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By F. E. Jaumot, A. Sawatzky

IT as long been recognized that there is a need for accurate systematic data on diffusion in solids. Originally, such data were needed to check existing theories but, more recently, it would appear that it could be used most advantageously as a guide to, or a check for, much needed extensions of the theory of diffusion. The awareness of the conditions which are important to experimental accuracy, the availability of the materials for accurate experiments, and the techniques have improved to the extent that it would now seem to an experimentalist that, unless extensions of the theory are made which take into account the fundamental parameters of the atoms, the electrons, and the lattice in some detail, the field of diffusion will rapidly become an empirical or semi-empirical field. The present series of experiments was designed to provide accurate data on the diffusion of the elements of the IB and IIB subgroups in silver; that is, to provide data on the diffusion in silver of three face-centered-cubic elements with roughly similar chemical properties, but with different atomic or ionic sizes and, similarly, for three noncubic elements. The elements of these two subgroups have different valences, so that the data will not give any significant information on differences due to the crystal structure of the solute. The present paper reports data on the diffusion of copper and mercury in single crystals of silver; the data for the other elements of the IB and IIB subgroups were reported previously by the authors1'2 and by Tomizuka and Slifkin.8 Experiment The general technique used was identical to that previously described1,2 and will not be repeated here. In all cases, the sectioning technique and high specific activity isotopes" were used. The short half-life of Cu64 made decay corrections more important than for the other isotopes, and necessitated around the clock shifts while data were being taken. Each section was counted at least twice (as was true for all longer half-life isotopes) and a monitor was counted along with each sample. Data for the diffusion of mercury in silver are presented at a greater number of temperatures than for the other solutes. This is a result of two circumstances. First, six (of 30) samples had to be discarded because of pitting or recrystallization which occurred during the diffusion runs, even though the samples had sustained high temperature prediffusion anneals. Either of these was a very rare phenomenon in the other experiments, and their occurrence in this case is considered in more detail below. Second, the curves of the logarithm of the activity of the sections vs the square of the penetration deptht were, in general, quite good, but frequently seemed to show one point to have high activity and the next point to have slightly low activity in terms of the best straight line. When this occurred, there was remarkable regularity of the high-low sequence. In any event, the results, as far as diffusion coefficients are concerned, were not affected by this amalgam effect. In fact, the mercury data had the highest internal consistency of any of the data. Results Diffusion of Copper in Silver—-Diffusion runs were made at eight temperatures In the temperature range from 700° to 950°C, for times ranging from 5 to 45 hr. A linear curve of the logarithm or the activity vs the square of the penetration depth was obtained for all samples. Table I summarizes the results for individual samples and Fig. 1 gives a plot 02 the logarithm of the diffusion coefficients as

Jan 1, 1958

By W. B. Gogarty, H. R. Bailey

Methods are presented for determining molecular diffusion coefficients by using data from, capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetate-orthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deter mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. INTRODUCTION The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media -has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximate1y proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators.4 Recent studies5,6 have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients? These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow,8-10 Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies 11-13 have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary -flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW—THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. For the case of laminar flow and with a fluid pair having equal densities and viscosities, the equation is given by

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By R. J. Sandrea, S. M. Farouq Ali

The results of an experimental and theoretical study of the effects of rectilinear impermeable barriers and highly permeable channels on the sweep efficiency and conductivity of a five-spot network are presented. The study was carried out using Hele-Shaw, and conductive sheet analogs for both. normal and inverted flood patterns. A functional relationship was developed which provides quantitative prediction of the above parameters; i.e., sweep efficiency and conductivity, for the nonhomogeneous system. To evaluate this, it is necessary only to measure the interference modulus of the obstacle using a simple expression. The results indicate that impermeable barriers, with an interference modulus greater than zero, always cause a decrease in the conductivity and the sweep efficiency of the pattern. On the other hand, permeability channels do not have a significant effect on these parameters, unless they are located along the streamlines. The study also discusses a method of formulating the difference equations pertaining to the two-dimensional Laplacian in a system containing rectilinear barriers. In addition, a technique is described for tracing the progress of a free surface, using marked particles, in a stream containing discontinuities SuCh as those occurring at the extremities of barriers. The above computational scheme was used in a digital computer program to simulate results of the Hele-Shaw analog. The computed values of sweep efficiency mere in good agreement with the experimental values. INTRODUCTION At the present time waterflooding remains the most widely used technique for the secondary recovery of oil. Among the numerous factors that affect the performance of a waterflood, the areal sweep efficiency constitutes one of the most critical parameters. It is a function only of the geometric distribution of the wells for a homogeneous medium and unit mobility ratio. Geological considerations, however, such as the presence of sealing faults or solution channels in the rock matrix, would generally exert an adverse effect on the areal sweep efficiency of a waterflood network. Surprisingly little information is presently available on the quantitative implications of such permeability interferences. It was the object of this investigation to consider the presence of rectilinear, impermeable and highly permeable interferences in an otherwise homogeneous five-spot pattern, and to analyze their effects on the resulting sweep efficiency and pattern conductivity. The experimental phase of the study was conducted using two different models: the Hele-Shaw flow cell and the field plotter. For experimental convenience, the geometric boundaries of the five-spot were assumed to constitute streamlines even in the case where the interference was asymmetrically placed with respect to a repeated five-spot pattern. A second object of the study was to develop a computational scheme for numerically calculating the pressure distribution in a five-spot flow pattern containing rectilinear, impermeable barriers, and to use this distribution to compute the sweep efficiency. EXPERIMENTAL PROCEDURE HELE-SHAW ANALOG The Hele-Shaw analog was used both as a visual model and for determining the sweep efficiency for systems involving impermeable barriers. The physical limitations of this model as a means of experimentally studying the motion of a fluid in porous medium have been adequately discussed elsewhere.2,7 Likewise, it can be easily verified that the analogy remains valid when a portion of the region between the plates contains an obstacle of the same thickness as the distance between the plates. The model used in this study was composed of

By C. Perez-Rosales

A statistical method for determining simultaneously some of the basic geometrical characteristics of porous media such as porsity, specific surface* mean pore width, mean grain thickness and absolute permeability is presented. The proposed method is characterized by its simplicity and the minimum amount of laboratory equipment that it requires. The experimental procedure used to evaluate the various geometrical characteristics is based 'pan the 'surface analysis Of a a In view of this fact the app1icability Of the method is limited to homogeneous and isotropic materials. INTRODUCTION The behavior of a fluid flowing through a porous medium depends, among other things, upon the internal geometry of the medium; hence the importance of developing efficient methods to determine the geometrical properties of porous materials. This paper describes a statistical method to determine simultaneously some of the basic geometrical properties of porous materials such as porosity, specific surface, mean pore width, mean grain thickness and absolute permeability. The mathematical formulation has been developed that the data required to calculate the various geometrical characteristics of a sample can be easily measured by analyzing a section of the sample with an evenly spaced grid. THEORY A simple way of obtaining information about the internal geometry of a porous material is to throw a point at random over a cross-section of a sample. l-Through this procedure the porosity can be detemined.l,2 By considering that the material is homogeneous and isotropic, and that the point is dropped many times, the porosity 4 is given by where N is the total number of times the point is thrown and n is he number of times the point falls within pore areas. Another simple manner of analyzing the structural characteristics of a porous material is to superimpose an arbitrarily long line on a cross-section so that its length is evenly distributed over the surface area. Through this procedure the porosity can also be determined. If L is the total length of the line, and 1 is the sum of the lengths of the line segments within void spaces, the porosity is given by 4 = —.1.............. (2) The advantage of this type of analysis is that geometrical characteristics other than porosity can be obtained. Thus, if c represents the number of intersections between the line and the perimeter of pores, it can be shown3 that the specific surface, defined as he surface area of pores per unit bulk volume, is given by To give a proper description of the internal geometry of a porous medium, it is necessary to define quantities that characterize the notions of pore size and grain size. Unfortunately, because of the complexity of porous materials, it is difficult to give exact geometrical definitions of what is meant by the ConCePtS of "poresl' and "grains", especially when dealing with consolidated materials. Never theless, one often talks about the "size of pores" and the "size of grains" without defining accurately the terms. A possible solution to this problem follows. Assume that an arbitrarily long line is placed on a section of a sample so that the line is evenly distributed over the surface area (see Fig. 1). 1n a system like this, each line segment within a void space will be, by definition, the pore width in a given location and direction. Consequently, if the

Jan 1, 1970

By C. E. Shoenfelt

There was a notable decrease in drilling operations in 1940 in all of the Rocky Mountain states except Montana, where the two large fields on the Canadian border, Cut Bank and Kevin-Sunburst, were espe-cially active. The expanding markets for Montana natural gas made necessary the more intensive development of such fields as Rowdoin, Cedar Creek and Devon. While there were no important oil and gas discoveries in 1940 in any of the Rocky Mountain states, a few small pools were opened, which may constitute separate areas but may prove with later development to be extensions of old fields. Some of the old fields were extended and deeper pay zones were discovered in others. These have given the areas greatly increased oil reserves and therefore are just as important as the discovery of new fields. The more important of the developments in 1940 are given, by states, in the following paragraphs. Colorado Hiawatha Field, Moffat County.—The Mountain Fuel Supply Co. began the development at Hiawatha of its oil reserves, which were discovered in about 1929, and late in the summer oil began moving from the field by truck to the shipping point at Rock Springs, Wyoming. The Hiawatha field of northwestern Moffat County was discovered in 1927 by the Sormir Petroleum Co., with the completion of No. r Florence Wilson for 4,5,000,000 cu. ft. of gas a day from a Wasatch sand lens at 2200 it. In later development of the field, oil showings were reported in several wells but no development of this resource was undertaken until 1940, when a test of the oil possibilities was started with the release in April of a location for No. 5-A Wilson on the S\W. SW. NW. of sec. 23-1zN-1ooW., on the east side of the field. The Well had an initial production of 327 bbl. of oil a day pumping from three Wasatch (Tertiary) sands between 2005 and 2540 ft. It was drilled to 2562 ft., where the 65/8-in. casing was cemented and gun-perforated at 2005 to 2125 ft., 2260 to 2335 ft. and 2513 to 2540 ft. At the end of the year, this well was averaging zoo bbl. of oil per day, pumping. Two other wells were drilled for oil on Hiawatha during the summer—one a small well of 60 bbl. per day and the other a small gas well. Powder Wash Field, Moffat County.—The development of the Powder Wash field in northwestern Colorado was resumed in 1940 by the Mountain Fuel Supply Co., with the release of a location for No. 2-A Musser in the CWL.NW.SE. of sec. 4-1rN-97W. The Powder Wash field was discovered in 1931 by the Mountain Fuel Supply Co. and the discovery well, No. I Musser, on C.NW. of sec. 5-IIN-97W., was completed at 2152 ft. in the Hiawatha member of the nonmarine Wasatch for-mation for an open flow of 34,000,000 cu. ft. of gas per day under a natural pressure of 685 lb. per sq. inch. Oil was discovered in the Powder Wash field on Nov. 26, 1936, in the company's No. I Carl Allen on the NE.SW.SE. of sec. 32-12N-97W. The oil production was

Jan 1, 1941

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By A. L. Jr. Pozzi, A. O. Garder, D. W. Peaceman

A new numerical method is proposed for the solution of multidimensional miscible displacement problems. Besides the usual stationary grid associated with numerical procedures, the method uses moving points for which positions and concentrations are computed each time step. Based on the method of characteristics for treating combined transport and dispersion, the method applies equally well to any number of dimensions and, in contrast with other numerical procedures, properly takes into account the physical dispersion, no matter how small. Extensive tests show that accurate solutions of one-dimensional problems can be obtained over a wide range of values of the dispersion coefficient, including zero. They also show that the moving points do not need to be uniformly spaced, and that increasing the number of moving points beyond 2/grid interval does not significantly improve the accuracy of the solution. Two-dimmsional calculations using the new method were carried out to simulate laboratory model displacements in which gravity caused overriding of solvent. Good agreement between observed and computed profiles and measured and computed concentrations of produced fluid was obtained for a viscosity ratio of 1.89; at higher viscosity ratios, fair agreement was obtained Computed results were found to be significantly affected by vertical dispersion, and negligibly affected by dispersion in the direction of flow, in agreement with conclusions based on experimental observations. INTRODUCTION Although miscible displacement processes are potentially of great economic significance, limited progress has been made in developing mathematical methods for predicting the outcome of a solvent flood. Because of the complexity of the partial differential equations which describe multidimensional miscible displacement, numerical methods are a natural approach to their solution. The task of finding suitable numerical approximations to one of the partial differential equations, which involves both dispersion and convective transport, has been particularly difficult. Dispersion in the absence of transport is described by the heat flow equation, a second-order equation of parabolic type. This equation has been very successfully treated by numerical methods. Transport in the absence of dispersion is described by a first-order equation of hyperbolic type. This equation has been treated numerically with some success in one dimension, both by Lagrangian and Eulerian techniques, 1.2 but extension to two or more dimensions has not been satisfactorily accomplished. Usually one of two things happens: either the numerical solution develops oscillations or it becomes smeared by artificial dispersion resulting from the numerical process. When transport and dispersion are considered simultaneously, this numerical dispersion may dominate the low physical dispersivicy that generally characterizes miscible displacement. Stone and Brian2 have developed a new difference equation for treating combined transport and dispersion in one dimension. By suitable choice of certain parameters, they succeeded in markedly reducing both oscillation and numerical dispersion. However, a satisfactory extension to higher dimensions has not yet been found. Peaceman and Rachford3 presented a centered-in-time and centered-in-distance difference equation combined with a 1,transfer of overshoot" procedure which was demonstrated to work well in one dimension. The technique was applied to the two-dimensional miscible displacement problem, but subsequent calculations with zero dispersivity showed little change in results compared with the calculations they presented. This indicates that their method involved a numerical dispersion of the same order as the physical dispersion. The present paper describes an alternate method for solving the combined transport-dispersion

Jan 1, 1965

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By H. F. Yancey, M. R. Geer, C. L. Allyn, R. H. Eckhouse

Four coals were treated in the Humphreys spiral concentrator, and the products were examined by float-and-sink and screen-sizing tests to determine fundamental performance characteristics. The efficiency of the separation between coal and impurity was shown to be influenced greatly by particle size. FOUR coals exhibiting different washability characteristics were washed in the Humphreys spiral concentrator and the products examined by float-and-sink and screen-sizing tests to determine the mechanics of the separation between coal and impurity. With one coal, each 1/2-in. increment of the full width of the stream in the spiral was examined separately to determine where each size and specific-gravity fraction of the feed was stratified. The basic performance characteristics of the spiral were found to be the same for all of these coals. The coarsest fraction of heavy impurity stratified so far out in the stream that it could not be removed through the refuse ports and thus either entered a middling product or contaminated the washed coal in the case of a two-product separation. Impurity particles finer than about 100-mesh also were carried out in the main body of the stream and therefore were not removed in the refuse product. Little loss of clean coal in the refuse occurred in sizes coarser than 28-mesh or finer than 100-mesh, but considerable coal of intermediate size stratified in the stream that was drawn off through the refuse ports. Because of this modifying influence of particle size, the spiral is unable to make an efficient two-product separation between coal and impurity without some retreatment. Recirculation of a middling product through the same spiral as a means of obtaining more efficient operation was not attempted in this investigation. The size and specific-gravity composition of the middling product are, however, such as to render it amenable to simple hydraulic classification for recovery of coal. Retreatment of a middling product would improve the efficiency of the spiral, but even when making a substantial amount of middling, considerable clean coal enters the refuse product. Consequently, retreatment of a combined refuse-middling product would appear to offer greater promise for providing maximum efficiency. Because of the sizing characteristics of the spiral, a classified feed can be treated with higher efficiency than is possible on a natural raw coal. For this reason, semiclassified feeds, such as silt-bank or classifier-underflow materials, can doubtless be treated with higher efficiencies than those shown for raw coals in this report. Performance is, of course, only one of many factors that enter into the choice of cleaning equipment. The fact that the one company now using the spiral for cleaning coal has built a second spiral plant is ample evidence that the inherently low efficiency of this unit may be overshadowed by the low operating costs afforded by its extreme simplicity. Introduction A number of factors enter into the selection of coal-cleaning equipment, and most of them bear directly on the final cost of prepared coal. One of these factors is performance of the cleaning unit in terms of the efficiency of the separation it effects between clean coal and refuse. The importance of performance in the selection of a coal-cleaning unit varies with the difficulty of the cleaning problem. Obviously, if the character of the coal is such that only certain types of cleaning units are capable of yielding a clean product meeting market requirements, performance is of prime importance. If, on the other hand, the cleaning problem is so simple that any type of cleaner will provide coal of suitable quality, performance is important only insofar as it affects costs by determining the amount of salable coal lost in the washery refuse. With the objective of providing the coal industry with information that is helpful in the selection of

Jan 1, 1951

By Hisaaki Takata, Nobukazu Nanko, Ichiro Izawa

INTRODUCTION Tochibora Mine belonged to Kamioka Mines, which are located in Gifu Prefecture, the cen- tral part of the Japanese main island, has occupied the important position as a main source of silver, lead and zinc for the smelter of Mitsui Mining & Smelting Co., Ltd.. The annual production of crude ore goes up to about 1 mil- lion metric tons with average grades of 20g/t Ag. 0.31% Pb, and 4.18% Zn. For the last 20 years, the mine has struggled with the depressed zinc metal price in yen and the escalation of operating cost, especially la- bour cost. For instance, prices of commodities and labour cost have been raised 8 times and 14 times respectively during this period. On the other hand, total operating cost has been con- trolled to increase 4.5 times. The productivity of the mine has been increased 4 times by means of improvement of individual works and adoption of perfectly mechanized trackless mining system to reform the mining method. Some improvements are presented as follows; Today, drifting is carried out by the tunnelling crew which consists of 9 operators equipped with 5 Mobile-Jumbos, 2 LHD's and a jeep for carrying and loading ex- plosives. In order to get the high utilization of these machines, each crew manages systematically and continuously adjacent 15 faces under the direction of a forceman. As a result, we have accomplished high advance of drift. Furthermore, raising is carried out by a set of the raise-borer in case of long raises like ore- passes and also by the stage blasting method in case of short ones like slot-cuts. Generally speaking, the sublevel stoping method is considered to be one of the best methods for various respects; high productivity, low cost, easy grade control and safety. This method has been introduced in Tochibora Mine since 1950 and is now widely applied to lodes that could not be mined before by this method be- cause of the shapes of them and the conditions of their country rock. Now we are convinced to be nearly accomplished for our method. This report presents some examples of the standard sublevel stoping method and its variations which are practised at the mine. STANDARD SUBLEVEL STOPING Up to 1979 since 1950 when this method was first applied at the mine, 17 million tons of crude ore have been produced by this method, which amounted to 55% of the total production of the mine. During three decades, the productivity has been increased considerably by means of trackless mining system using large-sized machines and etc.. In other words, mining efficiency has been increased from 20 tons/man.shift to 100 tons/man.shift at large stopes. Formerly undercutting was carried out above the drawing drift by jack-legs and small scrapers and then several cone-shaped glory holes were made by stopers between the undercut level and the draw level. But now, a undercut drift is driven in parallel with the haulage drift at the same level of it. And at the undercut drift, drilling upward is carried out by a large-sized machines like the fan drill in order to extract the broken ore directly at the drawing drift connected with the haulage drift. Simplification of the work as well as utilization of large- sized machines enables to get higher productivity. But if the deposit is comparatively wider and the broken ore around the middle part of the deposit cannot be extracted, several drawing drifts are driven to the deposit and in order to minimize dead ore at the final stage of operation, the

Jan 1, 1981

By C. A. Fothergill

An improved blotter model is described which makes use of a plastic sheet as base for the blotter field and pins to represent the input wells. The model is simple to construct and adapt and is particularly useful for demonstration purposes. Operational details are given. INTRODUCTION The blotter model was first applied to the investigation of oilfield problems by Wyckoff, Botset and Mus-kat,' primarily in order to demonstrate the flood patterns which could be expected from various arrangements of input and output wells in waterflooding projects. In recent years the model has been largely superseded for analog studies by the potentiometric and electric analog models which are more refined and versatile, since they can simulate the form, and, in certain cases, permeability variations which it is not possible to do with the blotter model. However, the latter is still used for analog studies where the reservoir can be represented as being uniform in thickness and permeability, and where a visual record of the flood advance is required. Ramey andNabor,2 for example, have applied the model to the investigation of areal sweeps in oil recovery by in-situ combustion. Because of its limitations, the blotter model can be used in general for only very simple arrangements of input and output wells, but within these limitations it has a definite advantage over all other types, in that it provides a picture of the advancing flood using the simplest and most easily constructed apparatus, by contrast with the gelatin model, for example, which requires more elaborate equipment. Moreover, the experiments can be quickly repeated and modified if necessary, whereas considerable time is required to prepare a gel field, compared with that required for the preparation of sheets of conducting blotting paper. For these reasons the blotter model can be very useful for demonstration and teaching purposes, enabling the student to experiment for himself with different arrangements of input and output wells. A model has been constructed for this purpose which is simple to operate and adapt. The model (Fig. 1) consists of a base platform or box, approximately 12-in. square, on top of which are screwed three lathes of 1/2 -in. square section to form three sides of a square 6 in. in length. This forms the support for a sheet of Cobex, transparent plastic, thickness .003 in., on which is carried the blotting paper representing the field. The plastic is flexible and relatively soft, and can be attached to the support by cellulose tape so that it can be easily removed when required. The input wells are represented by brass drawing pins pressed through the plastic sheet from the underside until the points are just projecting through the top; these are connected in the circuit as shown in Fig. 2. The sheet of blotting paper of required shape and size is saturated with a solution of 0.2 n-potassium sulfate to which has been added a saturated alcohol solution of phenol-phthalein at a strength of 10 cc/liter of stock solution. The surplus water is removed and the blotting paper placed in position on the plastic sheet making contact with the drawing pins and the sheet (which is an insulator). The anode consists of a second sheet of blotting paper cut as shown and saturated with the same solution. This is suspended from a laboratory stand, being connected to the conducting wire by means of a crocodile clip and making contact with the horizontal blotting paper at the projecting point. This is the method used by Ramey and Nabor and which permits the hydroxyl ions or colored front to reach the anode. As shown in Fig. 2, the electrical voltage used is 220-v DC and a shunt is placed across the terminals to step down the voltage as required. Further adjustment can be made as necessary using a lamp board in series with the shunt to obtain the

Jan 1, 1958

By Luiz C. Correa da Silva, Robert F. Mehl

A. D. Le Claire and R. S. Barnes (Atomic Energy Research Establishment, Harwell, Didcot, Berks., England)-—This much awaited paper admirably confirms that the Kirkendall effect is a true diffusion phenomenon and likely to be found in all diffusing systems. The most likely explanation put forward so far to account for the shift of interface is that the two components of the system, diffusing in opposite directions, do so with unequal rates so that there is a net loss of material from that half of the diffusion zone rich in the more rapidly diffusing component. This loss is accompanied, and at least partly compensated for, by a closing up or decrease in volume of this latter half of the diffusion zone and an expansion of the other half so as to tend to keep constant the overall volume per atom. This is manifest as a movement of the original interface. If this is a true picture of what is taking place then there are at least two important matters requiring further study."1—The quantitative relating of the observed shift with the independently measured separate diffusion coefficients of the two diffusing species."2—A detailed study of the mechanism and characteristics of the closing up process."We would like first to make a few remarks pertinent to these topics. In connection with the first of these, it is a pity that more and detailed measurements were not made on the Au-Ag system, the only one for which the separate diffusion coefficients of the two species have been measured.'" One of us (A. D. Le C.) has calculated from Johnson's results the shift to have been expected in samples D.2 and D.3. Darken4 showed that the velocity v with which the markers move is related to the separate diffusion coefficients Dau, Dag, by the eauation:"dN"v = (Dag — Dau "dx"dN"where .is the concentration gradient at the mark-ax"ers. Under certain conditions,4, 20 it can also be shown that:"Xm"v = "2t"where x, is the total marker shift after time, t:"dN". . xm = 2t (Dag — Dau) [9]"dX"Johnson measured Dag and DAu in a chemically homogeneous alloy and so his reported figures represent the true or ideal diffusion coefficients"; the same quantities in eq 9 represent the actual diffusion coefficients as would be measured in the presence of a chemical concentration gradient, so we need to multiply Johnson's reported values of Dag and Dau by the"1 before insert-dlogN "ing them in eq 9. 7 is the activity coefficient of Ag at the concentration prevailing near the markers which we shall assume to be - 50 pct. The values of the thermodynamic factor for N = 0.5 and the temperatures at which D.2 and D.3 were annealed were obtained from thermodynamic data quoted by Darken.' aN/ax was computed from the coefficient of inter-diffusion of Au and Ag given by Johnson on the assumption that in the samples D.2 and D.3, the concentration distance curve could be represented by the standard equation:""No is the original difference in concentration between the two halves of the couple, and + is the error or probability function."aN/ax at x = 0 is then given by:"adN/dx "2/nDt"and we assume that this represents the concentration gradient at the markers, although it is probable that the figure is slightly high."When all the appropriate quantities are inserted in eq 9, we find that the expected shifts are: for D.2, 0.0134 cm and for D.3, 0.0119 cm."The agreement between these results and those

Jan 1, 1952

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By Richards R. Vandervoot

T HE creep behavior of many polycrystalline metals at moderate stresses can be described by the empirical relationship: where Em is the minimum creep rate, A is a constant, a is the applied stress, E is the average elastic modulus at the test temperature, and D is the self-diffusion coefficient.&apos; This equation is generally applicable for strain rates of less than around 10-5 per sec and temperatures greater than about one-half the melting point in absolute units. Under these conditions atomic mobility plays an important role in the deformation process, and steady-state creep occurs when a dynamic equilibrium is reached between the generation and recovery of dislocation substructure. Although several theoretical mechanisms have been proposed to explain the creep of polycrystalline solids,2"4 the dislocation climb model2 is in accord with most experimental observations. The majority of creep data used to develop Eq. [1] came from metals with either the fcc or hcp crystal structures. However, on the basis of results for a and 7 iron as well as those for a and a thallium, Sherby concluded that the high-temperature deformation behavior of close-packed metals and bcc metals is probably the same.&apos; The greater creep resistance of fcc and hcp metals and alloys on a relative temperature scale was attributed to lower diffusivities in the close-packed structures. To further compare the creep properties of fcc, hcp, and bcc metals, creep data for all six bcc refractory metals were analyzed according to Eq. [I]. The results are shown in Fig. 1. The sources of information for the quantities used to prepare this figure are listed in Table I, except for high-temperature elastic moduli. The latter data were obtained from Refs. 28 and 29. The dashed lines in the figure represent the range and breadth of data analyzed by Sherby for fcc and hcp metals. In general, the deformation behavior of all of the refractory metals, ex- cept possibly that of tungsten, can be represented by Eq. [1]. This correlation is strong evidence of the similarity that exists between creep of pure close-packed metals and creep of pure bcc metals. At (Em/D) < 108, the results of Flagella and Tarr on tungsten (W-1 in Fig. 1) agree with the five-power stress law, while those of Green (W-5 in Fig. 1) show a seven-power stress dependence. Where (Em/D) > 108, the stress exponents for other data on tungsten were in the range 10 to 15. It is possible that the creep rate dependence on stress in this region is not a power law but exponential (i.e., Em - eßo). However, it was not feasible to differentiate between these two cases because of the steep slope and scatter in the data. Note the inflection point in the curve for the data of Flagella and Tarr (W-1 in Fig. 1). The slope of the line changes from 5 to around 10 at Em/D = 108. The breakdown of the fifty-power stress law at high stresses is not uncommon in other metals, and this phenomenon may result from nonequilibrium conditions in the material such as excess lattice vacancies produced by rapid straining.30 The mechanical strength of a polycrystalline metal is related to its microstructure. Attempts to establish the influence of grain size on the creep rate of metals and alloys have led to a wide variety of results. For example, the following effects have been observed: creep rate decreases as grain size increases;31&apos;32 creep rate decreases as grain size decreases;&apos;,33 creep rate is a minimum at some critical grain size and increases with either an increase or decrease in

Jan 1, 1969

By M. W. Cox, V. F. Hollister

EXPLORATION for metallic mineral deposits is carried on by those special adaptations of methods which the explorer believes will yield most economically or satisfactorily the particular answer sought. In this project the usual methods of geologic observation, recording, and interpretation, when combined with magnetic geophysical methods and geochemical soil sampling, led to disclosures of appreciable zinc mineralization where none was visible in surface exposure. Since 1945 considerable work has been done with geochemical prospecting methods, chiefly in determining the presence and distribution of various elements existing in minor amounts in rocks, soil, vegetation or waters of mineralized areas. Such work, in which the U. S. Geological Survey has taken the lead, finds a ready place in the field repertoire of the exploration geologist as a supplement, not a substitute, for other methods. The Chollet project was carried out in 1951 by the American Smelting & Refining Co. near its Van Stone mine in northern Stevens County, Wash., in the area shown in Fig. 1. The Van Stone mine is located in the Onion Creek drainage of the Selkirk Mountains, midway between the towns of Colville and Northport, Wash., and some twenty airline miles west of the Metaline mining district. Its zinc-lead orebodies, currently yielding about 1000 tpd of ore, occur as bedding replacement deposits in the middle Cambrian Metaline formation near an intrusive granodiorite contact. The target of exploration at the Chollet prospect was a similar geologic environment along the intrusive contact about 5 miles west of the mine. Geographic Setting The Chollet ground covers a north-facing slope at 3000 to 4000-ft elevation. Second-growth jack pine and tamarack with some hemlock and yellow pine make a thick forest cover. A heavy under-forest of alder, willow, and lesser shrubs occupies the draws, see Fig. 2. Grassy slopes appear at higher elevations. The lower slopes are underlain by a thick blanket of glacial till and alluvium so that outcrops are scarce; however, perhaps 50 pct rock exposure prevails at higher elevations. This part of northern Washington annually receives about 25 in. of precipitation, which largely falls as snow in the winter months. Summers are dry with occasional rainy periods. General Geology The Van Stone mine and the Chollet prospect lie along the southern margin of a westerly extending lobe of the Kaniksu batholith, one of the series of granodioritic masses that are intrusive into Cretaceous and older rocks in northern Washington and southern British Columbia. The margin is composed of complexly deformed Paleozoic sediments ranging in age from the lower Cambrian Maitlen phyllite on the east, through middle Cambrian Metaline formation (limestone and dolomite), to Ordovician Ledbetter slate on the west. In general the formations strike N10 to 50E and dip steeply northwestward, although dip reversals and minor folding occur. This general rock distribution is shown on Fig. 3. In this area the Metaline formation, which is the host rock for mineralization, appears to be of about 4000-ft thickness that can be conveniently divided into the same three units defined by Park and Cannon&apos; for the Metaline area. The basal part consists of 1000 ft of interbedded white limestone, argillaceous limestone, and gray silty argillite. The middle part, approximately 1500 ft thick, consists of fine-grained black, gray, and white dolomite. This unit also contains minor interbedded limestone. The upper part is a gray massive limestone about 1500 ft thick that grades upward into slaty limestone and slate capped locally by a thin black jas-peroidal dolomite which is either the uppermost member of the Metaline formation or the basal member of the overlying Ledbetter (Ordovician)

Jan 1, 1956

By E. J. Ripling, S. I. Liu

IT has been shown in a number of recent publications that much information on the mechanical behavior of metals can be gleaned by first deforming test specimens under one set of conditions, and then evaluating the effect of this deformation by means of a subsequent tensile test. A straining procedure of this type has been applied to study the flow behaviors of a number of metals.1, 2 In these studies the prestraining and testing were both tensile strains, while the straining temperature was varied between the prestraining and testing steps. These data indicate that there is a more or less general flow behavior exhibited by all metals which are pre-stretched at one temperature and then tested in tension at a second temperature. Prestraining a metal at a high temperature produces a lower yield strength during the subsequent low temperature strain than would the same total strain at the lower temperature. On reversing the order of the strains, low temperature prestraining produces a higher yield strength during the subsequent high temperature straining than would a single high temperature strain of the same magnitude. Unlike the flow behaviors, the fracturing characteristics of metals when prestrained under one set of conditions and tested under a second set of conditions is quite material dependent. The fracture behavior of a number of steels2" as well as of a commercially pure zinc,4 have been investigated by these two-step tests and was found to depend upon the position of the transition temperature with respect to the prestraining and testing conditions. Since these fracturing phenomena are complicated by the appearance of the transition temperature, it has been difficult to reliably define the basic effect of a two-step straining procedure in fracturing. Metals crystallizing in the face-centered cubic system do not exhibit transition temperature effects so that the mechanical characteristics obtained on these materials could serve as a base for two-step straining behaviors. Consequently groups of specimens of the aluminum alloy 24s-T4 were prestrained various amounts at room temperature in either tension or compression after which these strained specimens were further strained to failure, or tested in tension, at either room or some lower temperature. Other groups of 24S-T4 specimens were prestretched at various low temperatures after which these were tested in tension at room temperature. These straining techniques then made it possible to compare the behaviors of aluminum with the behaviors previously presented for steels. Material and Procedure The commercial aluminum alloy 24S-T4 in the form of 3/4 in. rods was used in this investigation. The material was subjected to the following treatments before machining: 1—resolution treating at 920" & 10°F for 45 min, 2—quenching in water at room temperature, and 3—aging at room temperature for four days. The re-heat treated material was then machined to either of the specimen shapes shown in Fig. 1. Fig. la shows the threaded-end specimen used for prestraining in compression. Fig. 1b shows the specimen used for both prestrain in tension and final testing. The material subjected to precompression in the form of the specimen shown in Fig. la was re-machined to the specimen shape in Fig. 1b for final testing. Prestraining in tension and final testing were done without any intermediate machining. All straining was performed on a 10,000 1b Riehle tensile testing machine. Tensile strains were conducted in a specially designed concentric fixture which produced an eccentricity of less than 0.001 in." The change in diameter at the minimum section of

Jan 1, 1954