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By L. G. Austin

Introduction My first contact with industrial milling was during the time I worked in the electricity generating industry in the United Kingdom. In visits to power stations to investigate either deposits in the boiler furnaces or polluting deposits settling around the stacks. I had to check the performance of the vertical coal pulverizers, since poor pulverization aggravated both problems. Naturally, then, when I came to the USA in 1957 to take a PhD in fuel technology at Penn State, I was put to work to review the science of coal pulverization. After this reviewing, I was completely confused. On one hand, there was a well-developed understanding of stress-strain equations, and a rap- idly developing knowledge of how stressed, brittle solids fractured, based on the Griffith crack theory. On the other hand, reading in the grinding literature gave me: • Kick's Law, which was clearly not correct in the light of modern fracture theory; • Rittinger's Law, which was also clearly not correct; • Bond's Third Law of Comminution, which was claimed to have something to do with the Griffith crack theory, but where the connection between the two was made by intuitive pseudo- scientific reasoning I could not accept; • the choice of mill motor power for the most common type of coal mill, the Raymond pulverizer, was calculated from the fan power required to move air through the mill. Although I could accept the empirical connection between the two, it made no sense from the point of view of fracture energy. Even today, most books or review chapters on size reduction start from these laws. incorrect statements abound in the literature, such as “the Hardgrove Index is based on Rittinger's Law," which it is not, "The Bond theory states that work input is proportional to new crack tip length produced in particle breakage," which is not true, etc. My own test work showed that these "laws" did not fit the data for grinding of coal. At about this time, Epstein (1 948) and Broadbent and Callcott (1 956), following the original work by R.L. Brown (1941) at the British Coal Utilization Research Association, proposed describing breakage as a series of fracture stages. I took their concepts and developed the basic differential equation for a batch grinding process continuous in time, analogous to a batch chemical reactor. Robin Gardner then joined the project and did his PhD on treating batch grinding in the same way as a batch chemical reactor. He found that the basic equation had already been partially derived by Sedlatschek and Bass (1 953) in Germany. We confirmed experimentally the validity of the equations for describing batch grinding (1 962) and formulated the equation describing steady-state continuous grinding in a fully-mixed mill. At about the time this work was published, Gaudin and Meloy (1962) and Filippov (1961) independently published essentially the same equations, but without experimental proof of the validity of the concepts. I will give a brief overview of what these beginnings had led to in the design of mills for size and power, and show some of the results of this more detailed understanding of grinding processes. Concepts of Fracture Mills such as tumbling ball, rod, pebble and autogenous mills and vertical mills such as the Raymond, and E-type apply compressive stress to lumps or particles relatively slowly. Compressive stress applied to a particle of an elastic brittle solid imparts overall strain energy to the solid and produces local regions of tensile stress, (Fig. 1) (Berenbaum and Brodie, 1959). Irwin (1949) showed from solution of the stress-strain solutions that a small hole in a region of tensile stress reduces stress concentration at the hole, that is, the tensile stress at the tip of a crack or flaw in a solid is much higher than the general tensile stress in the region. The longer the crack, the higher the stress concentration. Griffith (1920) hypothesized that when the regional tensile stress is large enough, then the chemical bonds at a preexisting crack tip are stretched to breaking point, as illustrated in Fig. 2. When the bonds break, the crack becomes longer, the tensile stress concentration increases, the situation is unstable and a crack opens up (propagates) a surface of tensile stress, creating its own tensile stress at the leading edge. Stored strain energy is converted to the kinetic energy of the moving stress field, which is analogous to sound propagation through the solid, so the crack tip accelerates to velocities approaching those of sound. The moving crack will pass through regions that were previously under regional compressive stress. The equations for "ideal" and "Griffith" strengths are where a is the intermolecular distance, y is Young's modulus, g is the energy

Jan 1, 1998

By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors' experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959

By C. B. Manula, H. Gezik

In planning modem-day mining operations, management needs to pass from the area of subjective decision-making to an area of objective decision-makirlg. Planning procedures currently being practiced by many mine managers depend primarily on common sense and trial-and-error methods which oftentimes never reach optimum solutions. For this reason, an attempt is made to provide an understanding of linear programming to solve production planning problems. More specifically, a linear programming model is proposed to solve the production scheduling problem as it was found to exist in the crushed stone industry. Optimal production scheduling is of prime concern here, since the industry has to cope with seasonal demands for its products. The solution, as determined through the application of the model, provides management not only with an optimal production schedule but also with the following information regarding the improvement of existing facilities: (I) the location of bottlenecks which limit production and profit; (2) the directions in which the company i fixed equipment should be expanded or modified; and (3) the evaluation of unused resources. Future trends in stone production will quite likely parallel those in the construction industry. Continued record expenditures for structures such as dams, highways, and buildings are the reasons for this accelerated growth. Production forecasts for the next decade are predicted to be around one billion tons with an approximate 7% annual increase. The problem of increasing production from 570 million tons in 1966 to 1 billion tons by 1976 offers no small challenge. This situation is further compounded by other problems and economic factors. Population expansion, government regulation, labor agreement, and changes in technology wd cause managers and operators to be confronted by many more complexities than characterize present-day operations. Some of these. problems and economic factors are: (1) In some metropolitan and other urban areas, easily accessible sources of stone are almost depleted. Transportation costs will be a prime concern of the industry. (2) Population growth has forced residential expansion to a point where many quarry operators must conform to urban and suburban regulations. (3) Government regulation in regard to air and water pollution, noise, and reclamation as well as zoning developments necessitate that crushed stone producers keep abreast of changing conditions and requirements. (4) The crushed stone industry operates under pressure of a highly competitive situation. Every company's objective is to retain a favorable marketing position by exercising great attention to production and marketing costs. This is rather difficult, since the crushed stone industry is one segment of modern mining which has to cope with a seasonal demand for its products. Among the problems posed here, the one of exercising great attention to production and marketing costs is of current interest to management. Under seasonal demand conditions, this problem creates further difficulties for managers who need to plan and forecast. STATEMENT OF THE PROBLEM Various methods of Operations Research have been developed to handle a problem whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. This paper describes the use of Operations Research methods to solve a production planning problem when demand is seasonal. The seasonal production planning problem is an important one because of the substantial costs associated with changing production, employment, and inventory levels to adjust to seasonal sales patterns. Most companies try to operate within reasonable levels of employment changes and hold inventories within storage capacities. In general, little or no attempts were made to develop minimum cosl schedules or to provide objective means to compare various production policies. When demand varies within a fixed time period, 11:-oduction requirements may be met by following one

Jan 1, 1970

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By E. L. Day

"In the early 1930s during the course of test work with a simple gold ore, it was evident that the time required to dissolve the gold by cyanidation was very much longer than should have been needed theoretically for the maximum size gold particles in the ore, A similar conclusion appeared to be valid for other gold ores. In a cyanidation system there are many factors which can influence the dissolution rate of gold, and a decision was made to investigate the more obvious variables, because a literature survey at the time showed that with the exception of the work of Yamazarki on the dissolution of silver in cyanide solution, virtually no attention had been given to this subject, Our work was not reported because the intention was to do this on completion of the Study, but owing to the demands on the Section's personnel for other work the investigation was never completed. Although other investigators have since studied the problem, the methods which we adopted and some of the conclusions may be of interest to metallurgists concerned with gold ore treatment.Form of GoldExperiments with gold ores were not possible because of the number of uncontrollable variables present in a gold ore-cyanidation system, therefore pure metal and reagents were used. Initially some experiments were carried out with gold leaf, but it was soon apparent that metal in this form was unsuitable because the uneven thickness of the leaf caused it to break up into pieces and. there was difficulty in determining precisely when complete dissolution had taken place, Numerous factors both expected and unexpected were found to influence considerably the results and much experimental work was necessary to establish the procedures which were finally adopted, Experiments were carried out with gold in the form of foil, wire, rings and sols. Finally, gold foil in the form of cylinders was adopted for most of the experiments although some work with gold in the sol form was included in the programme. Also some experin1ents were carried out with a gold ore to see if effects which were obtained with sodium chloride on gold sols were applicable to gold ores."

Jan 1, 1967

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By T. Tamura

It is known that the CaO-FetO-P2O5slag system has a wide liquid miscibility gap at steelmaking temperatures and this two-liquid slag phase has many advantages such as high activities of both FetO and CaO and high amount of P2O5. The phosphorus distribution ratio between the two-liquid slag and molten steel was confirmed to be higher than that between CaOsat.-FetO-P2O5slag and molten steel. The two-liquid slag may be useful for dephosphorization of molten steel and reduction of slag volume. Furthermore, the phase equilibrium of two-liquid CaO-FetO-P2O5slagsaturated with MgO was measured to determine the applicability of the two-liquid slag to dephosphorization in steelmaking process. Keywords: slag, refractories, solid solution, two-liquid phase, dephosphorization, steelmaking, phase equilibrium.

Jan 1, 2004

By Katarina Theander, Robert J. Pugh

In the flotation process, control of the stability of the froth is extremely critical. In the case where the froth is too stable then mechanical entrainment of particles can occur but in the opposite case, where the froth is too unstable and difficult to skimm-off, then a reduction in recovery can result. In minerals and deinking flotation, commercial fatty acids are used and may act as both both collectors and frothers. However, frequently the fatty acids are mixed with nonionic ethoxylated surfactants to give more effective froth control and increase the flotation performance. It is of interest to note from the surface chemistry literature, that such mixtures may cause synergistic effects in surface activity which may explain changes in bubble size, foaming and carry over of particles. In the present study, we have carried out foaming and drainage experiment with oleic acid and model nonionic surfactants; hexa(ethylene glycol) mono-dodecyl ether, C12E6 and tetra (ethylene glycol) mono-dodecyl ether, C12E4 both in separate and mixed systems. Frothing was carried out in a column, equipped with a series of conductivity electrodes which enabled the water content of the froth to be measured along the length of the column, during various stages of the drainage process. The variation in water content of the froth enabled the process to be characterised by distinct three stages; (a) an entrainment state where the water transfer from the bulk phase to the froth was dominant (b) a steady state when entrainment and drainage are balanced and no water is transferred to or from the froth and (c) the drainage step when drainage predominates and the volume of the bulk phase increases. We also carried out surface tension measurements on the oleic acid/ nonionic systems and related the results to the frothing and drainage performance. From the surface tension data, the adsorption interaction parameter of the mixed systems at the air/solution interface could be calculated and was found to depend on the oleate/ nonionic surfactant ratio. This value was related to the frothing performance and the results indicated a positive interaction parameter for the mixed surfactant systems which could explained the synergistic effects in frothing performance.

Jan 1, 2003

By F. J. Fayers, R. L. Perrine

For many years the problem of increasing ultimate recovery of oil from a reservoir has been a subject of interest to the oil industry. At present, a standard secondary recovery technique is to flood the reservoir with water once natural forces of the system are depleted. The permeability characteristics of the rock, together with interfacial forces which exist between the two fluids and the porous material. allow only part of the oil in the rock formation to be recovered by the water-flooding process. Laboratory experiments have shown that when detergents are added to the flooding water, the flow properties of oil in a porous rock arc improved. This improvement results in greater oil recovery. Even though higher recoveries are obtained using detergents, the extra cost associated with the method may make it economically unsatisfactory. To establish economic feasibility requires experimental laboratory measurement of fluid and rock properties together with a calculational procedure to predict field results. Pilot tests in the field may also be required. This paper presents a mathematical procedure for predicting detergent flood behavior. A number of reasonable simplifying assumptions are made to obtain a tractable system of equations. The resulting method may be regarded as a generalization of Buckley-Lev-crett' theory to solve simultaneously for water saturation and detergent concentration profiles. Consequently this type of calculation can be used in much the same manner as Buckley-Leverett theory is used to evaluate a water flood. The mathematical method employed is the so-called method of characteristics for solving hyperbolic partial differential equations. This application of the method is instructive because several other problems in reservoir analysis may be analyzed in a similar manner. FLUID FLOW EQUATIONS The flow behavior of oil and water without detergent through porous reservoir rock is usually expressed by Darcy's law and a continuity equation for each phase. If gravitational forces are neglected, vrg = kr (s)µr v p rg.........(1) vrg = kr (s)µr v p rg.........(1) ? pa va = F ?/?t (sd) where v is the volumetric flux, k represents permeability, S is saturation, and P the pressure. Fluid viscosity is denoted by 11, p is the density, 4 is porosity, and I the time. The subscripts w and o refer to water and oil. The capillary forces in the system lead to a difference in pressure between phases. This may be expressed by the relation: Pm -P0 =Pc(S).........(5) The capillary pressure? P,, is determined experimentally as a function of saturation. DETERGENT BALANCE EQUATION Addition of detergent to the water phase affects the flow properties of the system. Capillary pressure and relative permeability become functions of detergent concentration, c, as well as fluid saturation. That is: P--P (S,c) and k,,,.- - -- k,,,. At low oil saturation values, the presence of detergent reduces capillary pressure and reduces the relative permeability ratio. Detergents are surface-active and adsorb on rock surfaces. The quantity adsorbed, a, will depend on the concentration c of detergent solution and may also depend on the saturation; thus, a = a(S,c). In this analysis we have assumed that the detergents used are water soluble but not oil soluble, and their movement is therefore restricted to the water phase. The dispersion of detergent in water is neglected by comparison with transfer by flow within the system. Detergent movement is determined by the water flux and adsorption: ? cv m = -F ?/?t (cs + a) We will assume that the quantity of detergent in solution is too small to significantly change water density or viscosity. When the permeability and capillary pres-

By T. G. Carnahan

The Bureau of Mines conducted research to simulate in situ leaching of a porphyry copper sulfide ore. The purpose was to determine the effects on copper leaching of additions of NaCI to a conventional sulfate leach system and to analyze the oxidant requirements and the oxidation products that resulted from leaching of the sulfide minerals in the ore. Baseline sulfate and sulfate plus 2-pct-NaCl-leach-solution experiments employing 167-kg (367-lb) and 152-kg (333-lb) charges, respectively, were conducted. The minus 25.4-cm (10-inch) ore was leached at 90° C under flooded conditions with 2.8 MPa (400 psig) of oxygen bubbling through the system. Sixty-seven pct of the copper was extracted in 1,236 days of leaching in the NaCI experiment, whereas 47 pct of the copper was extracted in 913 days of leaching in the baseline experiment. Diffusion into and out of the ore fragments controlled the rate of leaching, which precluded enhancement of the leach rate by the chloride ions. The calculated oxygen consumption was 3.17 kg/kg of copper extracted in the baseline experiment and 3.46 kg/kg of copper extracted in the experiment to determine the effect of chloride ions.

Jan 1, 1982

By M. R. Tek, M. L. Katz

The flow of fluids in stratified porous systems, in which adjacent layers of the system are in communication over part or all of their common interface, in many instances involves crossflow between layers. A theoretical study has been made of the unsteady-state flow of slightly compressible fluids during depletion of bounded stratified porous systems. Consideration has been restricted to single-phase flow, with negligible capillary and gravity effects. Analytical expressions have been derived for pressure distribution and for (luxes at the producing face in two-layer systems with complete fluid communication between layers. These expressions occur in the form of double Fourier and Fourier-Bessel series. The method of extending the solution to any number of layers is demonstrated by deriving the equation for pressure distribution in a three-layer system. On the basis of the exact results for two-layer systems, certain generalizations regarding the behavior of stratified systems in general are presented. The performance of stratified systems, in terms of cumulative flux as a function of time, is shown to lie at all times between bounds established from single-layer theory. The upper bound is given by treating the system as a single layer with arithmetic average physical properties. The corresponding lower bound is the summation of the fluxes from each layer as treated individually. Variation in performance of stratified systems between the upper and lower bounds is determined by the extent to which crossflow occurs in the system. The principal parameters affecting the amount of crossflow are the vertical permeability of the system, the ratio of system thickness to "radius of drainage" and, for radial systems, the ratio of system thickness to interior radius. At very early times, the system performance is near the lower bound. As time and the radius of drainage increase, the per- formance tends toward the upper bound. INTRODUCTION One of the principal problems confronting the reservoir engineer today is the incorporation of the effect of reservoir heterogeneity into predictions of reservoir performance. The first part of this problem is the characterization of the actual reservoir heterogeneity in a mathematically useful manner.1, 2 It is then necessary to calculate the effect of this heterogeneity on the system performance. It is frequently possible to estimate this effect by comparison with the known behavior of an idealized system. One such idealized system is the stratified or "layer-cake" model. Many studies have been made of the behavior of stratified systems, from both a theoretical and experimental standpoint. The great majority of the theoretical studies have been concerned with systems of separated layers, with no fluid crossflow. Among the more noteworthy of such theoretical papers is that recently published by Lefkovits, et al,3 in which a comprehensive analysis was presented for the behavior of bounded stratified systems which are unconnected except at the wellbore. Three recent references have dealt with stratified systems including the effect of crossflow. Jacquard4 has presented mathematical derivations pertaining to depletion of two layer systems producing at constant rate. A doctoral dissertation by Katz5 contains analytical solutions and tables of results for pressure distribution and fluid flux during constant-terminal-pressure depletion of two-layer and three-layer systems with crossflow, together with tables of eigenvalues necessary in the computations. The dissertation also presents results from experimental studies of stratified systems using a heat-transfer analog model. This paper is largely based on the material in this dissertation. A third paper has been presented by Russell and Prats6 since completion of the work resented herein, containing mathematical derivations for and discussion of the behavior

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc has been used as an instrument for comparison of the absorption and sectioning techniques as a means of studying diffusion. Single crystal as well as poly-crystal samples were used asanda the temperature range of diffusion extended from 200° to 415°C. For temperatures above 200°C, the data indicate that the results obtained from the absorption technique agree with those obtained from the sectioning technique. The effect on the values of the diffusion coefficient of electroplating vs evaporation as a means of applying the tracer was investigated and no significant difference observed. It was found that an excess or deficiency of tracer did not materially affect the results obtained from the sectioning technique, but invariably caused errors with the absorption technique. NEARLY all self-diffusion experiments and many alloy diffusion experiments have employed radioisotopes as the instrument for following the diffusion. Of the various techniques in which radioisotopes are applicable, the two most widely used are the sectioning and absorption techniques. In the former, the diffusion coefficient is obtained from a curve of log concentration vs the square of the mean penetration depth. In the latter, the diffusion coefficient is calculated from a knowledge of the decrease in activity at the surface after diffusion. In spite of the importance of knowing the reliability of the diffusion data and the widespread use of these two techniques, they had not been directly compared experimentally on the same samples. Thus, such a comparison was worthwhile. The specific system chosen for this comparison was the self-diffusion of zinc, since the metal was readily obtainable in high purity, single crystals were easily grown, and the anisotropic features of the diffusion added an additional factor of interest to the comparison. Self-diffusion in both single and polycrystals was investigated, since the possibility existed that grain boundaries and grain boundary diffusion might produce different effects for the different techniques. Also, the effects of electroplating vs evaporation as a means of applying the radioactive tracer, and the effects of applying an excess or deficiency of tracer material were studied. The general experimental procedures and the mathematical analyses of both techniques have been described previously in some detail, and only those points essential to an understanding of the present work will be discussed here. The mathematical analysis of the sectioning data requires only a knowledge of the solution of Fick's equation. where C,, is the initial concentration, C is the concentration at depth x, D is the diffusion coefficient, and p is the absorption coefficient of the solvent metal for the radiation from the solute. Having obtained F from the experiment, the value of z can be read from a plot of F vs In z, and D can then be calculated if is known. The necessity of knowing the absorption coefficient causes most of the criticism of the absorption technique. It is very difficult to measure accurately under the conditions existing in the diffusion experiment, but it is absolutely necessary, as will be indicated briefly later. Portions of this problem have been discussed in detail elsewhere." The difficulties involved in the measurement of the absorption coefficient arise from three principle factors: the physical characteristics of the absorber, the geometry, and complex radiation spectra. The first two are heavily dependent upon the third. If

Jan 1, 1957

By Z. F. Oszter

This paper discusses the materials handling problems encountered in cement plants in the areas of raw and finished product grinding and cement storage. It illustrates by examples taken from actual installations, how optimum feed rate is maintained in grinding circuits with properly applied bin dischargers (vibrating hoppers, Mexican feed boxes and aerated bin bottoms) for materials with high moisture content and/or difficult handling characteristics. Initial operating problems with the equipment will be discussed and maintenance requirements will be indicated for comparison purposes. In a modern cement plant, properly functioning bins and feeders are as essential as process control, for no process control system, however sophisticated, can perform efficiently if raw materials do not flow into the plant processing facilities at the required time and rate. Most materials used in the manufacture of portland cement - such as silica sand, iron ore fines, crushed limestone, gypsum, clinker or cement itself-have difficult handling characteristics under specific conditions. High moisture content or even dampness due to condensation may create bin hang-ups, arching and ratholing, all of which result in improper functioning of the feeders or proportioning equipment. The occurrence of these problems in existing cement plants spurred a search for the corrective devices discussed in this article. The equipment investigated included bin dischargers in the form of vibrating hoppers for moist raw materials, Mexican feed boxes for clinker and aerated bin bottoms for cement. Operating experience with different types of bin dischargers showed that the actual performance of some did not come up to the expected level under prevailing operating conditions. The aim of this paper is to record the results of this experience and there- by aid designers and/or operators in selecting the most suitable equipment for their requirements. BIN DISCHARGERS (GENERAL) A discharger is a device that causes stored solids to flow out of a hopper without metering the rate of flow as a feeder does. The investigation discussed here encompasses the following types of bin dischargers used in a cement plant: (1) vibrating hoppers (horizontal motion), (2) whirlpool hoppers (horizontal and vertical motion), (3) aerated bin bottoms (air fluidization), and (4) Mexican feed boxes. Most of the bins used in the cement industry are of the plug flow type. Raw materials with difficult handling characteristics such as high moisture content may cause flow problems when fed through small openings (12 x 18 in.), even if two walls of the bin are vertical.' The most appropriate solution to these flow problems would be the installation of separate mass flow bins for the different materials such as silica sand, iron ore fines, crushed limestone and gypsum, with each bin correctly designed from test data obtained by measuring the flow properties of representative samples. However, limited storage capacity and plant space usually preclude this approach. Quantitative design of bins for flow based on measured flow properties of representative samples of the bulk solid to be handled is no longer an "engineering art," thanks to the basic research done on the flow of bulk solids in bins during the last decade.2, Where space limitations exist, however, or where improvements are being sought for equipment already installed, bin dischargers offer a satisfactory solution to flow problems. They can be applied effectively under flat-bottom bins or mounted to existing plug-flow bins with very little modification to these facilities. In both the foregoing cases, plug flow will be maintained, but the flow channel will be considerably increased so that it is larger than the discharger's bin-side diameter, and material flow can be sustained if the discharger is correctly selected. The main purpose of a bin discharger is to draw the bulk solids across the whole area of the bin outlet, to make the opening fully effective. As long as the bin-side opening of the discharger is large enough

Jan 1, 1969

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By AIME AIME

IN a recent technical paper of the Central Committee of the French Coal Mines (Note technique No. 198, by L. Lahoussay) the author points out that continuous in¬crease in depth of mine shafts makes it more and more necessary to look for appropriate means to reduce the weights and dimensions of the hoisting ropes. Increasing depth demands a larger section and weight for the cable if the useful load is not to be cut down at the same time. This naturally leads to increased cost per ton, and at the same time creates serious mechanical difficulties. The dimensions of the hoisting engine must be increased, acceleration at the start must be decreased so as to avoid periods of excessive peak power loads, and a longer time be allowed to slow down the speed of the hoist when applying brakes. The hoisting rope, upon which depend the dimensions and hence the mass of the hoisting engine, presents the greatest obstacle to the development of hoisting from greater depths. Evidently, for a given depth, the total weight of the rope can be notably reduced by utilizing a wire rope of decreasing section, approaching the theoretical logarithmic form. This is a solution frequently adopted for great depths. Of course, the weight of the rope could be easily' diminished by reducing the useful load, but it is certain that with increasing depth of mining, more effort must be made to confine the hoisting to a small number of shafts, and increase the load hoisted per trip.

Jan 1, 1933

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 million tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms. In 1951 an ambitious program aimed at the discovery of new orebodies and important extensions of abandoned deposits was launched by Attwood Copper Mines, Ltd. In this district so thoroughly searched by an earlier generation of prospectors, any orebody which had remained undiscovered must have little or no surface indication. Consequently, in addition to the basic detailed geological work, the program of exploration included magnetometer and self-potential surveys. Geological bets and geophysical anomalies were tested further, prior to diamond drilling, by a study of copper distribution in tree twigs and/or in the soil. The soil sampling and analytical methods used and some of the results seem of sufficient importance to warrant this paper. The authors had done some plant sampling in this and other districts, using the dithizone neutral-color-end-point method (Warren and Delavault, 1948, 1949; White, 1950),1-3 but they were unfamiliar with its soil application. Finally, after much experimenting in the field, they adopted the methods described here. These methods are not entirely original or defensible on theoretical grounds, but under field conditions of rapid sampling and analysis the results are reliable enough to be of use. Fig. 1, which shows the results of duplicate analyses of duplicate soil samples taken at 50-ft intervals across an anomalous zone, indicates the relative dependability both of the sampling and analytical methods. Sampling and Analytical Equipment A 2-ft piece of 1-in. solid drill steel, one end sharpened to a broad, conical point. The steel is marked at 1 ft from the point. A 2-ft piece of ½-in. black iron pipe, one end filed to a bevelled cutting edge. The pipe is marked at 1 ft 3 in. from the cutting end. A 3-lb hammer. A plastic or rubberized sheet about 18 in. square. Moisture-proof assay pulp envelopes. A 10-mesh seive made from window screen with the paint burnt off. A small assay spatula. A pan balance sensitive to 10 mg. Two ignition trays about 4 in. square, made of sheet iron turned up along the edges. A Coleman two-burner gasoline stove. An asbestos board about 5x8 in., used as a hot plate on the gasoline stove. A circular aluminum rack to hold 8 test tubes while refluxing (design of Almond and Morris). Pyrex Glassware Large refluxing test tubes, 25x200 mm, marked at 40 ml volume. Breakers, 20 ml. Pipettes, 1, 5, and 10-ml capacity. Graduate, 50 ml. Shaking cylinders, 100 ml, glass stoppers. Burette, 25 or 50-ml capacity, with holder. Chemical Supplies 1 N sulphuric acid. Hydroxylamine hydrochloride, solid crystals. Fisher Alkacid test paper. Copper standard solution. Dithizone standard solution 60 mg per liter. Water reasonably free of metals. Soil Sampling Method: The problem of how to take a soil sample is extremely crucial. The method outlined below, adopted after a number of tests, has the advantages of uniform pattern, uniform depth, and uniform size of sample. The area to be tested was marked off by chain and compass lines 100 ft apart, normal to the strike of possible ore deposits. Numbered stakes were set at 50-ft intervals along these lines and a soil sample was taken at each stake in the following manner. The drill steel was driven into the ground normal to the slope of the surface to the marked depth of 1 ft, moved slightly from side to side, then carefully withdrawn. The iron pipe was inserted to the bottom of this hole, tapped down to the marked depth of 1 ft 3 in. and withdrawn; the 3-in. soil plug in the

Jan 1, 1955