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By G. S. Cole, G. F. Bolling

Recent experitnents on crystal growth have indicated that thermal convection in the liquid influences the conditions of solidification and subsequent crystal characteristics. However, the important columnar-equiaxed transition in castings has not been examined as a function of this free convection. An experiment is presented here to demonstrate a change in the transition as convection is suppressed. Lead- and tin-based alloys were cast in stainless-steel molds either without special procedures or with thin grids placed horizontally across the tnold diameter in portions of the castings. While the grids allowed some diffusion of heat and mass transport to occur during solidification, massive fluid flow was hindered in the vegiotz of the grids. A larger percentage of columnar grains appeared in the grid region than in other parts of the special castings or than in all regions of normal castings. This structural difference can be explained in terms of thermal convection. THERE is little information about the possible effects of natural convection which may occur during the solidification of a casting. Ruddlel-3 has stated that the movement of liquid metal produced by convection might assist in the transfer of heat, but in the absence of confirmatory evidence he suggested that this idea be treated with caution. chalmers4 considers, but does not assess, the importance of fluid motion in casting, while Tiller5 suggests that, in liquid metals which have extremely high thermal diffusivities, the effects of thermal convection may be negligible. In addition, throughout the literature, there are statements indicating the possible presence of thermal convection but without proofs or evaluations of its influence. Natural convection may be divided into two categories: thermal convection, where liquid flow is due to density differences caused by temperature gradients in the liquid (e.g., liquid near a cold wall falling with respect to hotter liquid further away from the wall); and solute convection, where flow is due to density differences as a result of concentration gradients, see Wagner.6 In most instances thermal convection predominates over solute convection. Nevertheless, even thermal convection has not been studied in any detail and is difficult to handle, since it can vary quantitatively from one experiment to another depending upon the exact positions of heat sources and sinks or the attitude of the container with respect to gravity. In spite of these difficulties it is possible to realize that a higher rate of heat transfer must result with convection than in any situation where conduction acts alone. Thus, the degree of increased heat transfer is the important undecided question in considerations of casting. It will be demonstrated here that a reduction in convective flow leads to a suppression of the columnar-equiaxed transition in a casting and that this suppression is related to a decrease in the degree of heat transfer. Fortunately it is possible to do this by comparative rather than quantitative measures. The insertion of horizontal plates or grids into a simple mold does not appreciably influence heat transfer per se, but in reducing the allowable height through which colder liquid may fall freely it reduces natural thermal convection. This leads to a reduced fluid velocity, a different flow pattern, and an altered heat transfer which can be measured. EXPERIMENTS The alloys were prepared from elements of 99.9 pct nominal purity and cast into an uncoated 2-in.-diameter stainless-steel mold insulated at the bottom with a suitable refractory so as to ensure predominantly radial heat flow during freezing. Casting was performed either in empty molds or in molds containing grids or plates in various configurations . The grids were constructed of aluminum screen (1/32 in. thick) which was cut to the desired shape, cleaned in aqua regia, and coated with a mixture of 2 parts aqua dag graphite -1 part Sauereisen cement mixture, thus supplying a hard, protective, and insulating layer approximately 0.006 in. thick. The

Jan 1, 1965

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By P. G. Carpenter, R. G. Nisle, F. W. Bubb

It is the purpose of this paper to describe an electrical computer which has been constructed to solve the equations for vapor-liquid equilibrium in multi-component systems. The instrument consists of seven component-computing units each with proper indicating means and power supplies. Each unit is a resistance network with a voltage matching servomechanism, and each provides an output voltage proportional to the mol-fractions for vapor and liquid phases. These voltages are summed and matched with a reference voltage to provide the solutions. Any reasonable number of such units may be put together to make a computer. The theory and operation of the computer is discussed. A number of applications and examples of computer results are given. The computer yields the over-all vapor or liquid fraction to a probable error of 0.002. An interpolation method is described which reduces the probable error to 0.0002. INTRODUCTION The process known as Flash Vaporization may be described as follows: A mixture of known composition of relatively volatile components is allowed to come to thermodynamic equilibrium at some given temperature and pressure by any path whatsoever. In general, a vapor and a liquid phase will be present at equilbrium. The problem is to determine the fractions of the mixture in the vapor and liquid phases, and to determine the mol fractions of the various components in each phase. The relations that exist between these various quantities at equilibrium are well known and will be given later. These equations are difficult to solve, yielding only to trial-and-error methods. The virtues of the analog computer are its speed and the automatic character of its calculations. The device is operated by turning a crank which varies the value of v, the total vapor fraction. This actuates a number of servomechanisms which perform automatically all computations. This computer facilitates the solution of such problems as (to mention a few] : Analysis of separator operation, studies of changes in composition of reservoir fluids with pressure decline, and analysis of natural gasoline plant operation. Examples of some of these problems are given in detail later. STATEMENT OF THE PROBLEM The essential equations are xm = 1+(km-l)v . . (1) Kmzm ym =------------------------. . (2) 1 + (Km-l)v ; n n S S xm= --------------------=1 1 + (Km-l)v m = 1 m=1 ......(3) n n S = S Km Zm =1 S ym 1 + (Km-1)v m=1 m = l ......(4) where ym = Vm/V = Mol fraction of m-th component in vapor phase. xm = Lm/L = Mol fraction of m-th component in liquid phase. Zm = Fm/F = Mol fraction of m-th component in mixture. KM = ym/xm = Equilibrium constant for m-th component at the given temperature and pressure. v = V/F = Mol fraction of vapor in the mixture. F = Total mols of a mixture of n components. V - Total mols of vapor in the mixture. L = Total mols of liquid in the mixture. Fm = Total mols of m-th component. Lm = Mols of m-th component in liquid phase. Vm = Mols of m-th component in vapor phase. Assuming the total mols of the mixture F and its composition (all the Fm) to be known — either from a quantitative analysis or from the amounts put together to make the mixture — the zm = Fm/F may be regarded as known quantities. From the given temperature and pressure of the mixture the K., are known (principally from experimental data). The primary problem is then: having given all the zm and Km to calculate v and all the fractions xm and ym. Having calculated these ratios, it is a simple matter to calculate V. L. Vm, Lm from their defining equations. SOLUTION OF THE PROBLEM Basic Computer Unit The computer consists of n units, each of which provides voltages xEo and YE, proportional to x and y as in

Jan 1, 1950

By J. Geertsma

The relationship between porosity and the speed of propagation of acoustic waves in fluid-saturated porous rocks as measured by the Sonic log and by ultrasonic tecbniques is analyzed. Biot's continuum theory 1 is used to explain the difference in acoustic wave propagation between a dry and a liquid-saturated porous material. The porosity is a variable in this theory. However, the acoustic wave propagation in the dry rock depends too on porosity, and this dependence is not predicted by the theory. Frequently in dry sandstones, a nearly linear relationship between reciprocal acoustic wave velocity and porosity is observed in the low-porosity range. The physics behind this behavior is outlined. An empirical relationship of the form, 1/v = A + F, applies accordingly for many porous dry rocks, provided the porosity is the only variable. The presence of a liquid in the pores changes the value of B, and this change is found to be in agreement with the Biot theory. The time-average relation introduced some years ago2 results in an equation of the same type — 1/V = F/Vf + (1 - F)/Vr — but is not based on a sound physical picture. Still, this relation sometimes predicts approximately correct A and B values. Carbonate rocks with their complicated pore structures sometimes show a different relationship between wave velocity and porosity, unfavorable for log interpretation. Examples are presented. The simultaneous presence of calcite, dolomite and anhydrite, with their different grain densities and matrix compressibilities, complicates acoustic-log interpretation in carbonate rocks still further. Other complicating effects of acoustic-log interpretation are discussed. They are related to the influence of shale streaks and natural fractures on the average wave velocity observed by the logging tool and to the effect of adsorption phenomena on wave propagation in unstressed rocks particularly in sandstones. INTRODUCTION The velocity of propagation of sound waves in porous sediments as a function of depth is a quantity frequently measured. Velocity loggers of various d-sign may be used, for which velocity is defined as the. distance between a wave generator and a wave detector (one-receiver system) or the distance between two wave detectors (two-receiver system), divided by the shortest time required for a vibrational pulse to cross this distance. Velocity loggers ale used to assist in seismic prospecting, to differentiate between the various types of sedimentary rock layers, and also to determine rock porosity and pore fluid content. This paper is especially concerned with the relation between velocity and porosity and the effect of the pore fluid. Most velocity-log interpretation in terms of porosity is based on a formula advocated by Wyllie, et al,2 suggested earlier by Hughes and Jones,3 and known as the "time-average relation". This formula app1ies for a model consisting of a layered system of parallel alternating slices of a solid and a liquid, crossed by the wave path perpendicular to the interfacrbs. This must be an unsuitable model for the derivation of wave propagation properties of liquid-saturated porous media. It suggests that only rock matrix and fluid properties influence the wave velocity. The surprising fact, nevertheless, is that applications of this formula to clean sandstones under specific conditions (sufficient effective stress) results in porosity predictions which are close to reality. Other authors, such as Gassmann,4 White and Sengbush,5 Brandt,6 and Hicks and Berry,7 make use of more realistic models to arrive at a wave velocity formula for porous sediments. Their models consist of various liquid-saturated packings of frictionless spherical grains and are, therefore, also highly idealized. A number of experimental results obtained in the laboratory can be better explained with these model theories than by the time-average relation. A study of a general character, not depending a priori on a special model of the porous structure, was still lacking.

By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956

By G. W. Doepel, W. P. Sibley

A three-dimensional, multilayer, mathematical model has been developed for predicting performance by mis-c.ible displacement. Areal and vertical coverage, total gas-oil ratio, propane-oil ratio and oil-recovery factor for the multilayer system are computed as functions of hydrocarbon pore volumes of solvent injected. The technique has been programed for use on the IBM-7090 digital computer and was used in calculating perfortnance for continuous miscible displacement of a five-spot, 50-layer .system. Results reported are based on the use of published laboratory data for a single, uniform five-spot layer. However, the technique is sufficiently generalized to calculate performance of any system of layers of any pattern configuration and mobility ratio, provided data are available to describe perfortilance of a single layer. The technique has also been adapted for predicting oil recovery resulting from various gas-driven slug sizes. The results presented for both continuous and slug-type injection show, that permeability variation has 0 significant effect on oil recovery but that solvent composition, within the range studied, has a lesser effect on oil recovery. INTRODUCTION Experience from many of the miscible-phase displacement projects currently in operation indicates that the injected solvent flows preferentially through the more permeable zones in the reservoir. This preferential solvent flow in the high-permeability streaks results in a reduction of vertical coverage (C,) and an attendant decrease in oil recovery. The multilayer technique presented in this paper uses areal coverage (C.,) data for a single layer from the literature and from laboratory measurements of displacement efficiency (herein referred to as microscopic coverage, C,,) to calculate areal coverage (C,) and vertical coverage (C,) for the multilayer system. Oil recovery for the multilayer system is obtained as the product of (Ca) (Cm) (Cv). It is assumed that C, in a single layer is 100 per cent; therefore, (C,) (Cm) is a measure of oil recovery from that layer. Data presented in the literature for a single layer generally deal only with areal coverage and/or microscopic coverage —but seldom specifically with oil recovery. Nevertheless, this technique is flexible in that either Ca and C,, of an individual layer or a direct measurement of oil recovery for the layer may be used. In developing this technique, the problem arose concerning a method of determining the relative amounts of solvent that will enter each layer during any increment of solvent injected. To solve the problem, a dimensionless equation was derived for expressing solvent injected into each layer as a fraction of total injection. A finite-difference method was applied in integrating the equation to determine oil recovery for the system of layers as a function of pore volumes injected. The technique subsequently was programed for solution on a digital computer. The method was applied to predict performance of a deep California reservoir under continuous miscible displacement and has been extended for calculating oil recovery as a function of slug size for gas-driven slug injection. The technique may be applied to any petroleum reservoir that can be adequately represented as a layered system, by considering permeability variation,1-3 permeability range and average permeability. Each layer is then assigned its appropriate permeability, porosity and hydrocarbon saturation. RESERVOIR VOLUME CONTACTED BY SOLVENT It has been recognized for some time that high microscopic coverage (C,) can be obtained by injecting a miscible agent, such as propane, into an oil reservoir. These high values of C,,, have been demonstrated in the laboratory and are normally between 80 and 100 per cent, depending on solvent and reservoir oil composition as well as on reservoir temperature and pressure. In miscible-phase displacement, because there is no interface between solvent and oil, effective permeability to solvent is the same as that to oil. (This assumes that oil saturation has not changed and that water is immobile.) Consequently, mobility ratio (M) simply reduces to that of viscosity ratio . Perrine4 and Habermann5 have shown that large

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper&apos; showed that the transfer obeyed first-order kinetics. The second&apos; presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.&apos; It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By C. L. Pillar

INTRODUCTION The location, size, character of the ore de- posit and its adjacent formations will deter- mine the mining system best used for its ex- traction. The mining system chosen will have to be engineered to suit the ore deposit and the people that will extract it. What can be done in the Philippines cannot always be accomplished in the upper Northwest Territory of Canada. Mining operations developed under a free enterprise system are planned to achieve a satisfactory return on the capital required to place them into production. Hence, the choices made in planning and developing the mining system must be dictated by sound economics. The mining system planned must favor: 1. Maximum ore extraction of the deposit with minimal grade dilution. 2. The amount of capital expenditure used to develop and equip the mine must be in harmony with the financial policy of the group yet be sufficient to provide a reliable mining system. Excessive frills and extras that are not required for efficient, safe production should not be provided. 3. Mine production costs are determined by the amount of men, material, equipment and energy used in the production process. These must be kept to minimal limits in order to insure dependable, low cost production. Extras that later are needed in the production operation can be added as required by the operator. Basically block caving is a mining system that is normally used to extract deep seated, massive, low grade deposits of copper, molybdenum and iron where stripping ratios for open cast mining are economically prohibited. The caving system is limited in its selectivity. It is a mass production type of underground ore extraction that under favorable conditions is one of the most efficient, low cost mining systems in the world today. Usually block cave mining systems are large. They are capable of producing ore at a rate of 10,000 to 100,000 tons/day from large deposits at costs that are comparable with many open cast mining systems burdened by high waste to ore ratios. Block cave mining systems differ basically in the plan of the area layout, the method of undercutting and the method of draw. The balance of the mining system is the mechanical transportation of the drawn ore to the surface, the mine supply, drainage and ventilation systems. This paper deals mainly with the methods of draw. The method of draw to be used in a block caving system dictates the development plan of the mining area, is highly influential in the method of undercutting to be employed and the supply and ventilation system to be used. There are three basic methods of draw commonly used in today&apos;s operations. They are: Gravity draw Slusher draw LHD draw The type of draw planned will have a major affect on: Capital expenditure and time required to bring a deposit into production. Productivity, efficiency and cost of the production operation. Percent recovery of the ore deposit in both tonnage and grade. Degree of production reliability Fundamentally the type-of draw used must be compatible with the physical characteristics of the deposit to be extracted and the financial position of the mining operation. The type of draw chosen must work to advantage with the size, configuration, depth, strength and fracture pattern of the deposit and its adjacent formations. It must favor the financial protection of the planned mining operation. A Gravity Method of Draw requires a finely fragmented, easy flowing product from the caving action of the deposit. To obtain the desired economic advantage the ore deposit must also have sufficient area and height of column to permit minimal development cost on a per ton basis. The gravity system re- quires the maximum amount of development openings and uses the minimum amount of mechanized equipment of all the caving systems. It is unskilled, labor-intensive and is highly sensitive to size of ore fragmen-

Jan 1, 1981

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,&apos;"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,&apos;"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-&apos; cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By D. J. Carney, E. Richard Randolph, E. Van Meter, J. J. Oravec, Stanley H. Ward, Gerald J. Anderson, Rolland L. 203-000-000-005 Blake

DURING the last 30 years the inductive electromagnetic method has been used chiefly in the search for massive sulphide mineralization. This application has met with varying degrees of success and in recent years has resulted in discovery of several large orebodies. Little has been written concerning its use in exploration for soft iron ores, but one of the present authors has reported on experiments with massive magnetic deposits.&apos; To augment the exploration tools available to geologists in delineating iron orebodies, Cleveland-Cliffs Iron Co. and McPhar Geophysics Ltd. undertook in 1953 to apply the inductive electromagnetic method to Cleveland-Cliffs properties in the Lake Superior region. As a result of this project, equipment has been developed that enables simultaneous transmission of two audio frequency waves, and the field technique and interpretative procedure involved have furthered exploration in the district significantly. Thus far, inductive electromagnetic application in the Lake Superior region has been only a development tool, that is, it is used to locate obscured contacts and faults as a part of property expansion and development. However, its application to primary reconnaissance of unexplored areas may be feasible in the future. The method has assisted in placing drillholes efficiently, and the elimination of excess drilling foot-ages and/or actual elimination of unnecessary holes has amply justified the expense of the geophysical survey. Cost of the field work involved is comparable on a per station basis to the cost of a magnetometer or superdip survey. Since observations require no reduction, i.e., are directly interpretable, overall expenditure is low, and the scope and detail of the survey can be adjusted in the field as geological- geophysical correlation becomes evident. To a great extent, this eliminates the second-guessing so commonly arising after office calculations are completed on data obtained with other types of geophysical surveys. This unique feature of field interpretation and its associated intimate feel of the project area, is, perhaps, one of the most valuable aspects of the inductive electromagnetic method as applied to iron ore exploration. Basis of Method Fundamentally, the method involves transmission of an alternating electromagnetic wave, of a chosen audio frequency, which permeates the ground materials in the vicinity of a transmitting, or primary, coil, see Fig. 1. This wave, or field, induces an electric current in any conductor on which it is incident. The flow of an alternating current in a conductor sets up its own, or secondary, radiating electromagnetic field. These two fields form a resultant whose configuration depends on the following characteristics of the subsurface conductors: 1) size, 2) shape, 3) electrical conductivity, 4) magnetic permeability, and 5) frequency of the transmitted wave. To a lesser extent the resultant is also dependent on material adjacent to the conductor, topography, and surface conductivity. For illustrative purposes, the primary, secondary, and resultant fields may be represented by vectors. In operation, the direction of the resultant vector is measured by a small receiving coil tuned to the frequency of the transmitted wave. Generally speaking, the method can be compared to the transmission and reception of the familiar radio broadcast, with special variations permitting measurement of the effect on reception of intervening materials. Field Technique Mechanics of field operation are simple. The mast is set up in a vertical position and is then guyed in place. The transmitting loop then is raised by means of a sheave at the top of the mast and the coil connected to the motor-generator. A special plane table is clamped into position on the mast and the loop is plumbed. The plane table is oriented according to a grid system established over the project area. By means of this plane table it is possible

Jan 1, 1956

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,&apos; Rutter and Chalmers,&apos; Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-&apos;, c&apos;,, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c&apos;, — c",), , , = tic&apos;, (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick&apos;s first law it follows that uc&apos;,,(s = 0) (1 ~K) == - D(dc&apos;,,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By T. J. Neil, C. B. Manula, O&apos

This paper describes a simulation model developed to analyze truck haulage problems as they are found in the open pit mining and construction industries. The model, using a computer, cycles trucks between their assigned loading and discharge points over a measured haulage route. Required parameters for model operation include the number and type of operating trucks and loading units, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each origin. Equipment performance characteristics, system profile characteristics, and service time distributions are also included. Records are kept of all waiting times at the loading and discharge points and of any truck interference on the haulroads (moving queues), and a current journal of ore and waste production is maintained. In the pursuit of reduced truck haulage costs, management is confronted with three particular problems in truck and shovel mines. 1) What is the best assignment of trucks to shovels in the system? 2) If new equipment is needed, which new shovels and trucks will operate most effectively in the system? 3) Are any physical changes in the haulage layout warranted to increase productivity? For small open-pit mines the answers to these questions may be obvious. However, for larger operations complex problems are encountered with production and system configuration relationships usually being unknown. The mining simulator discussed here was developed to aid management in evaluating alternative pit-haulage schemes to reduce the risk involved in the selection and assignment of equipment in open-pit truck and shovel mining systems. There are two fundamental differences between this model and other truck haulage simulators: one is a difference of degree, the other a difference of kind. This model can simulate more complex systems than previous models by allowing transportation of material from multiple mine faces to multiple mine destinations and by being readily adaptable to a wide variety of mine layouts. The second difference that characterizes the model is the standard simulation of truck movements. This technique enables each vehicle to perform according to its mechanical capabilities and the physical profile of the haul road. Among the similarities between other truck haulage simulators and this model are the recognition of the probabilistic nature of certain service times in the system and the use of a digital computer to operate the model. The computer inherits the staggering computational and bookkeeping work loads and provides a means for compressing the time scale by allowing several days&apos; operations to be simulated in a matter of minutes. DISTRIBUTION SYSTEM Basic aspects of the system analyzed here may be brought into focus by referring to Fig. 1, a schematic of the typical open pit truck-shovel operation programmed into the simulation model. A single stage materials handling scheme is employed to transport both ore and waste. Loaded trucks are directed to a crusher or stockpile if ore is being mined, while overburden is conveyed to a waste dump. Each shovel has a given number of assigned trucks and has two associated haulage routes, one for waste and one for ore. Up to 5 shovels and as many as 10 trucks per shovel (or a total of 50 trucks) can be operated in the model. Essentially the model, using a computer, cycles trucks between their assigned shovels and the proper discharge points over measured haulage routes. Required input parameters for model operation include the number of shifts to be simulated, operating time per shift, number and type of operating trucks and shovels, maximum truck acceleration and velocity, a realistic vehicular deceleration rate, and the ratio of ore to total material loaded at each shovel. Equipment performance characteristics, system profile characteristics, and service time distributions are

Jan 1, 1968

By A. S. Michaels, M. C. Porter, A. Stancell

Previous laboratory studies have demonstrated that the injection of small quantities of reverse wetting agents during water displacement can increase oil recovery from unconsolidated porous media.9 In the present investigation, an attempt has been made to determine more fully the effects of reverse wetting treatments and to clarify the mechanism by which increased oil recovery is effected. Water-oil displacements were performed in beds of 140-200 mesh silica sand. Hexylamine slugs (injected after 0.25 pore volume of water throughput), when adequate in size and concentration, were effective in promoting additional oil recovery. Their effectiveness increased with the quantity of amine injected. However, slugs of sufficient size and concentration to stimulate oil production at water flow rates of 34 ft/day did not do so at 4 ft/day. Visual studies in a glass grid micromodel have shown that the stimulation of oil production, via ayueous hexylamine, is a result of transient changes in the oil wettability of the pore walls. if the amine slug is of sufficient size and concentration to induce significant changes in the adhesion-tension, large continuous oil masses will be formed. if the superficial water velocity is high enough to result in rapid desorption of the amine, a favorable "wettobility gradient" may be established across the masses; under such conditions, high oil mobility is observed, and increased oil recovery results. INTRODUCTION It is generally agreed that the efficiency of oil displacement by water in porous media is limited in part by capillary forces which cause the retention of isolated masses of oil — resulting in the so-called "irreducible minimum oil saturation". Recent estimates10 indicate that there are about 220 billion bbl of petroleum in United States reservoirs which are not economically recoverable with present techniques (such as water flooding). This amounts to almost five times the known recoverable reserves. It has been recognized for some time that a suitable alteration in the water-oil interfacial tension and/or the contact angle, as measured between the water-oil interface and the solid surface, should result in better displacement efficiency. Surface active agents can be used as interfacial tension depressants to accomplish this objective,1,2,7 but unfortunately, the additional oil recovery is seldom commensurate with the treatment cost. In contrast to interfacial tension depressants, the effect of contact angle alterations on water-oil displacements has received relatively little attention in the literature. It is known that the wettability affects the displacement process.3,4,11 Displacements in water-wet systems generally result in lower residual oil saturations than those in oil-wet systems. The effect of "&apos;transient" wettability alterations concurrent with the displacement process have been investigated by Wagner, Leach and coworkers,4,11 wherein it has been demonstrated that the establishment of water-wet conditions during water flooding of oil-wet, oil-saturated porous media is accompanied by significant increase in oil displacement efficiency. Michaels and Timminss studied the effects of transient contact angle alterations resulting from chromatographic transport of reverse wetting agents through unconsolidated sand. It was demonstrated that chromatographic transport of short-chain (C4 through C8) primary aliphatic amines can improve oil recovery and that the recovery increases with the quantity of amine injected (i.e., with either the amine concentration or the volume of the slug injected). Circumstantial evidence indicated that the increased displacement efficiency resulted primarily from transient changes in wettability of the porous medium. In the Present investigation. additional information has been obtained on the effects of reverse wetting treatments and the mechanism by which increased oil recovery is accomplished. Hexylamine slugs of varying size and concentration were chromato-

Jan 1, 1965

By R. F. Steigerwald

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

Jan 1, 1970

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy&apos;s law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy&apos;s law,