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By F. W. Jessen, R. W. Durie

The development in the laboratory of mall salt cavities illustrated that the rate at which salt dissolved was affected by the rate at which fresh water was injected into the cavity. Experiments carried out with small salt cores indicated, however, that the rate of salt removal with forced convection was not significantly different from that with natural convection, provided the flow was in the laminar range. The rate of salt removal was apparently controlled by the water salinity, which was indirectly determined by the rate at which fresh water was injected. With turbulent flow at the salt surface, the rate of salt removal could be increased several-fold with the same salinity in the cavity. A quantitative evaluation of the rate of salt removal under natural convection was attempted by using techniques developed for the analogous heat convection system. The values of the rate of salt removal obtained experimentally were considerably greater than the calculated values due to surface irregularities. To determine the effect of these irregularities, the rate of salt removal was found for a smooth surface by experimentally determining the rate of salt removal as an irregular surface developed and then extrapolating this trend back to initial time. Excellent agreement between the experimental and calculated values then were obtained. INTRODUCTION Underground cavities leached from massive salt formations have been used extensively for many years for storing LPG products. The development techniques for storing methane gases in the liquid state at a low temperature leads to speculation that underground salt cavities of controlled geometry may be quite important in this field. In any case, the increasing number of salt cavities used for storage indicates an impending need for a better knowledge of the washing process to efficiently develop maximum storage volumes within specified regions. It is the purpose of this paper to discuss some aspects of -the mechanism of the dissolution of salt in the formation of cavities of controlled geometry. Although no attempt is made to resolve the problems that may be associated with the storage of methane in the liquid state in salt formations, the fact that salt cavities can be formed at reasonable cost would appear to justify investigation in this direction. Further, underground cavities have the advantage of allowing storage at higher pressures (and hence higher temperatures) than surface installations. Although the thermal conductivity of salt is somewhat higher than frozen earths, 0.017 cal/(sec) (cm)(c) for salt at 32F vs 0.005 cal/(sec) (cm) () for ice at this temperature, this disadvantage is offset by the higher storage temperature in underground cavities. For example, at atmospheric pressure, the temperature of liquid methane would be —258F. In a storage cavity at 2,000 ft, the pressure would be approximately 1,000 psia, which would allow a storage temperature of -9OF. The formation temperature would be roughly 110F at this depth, hence the total temperature differential would be 200F. Under surface storage conditions the corresponding temperature difference would be some 333 F (75 F + 258 F). The results of this difference can be compared more readily by substituting the appropriate values of thermal conductivity, temperature difference, heat capacity and density into the solution of the diffusion equation for the unsteady linear conduction of heat. For the underground salt storage, the heat flux is 15cal/(sec) (sq cm), where t is the time in seconds from the initiation of the cooling. For the surface system, and using the thermal properties of ice at the average temperature, the corresponding figure is 21cal/(sec) (sq cm). Hence, the heat losses through ice under surface conditions would be some 30 per cent higher than the underground salt storage. This ratio would vary, considerablv. Of course, for other conditions, but it indicates that an advantage over surface facilities may be obtained by storage in underground salt cavities.

Jan 1, 1965

By R. L. Slobod, B. H. Caudle, E. R. Brownscombe

An earlier publication has discussed three methods lor obtaining relative permeability data on small core sample-: and the apparatus and technique for the capillary pressure displacement method. This paper describes the apparatus and technique for the solution gas and the dynamic displacement methods and presents a routine procedure for obtaining oil-gas and water-oil relative permeability data. Theoretical and experimental considerations are presented to show that the end effect commonly associated with the dynamic flow mechanism is extremely small where constant rates are employed in the flowing phase. An effect of flow rate on relative permeabilities obtained by the dynamic system is found only when gas is one of the flowing phases and this effect is ascribed to a form of channeling in the capillary system. The apparatus and procedure* used to obtain relative permeability data with three phases flowing are described and some preliminary results of the use of this method are shown. INTRODUCTION In a previous publication from this laboratory there appeared a brief discussion of the concepts behind three basic methods for obtaining relative permeability data.' These three methods were called the capillary pressure displacement method. the solution gas displacement method, and the dy. namic displacement method — the names being suggestive of the type of process used for obtaining the desired saturation prior to making the permeability measurements. In the same publication, the apparatus and technique for the capillary pressure displacement method were described and some typical results obtained by this method were presented. This paper will present: 1. The routine procedure used to obtain complete relative permeabilitv data (In small core samples with two phasec flowing; 2. The experimental techniques for the solution gas and dynamic displacement methods for obtaining relative permeability data; 3. The results of some studies on the mechanism of fluid flow through consolidated porous media; and, 4. The preliminary results on the determination of relative permeability for a system in which three phases are flowing. TECHNIQUE AND APPARATUS FOR THE DETERMINATION OF RELATIVE PERMEABILITY WITH TWO PHASES FLOWING In order to obtain relative permeability data on a small core sample which will describe the various phases of reservoir depletion. it is necessary that the methods used duplicate, as closely as possible, the various mechanisms involved in rescbrvoir depletion. It is important that. in any type of relative permedbility determination. the core be originally at virgin reservoir conditions with respect to the fluids within the pore *paces. (for example. oil used to displace water from core until connate water saturation estahlished). and that the subsequent saturation changes in the core be analagous to tile reservoir depletion mechanism for which the data are to he used. PROCEDURE OF DETERMINING RELATIVE PERMEABILITY DATA WITH TWO PHASES FLOWING A standardized procedure has been set up for obtaining relative permeability data and other information on small core samples. This procedure essentially consists of 11 steps as shown below: 1. Determination of tile capillary pressure curve.'! This information is used to help select samples for relative permeability determinations and to charactrrize. in general. the pore size distribution of the sample. 2. Determination of the specific permeabilities to air, oil. and water. These values are those on which the relative pern~eahility calculations are based. 3. Reduction of the core to connate water by an oil drive using the high speed centrifuge. 1. Determination of the critical gas saturation value and the associated relative permeability to oil by the solution gas drive method. 5. Determination of the relative permeabilities to oil and gab in the region where both phases are flowing by the capillary presqure method. 6. Reduction of the sample to residual oil in the centrifuge by an air drive. and the determination of the relative permeability to gas at this point.

Jan 1, 1951

By M. T. Simnad, R. F. Mehl, L. Yang

Techniques for studying marker movement in K-Rb interdiffusion have been worked out. The results indicate that Rb diffuses faster than K and that the ring mechanism of diffusion cannot be the dominant one operating in this case or probably in cases involving other alkali metals, despite their low ion core repulsive energies. SEVERAL theoretical attempts have been made in the past decade to elucidate the mechanism of diffusion in body-centered-cubic metals. No general agreement, however, has been reached by different authors. Zener,1 and later LeClaire,2 on the basis of a correlation between the entropy of activation for self-diffusion and the temperature dependence of the elastic constants, predicted that a ring mechanism should operate in the diffusion of body-cen-tered-cubic metals. Paneth3 calculated the activation energies of various ring, vacancy, and interstitial mechanisms for the self-diffusion in alkali metals and concluded that the most likely one was based on the linear motion of "crowdions," which is in fact a different form of interstitial diffusion. Fumi,1 however, showed that the experimental values of the activation energies for self-diffusion in the alkali metals could be better accounted for if the diffusion process in these metals was assumed to follow a vacancy mechanism. The same conclusion was reached by Kojima5 for the self-diffusion in lithium. Experimental evidences published during the past few years seem to exclude the ring mechanism as the predominating one in the diffusion of body-centered-cubic metals. For instance, maker movement has been observed in ß-brass, first in this laboratory" and later by Resnick and Baluffi.5 Shewmon and Bechtoldh also found marker movement in the body-centered-cubic system Ti-Mo and showed that the argument which led Zener and LeClair to favor a ring mechanism was not incompatible with a vacancy mechanism. In spite of this, it seemed to the authors that further experimental tests should be made by studying the Kirkendall effect in body-centered-cubic systems that characteristically have small ion core repulsion, such as the alkali-metal systems. Since the ion core repulsion term constitutes the main part of the activation energy needed for the rotation of a ring, such a test should be the most critical of all. The system K-Rb was chosen for experimental study because these metals form a continuous series of solid solutions. Experimental Investigation Owing to the extremely active nature of these two metals, a brass dry box (18 x 11 x 10 in.) was built for making the diffusion couple. It had a big lucite window on top, two side ports through which neo-prene-rubber gloves were inserted, and another side port covered with an optically flat-glass window for microscopic examination of the sample. Inside the box there were a circulating fan driven with a rotating horse-shoe magnet located outside the box, a heater used to generate potassium vapor for getter-ing the box, and a cold trap for keeping the inside of the box cool. Chemically pure grade K and Rb were triple distilled before they were transferred in vacuum into cylindrical steel molds kept in pyrex-glass ampules, Fig. 1. The latter together with the tools needed for making the diffusion couple were put into the dry box. After the box was flushed with purified argon and gettered with potassium vapor, generated from a heated steel crucible inside the box, the glass ampules were broken and the mound on the top of the alkali-metal ingot was cut off with a razor blade to yield a flat surface. To make the diffusion couple, one K ingot and one Rb ingot were pushed out of the molds together with their steel supports by screwing a metal plunger into the bottom of each mold. They were then laid on a brass cradle inside the assembling carriage (shown separately in Fig. 2) with the flat faces opposite to each

Jan 1, 1959

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.' Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts' Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg's method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By K. C. Hong, R. B. Jensen

The problem of determining the optimum set of steam volumes and cycle lengths for a single well undergoing multicycle steam stimulation in order to maximize the cumulative discounted net income has been formulated mathematically and programmed for a digital computer. The mathematical fonnulation of the problem and the method for its solution are discussed in this paper. The oil production performance during each stimulation cycle was simulated by either a constant percentage or a harmonic decline. Using simple analytical expressions for production performance, the cumulative discounted net income and cumulative time of operation were related to the pertinent process and cost parameters and two principal process control variables (cycle length and steam injection volume). The discrete maximum principles was used to transform the equations for cumulative time of operation and cumulative discounted net income into a set of simultaneous equations. The simultaneous equations then were solved by trial and error on a digital computer to determine the set of cycle lengths and stem injection volumes that gives maximum cumulative discounted net income over the project life. INTRODUCTION Steam stimulation is a process for improving the oil recovery rate from wells producing high-viscosity crudes. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three phases: steam injection, soaking (steam condensation), and production. Significant increases in production rate following the stimulation operation result from heating the reservoir around the wellbore. As heat is removed with produced fluids and dissipated into nonproductive formations, the production rate declines, usually to near the prestimulation value. Typical production responses are given in case histories reported by Owens and Suter,l and are depicted in Fig. 1. Duration of the production phase is equal to the time for the oil production rate to decline to some specified value and is called the cycle length. (Cycle length is defined as the producing portion of the cycle and does not include the downtime required for steam injection and soaking operations.) Termination of the production phase coincides with the start of steaming for the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable. Models 2-4 have been developed to simulate behavior of a single well during one cycle of steam stimulation and have been used to investigate the effects of system and operating conditions on the production responses. However, these investigations have not shown how the models can be used to determine a most profitable set of operating conditions for a multicycle stimulation project. Perhaps these models are too complicated mathematically to be adapted readily to an optimization study. This paper presents a method for optimizing a multicycle steam stimulation project based on simple production performance models. First, the performance of a steam-stimulated well during each cycle was simulated by either a constant percentage or a harmonic decline model. Using these simple analytical expressions for production performance, the cumulative discounted net income (before tax) and cumulative time of operation for each cycle were related to the pertinent process and cost parameters and two process control variables—the cycle length and the steam injection volume. Finally, the profit function to be maximized was formed. The analogy between the above problem and problems of optimizing multistage decision processes that have been reported extensively in the chemical engineering literatures5-10 in recent years has led this investigation to the use of the discrete maximum principle.5-7 This principle was used to transform the equations for cumulative discounted net income and cumulative time of operation into a set of simultaneous equations characterizing the optimum operating conditions in terms of the two control variables. These equations

Jan 1, 1970

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

IN a search for an improved conductor for use in field wire for the L. S. Army Signal Corps, an alloy of copper and silver was developed from which it was possible to obtain 29 B & S ga. strands with tensile strengths in excess of 160,000 psi combined with an electrical conductivity of over 70 pct IACS. Such a favorable combination of strength and electrical conductivity has not been reported previously in the rather extensive literature covering this subject. The properties obtained from various binary alloys of copper and silver, together with the method of fabrication of these alloys which has been developed to obtain the properties desired in fine wire strands, are discussed in this paper. LITERATURE The effect on the electrical conductivity of copper of the various elements in solid solution is shown in Fig I, taken from published data by J. O. Linde and others.' It will be noted that silver in solid solution depresses the electrical conductivity to a lesser extent than any other element for which data are given, and is followed rather closely by cadmium, and then by chromium. Zinc, which lies between cadmium and chromium, has so high a solid solubility in copper that the data for zinc are scarcely comparable to the data for the other two in the range covered. Not many data are available on the strain hardening of copper-rich Cu-Ag alloys. Corson2 reports a 3 pct Ag alloy properly cold worked and annealed to have 100,000 psi tensile strength and 90 pct IACS conductivity. On straight cold working, Hessenbruch3 reports 101.000 psi for a 5 pct Ag, 0.3 pct Be alloy, and 129,000 psi for a 30 pct Ag, 0.5 pct Be alloy. Here it would he expected that much of the strain hardening came from the silver content of the alloys. The copper-rich side of the Cu-Ag diagram, according to Stockdale,4 is shown in the upper part of Fig 2. The electrical conductivities for copper-silver alloys annealed at 750 and 350°C, taken from the work of Johansson and Linde,5 are shown in the lower part of Fig 2. The sloping line corresponds to the conductivity of solid solutions of silver in copper, and the horizontal offshoots correspond to the conductivity of the two-phase alloys in equilibrium at the two temperatures shown. The electrical conductivities are very high, even for the 750°C anneal. The potentiality for age hardening from supersaturated alpha copper solutions appears to be excellent from the solubility line, but Smith and Lindlief6 have shown that the response to age hardening of solution-annealed alpha alloys is not good. They found that the tensile strength of a 5 pct Ag alloy aged at various temperatures was not as great as in the quenched condition, even though, anomalously, the hardness increased from RB68 to RB78 by annealing for 4 hr at 400°C after a 750°C quench. Weist7 also found that the alloys increased in hardness

Jan 1, 1948

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10'6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

By Vaughn Moyer

A method for incorporating well drawdown effect into reservoir calculations is presented in detail, together with examples of its use for widely divergent conditions that could be normally encountered in oil reservoir sands. Tentative conclusions as to the effect such factors as permeability, producing interval, well spacing, or well damage caused by completion or repair practice could have upon economic ultimate recovery are reached. It is carefully pointed out that the conclusions reached are subject to limitations indicated in the text, and placed upon all calculations made in the paper. Introduction Papers have been presentedl-3 in which theoretical depletion histories for reservoirs under equilibrium conditions and no appreciable well-bore drawdown pressure are determined. However, except for a limited number of cases, appreciable drawdown Pressures in a well bore exist, and Pressure and saturation gradients consequently vary throughout a reservoir. This Paper is an attempt to incorporate well-pressure drawdown into reservoir history, and to analyze certain factors, such as those involving recovery, well spacing, and productivity index, from the standpoint of permeability and drainage radius. BY incorporation of drawdown into reservoir history, it is believed that theoretical considerations will more closely approxi- mate actual reservoir behavior experienced in an oil field. For purposes of simplification, a solution gas-drive type field1 without primary gas cap, has been selected. Basic Data and Assumptions Details of equilibrium saturation conditions for no drawdown production for various pressures in a reservoir are deter-minable by methods described by several are permitting the construction of a curve of oil saturation vs Pressure for any selected combination of initial interstitial water and hydrocarbon saturation (Fig I). This curve is then a description of equilibrium saturation conditions at any given pressure in a reservoir. Developing the above, details of saturation and flow permeability may thus be determined for any increment or portion of a well drainage area or reservoir. In this manner the effect of pressure differential (drawdown) may be incorporated into reservoir and well drainage considerations. It is pointed out that this method thus makes use of no-drawdown equilibrium production data, superimposing a draw-hwn effect upon them. It also assumes that net flow conditions in any considered increment of reservoir are not materially altered by the entrance of fluids from other increments into them, but approach equilibrium for the existing pressure and saturation (i.e., each increment behaves in more or less independent fashion, dependent largely upon the equilibrium considerations mentioned above)

Jan 1, 1948

By Vaughn Moyer

A method for incorporating well drawdown effect into reservoir calculations is presented in detail, together with examples of its use for widely divergent conditions that could be normally encountered in oil reservoir sands. Tentative conclusions as to the effect such factors as permeability, producing interval, well spacing, or well damage caused by completion or repair practice could have upon economic ultimate recovery are reached. It is carefully pointed out that the conclusions reached are subject to limitations indicated in the text, and placed upon all calculations made in the paper. Introduction Papers have been presentedl-3 in which theoretical depletion histories for reservoirs under equilibrium conditions and no appreciable well-bore drawdown pressure are determined. However, except for a limited number of cases, appreciable drawdown Pressures in a well bore exist, and Pressure and saturation gradients consequently vary throughout a reservoir. This Paper is an attempt to incorporate well-pressure drawdown into reservoir history, and to analyze certain factors, such as those involving recovery, well spacing, and productivity index, from the standpoint of permeability and drainage radius. BY incorporation of drawdown into reservoir history, it is believed that theoretical considerations will more closely approxi- mate actual reservoir behavior experienced in an oil field. For purposes of simplification, a solution gas-drive type field1 without primary gas cap, has been selected. Basic Data and Assumptions Details of equilibrium saturation conditions for no drawdown production for various pressures in a reservoir are deter-minable by methods described by several are permitting the construction of a curve of oil saturation vs Pressure for any selected combination of initial interstitial water and hydrocarbon saturation (Fig I). This curve is then a description of equilibrium saturation conditions at any given pressure in a reservoir. Developing the above, details of saturation and flow permeability may thus be determined for any increment or portion of a well drainage area or reservoir. In this manner the effect of pressure differential (drawdown) may be incorporated into reservoir and well drainage considerations. It is pointed out that this method thus makes use of no-drawdown equilibrium production data, superimposing a draw-hwn effect upon them. It also assumes that net flow conditions in any considered increment of reservoir are not materially altered by the entrance of fluids from other increments into them, but approach equilibrium for the existing pressure and saturation (i.e., each increment behaves in more or less independent fashion, dependent largely upon the equilibrium considerations mentioned above)

Jan 1, 1948

By S. J. Aresco, George E. Keller, J. Visman

INTRODUCTION The accurate sampling of coal, as with most minerals, is a difficult task. Coal is a very heterogeneous material made up of different types of coal and varying amounts of mineral matter. The product as mined may contain all of the layers of coal and impurities found in the seam as well as portions of the strata above and below the coal seam. The preparation plant is the device to size, crush and/or remove impurities so that the coal may be shipped as a saleable product. Sampling may be needed at many stages in the preparation process. Although this chapter is mainly concerned with sampling in connection with preparation processes, the principles will apply to all coal sampling. The main reasons for sampling in connection with coal preparation are: 1. To determine the washability characteristics of the raw coal by means of float and sink tests. These may be used for the design of a preparation plant, prediction of results to be obtained or for monitoring raw coal delivered to the plant. 2. To check the performance of various operating units in the plant, either by float and sink tests or chemical analyses. 3. To determine the analytical characteristics of the products produced, such as moisture, ash, Btu, sulfur, etc. HISTORY The earliest accepted methods of sampling coal in the United States were given in U. S. Bureau of Mines publications by J. A. Holmes,1 G. S. Pope2 and A. C. Fieldner.3 The American Society for Testing and Materials more or less adopted the methods proposed by the U.S. Bureau of Mines in their Standard D-21-1916, and it remained a standard for many years. Briefly, the standard called for a 500 pound sample for coals less than. 3/4 -in. in size and a 1,000 pound sample for all coals over ?4 -in. in size. No mention was made of increments but there was an instruction that the sample should spread over the coal to be sampled. Sample preparation was by hand crushing with the alternate shovel method for reduction to 250 pounds followed by coning and quartering below 250 pounds. Obviously, with the amount of work involved, this method of sample preparation was rarely followed. This method of preparation resulted in samples that were practically air dried because of long exposure while crushing, shoveling and quartering. In the late nineteen twenties and early nineteen thirties, studies for more practical methods were begun. Dr. E. S. Grummell4, Imperial Chemical Industries, Ltd, London, summarized the work to date at the

Jan 1, 1968

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By W. A. Weimer

Australia, the land of the kangaroo, koala, and the platypus, is often referred to as "down under" by people of the Northern Hemisphere. It is a tropical land and has very little freezing and thawing; consequently the in-place rocks are near the surface, exposing some of the unaltered mineralization. This type of geology induces the prospector and miner to search for minerals which lie at his feet (or not far under them), and it is adapted to open cut surface mining. Some of the rules and regulations applicable to exploration and mining in Australia will be interesting and helpful towards understanding acquisitions and control of minerals. They are common and basic to the United Kingdom. Throughout Australia practically all minerals are the property of the Crown (government), and their exploration and exploitation are administered by the state Department of Mines. Surface owners, or land lessees, do not control the minerals. Their mining codes protect the prospector. If a prospector obtains a permit, "miner's right," it entitles him to search for minerals any place within the state, only holding him responsible for damages he may incur in his exploration. If he finds something of interest, he may then apply for an authority to prospect, which gives greater latitude and protection in his work to develop the find. However, he will be obligated to spend a minimum specified amount to exclusively hold an area. He will be required to furnish maps, analyses, and geological data to the Mines Department. Presuming that he has located something economically valuable for mining, he may then apply for a mining lease or be granted a franchise to produce a specific material. It will contain a quantity clause so that the area cannot be held indiscriminately without production of the mineral. The states have Bureaus of Mineral Resources, Geology, and Geophysics that keep constantly abreast of the search for minerals and often do much of the drilling and deep boring to promote geological study for the states.

Jan 1, 1969

By R. P. Marshall

This note describes positive evidence that hydrogen in titanium alloys diffuses under the influence of a thermal gradient. The experiments confirmed the expected similarity of this system to the H-Zr system and produced qualitative information on the magnitude of the heat of transport for hydrogen in titanium alloys. This effect has practical importance in applications where titanium alloys operate in a thermal gradient under conditions such that hydrogen embrittlement may develop within the expected lifetime of the structure, for example in supersonic aircraft service. The theories of thermal-gradient diffusion may be found in recent reviews and experimentation in this field by Shewmon,1 Sawatzky,2 Markowitz,3 and Darken and Oriani.4 The basis for Soret thermal diffusion is the "heat of transport", denoted by Q*. This is an energy term for the amount of heat (energy) transferred by atomic diffusion, and can be either positive or negative signifying a driving force for atomic diffusion to the cooler or hotter region, respectively. Experimentally, Q* is determined by plotting the natural logarithm of the point-to-point concentrations after exposure to a thermal gradient vs the respective point-to-point temperatures in units of the inverse absolute temperature scale. The slope of the straight line is Q*/R, R being the gas constant. For the titanium experiments, specimens (3 by 1 by 1/16 in.) of a) commercially pure titanium, b) the 8 Al-1 Mo-1 V titanium alloy, and c) the 6 A1-4 V titanium alloy were exposed to thermal gradients of 6° to 115°C per in. for 18 days at 250° to 550°C. The temperature gradient was in the direction of the 3-in. dimension. The hydrogen concentrations existing after exposure were determined on sections of the specimens by vacuum extraction. Three sections of unexposed sheet of each alloy were analyzed as standards to allow a check for hydrogen

Jan 1, 1965

By H. H. Stoek

A STUDY of American coal mine practice shows two of its distinctive features to be: A greater number of accidents per thousand employees than in any of the other leading coal-producing countries; a much greater percentage of the coal lost than is the case in any of the other leading coal producing countries. Although our subject is mainly concerned with the second feature, any consideration of mining methods should include safety, efficiency, and economy or costs. If in defense of our wasteful mining the argument could be offered that it was necessary on account of safety, and that it is carried out with less loss of life than is the case in other countries the plea for conservation of coal could not be so strongly urged. But when we are wasteful of both life and property, the subject merits more consideration than it has received. Some coal operators will doubtless say that the unit of accidents should be the number per million tons produced rather than per thousand employees, for by adopting this unit America probably stands in the lead rather than the lowest among the countries. However, vital statistics are not usually so expressed by other governments, by life and accident insurance companies, or in other industries, and it is merely begging the question and attempting to bolster up a bad condition to adopt a peculiar unit for the statement of our accidents. For many years the statement was made by various agencies, and was unchallenged, that "For every ton of bituminous coal mined in the United States a ton had been lost in the way of pillars left in the mines." This statement was undoubtedly true for many years, and although some progress has been made in the past decade looking to a higher extraction, and in some districts very decided progress, the loss is still great; and, although no exact data can be given, it is probable that for the United States as a whole at- least one ton is lost for every two mined.

Jan 2, 1922

By Benjamin C. Greene, H. Beecher Charmbury

Water is a most remarkable substance, essential for life of all kinds. As well as needing water to survive, man has always used it for agriculture, transportation, recreation, and many other things. When our country was young and inhabited by few people, the streams, rivers, and lakes were able to provide all the clean water needed by man and take away all the wastes created. However, with our growing population and an ever-increasing demand for goods and services, the public, industry, and government at all levels have become acutely aware of the need to manage the nation's water resources more efficiently. Abundant energy from many sources has helped this nation to become the greatest industrial nation in the world. Coal has contributed a major portion of this energy, generating electricity, running railroads, and maintaining national security during wartime. The result has been the highest standard of living in the world and a time of widespread economic prosperity. The use of water in coal mining is somewhat different from its use in most industries. With the exception of water used in cleaning plants, for underground dust control, and for fire protection, most of the water en- countered in coal mining operations serves no useful purpose. In other words, it is an undesirable element and must be removed, otherwise it will interfere with operations, cause potential water quality problems, and may even stop operations by flooding. In the past, removing water from working areas of most mines was usually a fairly simple matter. Pumps with piping were installed at sumps or low spots in the mine and the water was pumped to the surface or to drainage control facilities constructed for the operation. Ditches were often used to collect and drain the water by gravity to the outside or to main sumps for pump discharge. In either case, the water was allowed to flow into the nearest stream or river. The concept of "water is water" was generally accepted without too much concern for what was in

Jan 1, 1981

By Edgar L. Collis

NO industry or group of industries is more deeply interested in the influence exerted by atmospheric dust than that concerned with the getting of coal and of metalliferous ores. The coal miner in the past has mainly been interested on account of the part played by coal dust in the occurrence of explosions; but investigation is revealing that coal miners experience, at least on certain coal fields, unduly high mortality ascribed to lung diseases, some part of which may reasonably be attributed to dust inhalation, and that a small group of men employed in sinking shafts and driving roads through sandstone rocks experience troubles identical with those that afflict many metalliferous miners. Coal Mining The Registrar General for England and Wales issues information every 10 years concerning the mortality experienced in various industries. The records dealing with coal mining are of particular interest, since they are given separately for each of the largest fields. When examined they exhibit the coal miner with a favorable death rate on the whole when compared with all other occupied males; but they reveal great differences on the different fields; thus the Lancashire miner in 1900-2 had a comparative mortality from all causes of 1006 as against a figure of 675 for the Nottinghamshire and Derbyshire miners, and in 1910-12 of 941 as against 570 for Nottinghamshire. When mortalities due to four only of the great causes of death are subtracted from the total the differences are greatly reduced; these four causes are phthisis, pneumonia, bronchitis and accidents. Thus for 1910-12 more than one-half of the mortality in Lancashire, 478 out of 941, is so accounted for, but less than one-third of the mortality in Nottinghamshire, 184 out of 570; the latter fraction compares with that for all males, 293 out of 790. Exactly why the accident mortality varies thus with those for the lung diseases has not been determined; the fact, however, points to an interesting association between health and so-called "accidental" occurrences.

Jan 1, 1927

By E. G. Bailey

The bituminous coal industry faces a real problem, if it desires to retain the position in the power-generation field to which it is economically entitled. More power is probably produced today for electrical energy, for steam-driven and steam-heating industries and processes, for transportation by rail, water, highway and air, collectively, than ever before, and yet the total bituminous coal production has decreased about 38 per cent, from 575,000,000 tons in 1926 to 357,500,000 tons in 1934. It is not the intention of the writer to recommend coal as a fuel for automobiles and airplanes, but rather to point to these forms of transportation as being responsible in a very measurable degree for reducing the coal consumed by railroads. Petroleum products may still further reduce consumption of locomotive fuel through the extension of the use of Diesel-driven trains. Oil-burning steam-driven locomotivcs are replacing coal in some places, where railroads operating high-speed passenger trains are willing, temporarily at least, to pay a premium for the fuel that is low in ash and produces less smoke and practically no cinders. In the navy and ocean-going passenger ships, oil is so firmly established, and has such definite advantages over coal as formerly fired, in steaming radius, in ease of bunkering, cleanliness, and reduction in firing labor, that very outstanding developments in the handling and burning of coal will be rcquired in order to replace oil. For freighters on the Great Lakes, coal is the logical fuel, but there is great and immediate need of radical improvements in its use, else that market also may be lessened. It is not within the scope of this paper to discuss in detail bituminous coal for either locomotive or marine use, but, rather, generation of power in stationary plants, consisting of electrical generating stations and that very large group of miscellaneous industrial plants, such as paper, rubber, textile, steel and other industries that use electrical, mechanical, and steam power, derived from either hydro or some form of fuel.

Jan 1, 1936

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By E. G. Bailey

The bituminous coal industry faces a real problem, if it desires to retain the position in the power-generation field to which it is economically entitled. More power is probably produced today for electrical energy, for steam-driven and steam-heating industries and processes, for transportation by rail, water, highway and air, collectively, than ever before, and yet the total bituminous coal production has decreased about 38 per cent, from 575,000,000 tons in 1926 to 357,500,000 tons in 1934. It is not the intention of the writer to recommend coal as a fuel for automobiles and airplanes, but rather to point to these forms of transportation as being responsible in a very measurable degree for reducing the coal consumed by railroads. Petroleum products may still further reduce consumption of locomotive fuel through the extension of the use of Diesel-driven trains. Oil-burning steam-driven locomotivcs are replacing coal in some places, where railroads operating high-speed passenger trains are willing, temporarily at least, to pay a premium for the fuel that is low in ash and produces less smoke and practically no cinders. In the navy and ocean-going passenger ships, oil is so firmly established, and has such definite advantages over coal as formerly fired, in steaming radius, in ease of bunkering, cleanliness, and reduction in firing labor, that very outstanding developments in the handling and burning of coal will be rcquired in order to replace oil. For freighters on the Great Lakes, coal is the logical fuel, but there is great and immediate need of radical improvements in its use, else that market also may be lessened. It is not within the scope of this paper to discuss in detail bituminous coal for either locomotive or marine use, but, rather, generation of power in stationary plants, consisting of electrical generating stations and that very large group of miscellaneous industrial plants, such as paper, rubber, textile, steel and other industries that use electrical, mechanical, and steam power, derived from either hydro or some form of fuel.

Jan 1, 1936