number of allowable ways. The probability process described depends upon the fact that particles falling through a network will segregate across the sizing surface even though all openings are larger than the particles. The degree of segregation is dependent upon the particle size and the trajectory applied by the sizing network to each falling particle. Specifically, the process utilizes a maze made up of screen cloth to control the path of a particle in free fall as illustrated in Fig. 1. The usefulness of this probability sizing process is dependent upon the degree of efficiency of an effective maze. Primarily, a maze must be extremely flexible to meet the multi-faceted nature of solid particles and, at the same time, the degree of control must be reproducible so that a desired separation is predictable. Dr. Fredrik Mogensen has formulated a maze that is not only flexible and easily controlled, but, mote importantly, easily adaptable to a working machine.

Jan 1, 1970

By J. D. Forrester

Many have been prone to credit the decline of professional interest in some branches of mineral industry education to the industrialists and other agencies who use our graduates. We hear the cry that industrial salaries are too low, opportunities for advancement do not exist, and the mineral industry specifically and generally is not interested in the engineer's efforts. Perhaps the time now has come when we should "dress-ranks," examine our practices, and publicize and encourage advanced technical training instead of laying all our troubles elsewhere. There can be no doubt but that industry is interested and stands ready and willing to co-operate. This is demonstrated by the numerous grants-in-aid and co-operative industrial projects which have been made available to those relatively few schools which have been encouraging graduate study and research. There is no dearth of research problems in any of the mineral industry fields and the sooner we realize the great opportunities for constructive, technical research in all areas of our profession the sooner we will reap the benefits of our engineering enterprises by closer liaison and broader understanding with industry. An analysis is offered here of the status of graduate work and research in various phases of mineral industry education in the United States. It is

Jan 1, 1949

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb' has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- '' watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By G. L. Oldright

THE development of the reverberatory furnace for smelting copper ores up to 1912 was described by E. P. Mathewson1 with details concerning the great changes in dimensions of the furnace. Hayward2 tabulated similar data, giving developments up to about 1924, in his revision of Hofman's Metallurgy of Copper. DEVELOPMENT OF PRESENT SMELTING PRACTICE Dimensions of Furnace Very great changes were made in the dimensions of the smelting hearths of the furnaces in the period from about 1800 to 1906, the length increasing from about 11 to 116 ft., and the width from 8 to 19 ft. During this time the tonnage smelted increased from about 9 to 250 tons per 24 hr., and the tons of charge smelted per ton of coal increased from 0.77 to 4.3. Dr. Mathewson3 noted no great difference in the "fuel ratio" (i. e., the amount of charge smelted per ton of coal) as the furnace at Anaconda was increased in length by stages from 85 to 116 ft. (The percentage of copper in the slag, however, was lowered from 0.42 to 0.36 per cent. The other components of the slag were not given.) Lump coal fired on grates was the fuel used during this period. The practice in operating the furnaces over such a length of time naturally varied considerably, and there were differences in composition and nature of the charge, yet it may be considered that the improvements made were due largely to increases in the size of the furnace used. Doubt-less some credit should be given to improvements in operating technique, like changes in the methods of firing the lump coal. However, the greater part of the advance was probably due to factors influencing the

Jan 1, 1928

By A. H. Smallbone, R. Lathe

Considerable efforts have been expended to apply multiple regression techniques to quantitative determinations in x-ray fluorescence analysis. Multiple regression has been shown to be an effective method for correlating x-ray fluorescence intensities to elemental concentrations. Although many other techniques have been devised to solve the problem of matrix effects in x-ray fluorescence analysis, there are few as efficient in terms of storage requirement or ease of programming for digital computers as the multiple regression method. In the case of ore slurry, it has the additional advantage of allowing a unified approach to the problems of slurry density correction and matrix effect corrections. The data used in the present work were obtained with an on-stream x-ray analyzer capable of analyzing 15 slurry streams for as many as nine elements simultaneously. One of its fixed monochromators was set to accept scattered radiation at a discretely selected wavelength as a means of monitoring the slurry's pulp density. The data were reduced to obtain the correlation equations and a computer program combining slurry density with matrix corrections was written in FORTRAN IV to calculate concentrations.

Jan 8, 1969