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By O. W. Rees, Gilbert H. Cady

Unit coal calorific values represent a close approach to pure coal values; they possess characteristics theoretically inherent in the latter values. They are essentially uniform in the same seam for areas possessing essentially uniform geological environment. They are higher in older than in younger coals in most cases, and in deeper than in shallower coals. In general, they display characteristics closely in accordance with expectation assuming that they are essentially indices of rank. Because it possesses these characteristics, the unit coal value is essentially a standard value, characteristic of each bed in each local region. Hence it can be used as a basis for determining the accuracy of results in newly established laboratories, or when new equipment is installed, or in checking the results of different laboratories, or even in determining the character of coal as mined or prepared if ash, moisture and sulfur values are known. DISCUSSION (A. C. Callen presiding) R. P. Hunson,§ Wayland, Ky. (written discussion).—One of the interesting observatioris made by the authors is that there is a more or less definite correlation between unit coal calorific values and the geological environment of the coal bed. It is very interesting to note that, in general, the unit B.t.u. value increases with the increase in the probable original depth of burial, and that each seam tends to increase in calorific value toward the areas of diastrophic instability. It is generally conceded that Parr's formula, for determining unit coal values, is about as accurate as any formula subsequently proposed for the same purpose. In his formula, Professor Parr did not differentiate between the sulfur present as iron pyrites and that present as organic sulfur. However, the practical application of the formula has shown that this is of little consequence. I agree with the authors that unit coal calorific values are useful ill determining the accuracy of calorimetric determinations, and in determining the character of the

Jan 1, 1934

By W. R. Hibbard

T has been proposed1 on the basis of slip and flow I- that the ideal deformation texture of cold rolled face-centered cubic metals is (110) [112]. As pointed out recently by Brick,' this theory does not account for the difference between the pole figures for cold rolled copper and 70-30 alpha brass, which develop strikingly different spreads from the ideal orientations. It does suggest that the pole figures might be similar for these two metals if they are rolled sufficiently. This has been found to be the case for cold drawn wire.' Experimental Procedure: Four inch sections of cast cakes of copper and 70-30 alpha brass were obtained through the courtesy of the Bridgeport Brass Co. Pieces from these cakes were cold straight rolled 99.993 pct reduction in thickness with the assistance of the Remington Arms Co., Bridgeport, Conn., and by the use of pack rolling. Pole figures were made using the X ray camera and techniques described by Brick.' These pole figures were not significantly different from those previously published for the same materials rolled 98 pct. Eight thicknesses of this strip were then pack rolled. This material failed completely and extensively in tension as shown in fig. 1, developing wavy transverse fractures and bulges. No further work could be done on these samples. Summary: Within the range of this experiment, no attainable amount of cold rolling would cause the pole figures of cold rolled copper and 70-30 brass to become similar, in spite of the fact that such a similarity is predicted by theory.' References W. R. Hibbard. Jr. and M. K. Yen: Trans. AIME (1948) 175, 126. Met. Tech. Feb. 1948. TP 2334. ²R. M. Brick: Trans. ASM (1949) 41A, 99. 3W. R. Hibbard, Jr.: Trans. AIME (1949) 185, 598, Jnl. of Metals, Sept. 1949. "R. M. Brick: Trans. AIME (1940) 137, 193. 'R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675.

Jan 1, 1951

By J. B. Dilworth

In estimating the investment-value of a mining-property or plant, the value of which decreases with operation, it is often necessary to know the sum which must be set aside periodically from earnings either to renew the plant at the end of its life, or to return the capital involved when the earningpower of the investment has ceased. In such cases it is manifestly incorrect simply to divide the total amount to be retired by the 'number of periods (usually years) during which the investment shall be active, as the sums periodically withdrawn have a certain interest-earning power varying with the length of time they are held and with the opportunities afforded for their investment. But though the interest may be considered to accumulate regularly year by year, yet the rules and tables for compouiid interest do not apply, owing to the addition of a fixed amount of new money to the total at the beginning of each period. Briefly stated, the problem of sinking-funds is, to find the amount of money which must be periodically set aside at a certain rate of interest, regularly compounded, to yield a certain sum in a given length of time. In most practical cases the interest is compounded and the fresh amount added at the same time—usually once a year—and on this basis the problem may be solved as follows : Let S = total amount to be retired, Let T = interest rate : R = 1 + r, Let n = life of tlie sinking-fund or the amortization-period, Let L = the sum set aside at the end of each year. Then the amouilt of the sinking-fund at the end of first year is 2, which at the end of n years will have illcreased by compound interest to IRn-l. Similarly, another amount, x, will be set aside at the end of second year, which will in turn increase

Jan 1, 1911

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

CONTENTS PAGE Ross, J. M. and WAYLAND, R. G.-Mining Methods at the Homestake. Discussed by Benjamin F. Tillson, R. M. Raymond, I, H. Barkdoll, Arthur Notman 1 EMMEL, RUDOLPH.-Mining Methods in Zaruma District, Ecuador. Discussed by Rudolph Emmel, George A. Packard, Fred Hellmann, R. M. Raymond, Arthur Notman 2 MISHLER, R. T. and BUDROW, L. R.-Methods of Mining and Ore Estimation at Lucky Tiger Mine. Discussed by Fred Hellmann, Benjamin F. Tillson...4 PARK, JOHN FURNESS.-Mining Methods of Jarbidge District. . Discussed by R. S. Lewis : 5 Mining Methods at the Homestake Discussion of the paper of A. J. M. Ross and R. G. WAYLAND, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1408-A, with MINING AND METALLURGY, February, 1925. BENJAMIN F. TILLSON, * Franklin, N. J.--It requires a good deal of timber to operate, especially the caving systems. An important function in mine operations now seems to be forestry and to operate a timber tract in order to insure a supply of timber. By depleting the timber resources of your section, you only increase your costs later when timber must be brought in from the Pacific Coast or the East. Our experience has been that any square-set method of timbering is the most expensive. Timbering for stoping systems, top slicing if you will, although it uses a large volume of time does not require as expensive timbering as the square-set method; also it does not require as long a life for-the timber, so that such wood as birch and maple, which have strength but not long life under the fungus conditions in the mine, may be used. All the drifts in the orebody are thoroughly timbered, and it has required a lot of timber. If we had it to do over, we would spend a lot more money in the development of rock drifts; as a matter of fact, we must ultimately come to that any way.

Jan 6, 1925

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

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

The theory of the differentiation method for the Couette flow experiment is reviewed. Particular attention is given to the requirements on data analyses in the case of the class of non-Newtonian materials described as viscoplastics, i.e., materials characterized by a yield point or yield stress. Here changes in boundary conditions arise when the shearing stress attains a critical value with the result that the form of the basic integral equation for Couette flow is determined by the flow conditions existing during the measurement. INTRODUCTION In the preceding papers in this series,l,2 the salient features of the differentiation method of rheological analysis in Poiseuille-type flow were discussed. It was shown that a dual differentiation-integration method analysis of the Poiseuille flow of idealized generalized Newtonian and visco-plastic models could be used to develop a spectrum of highly sensitive response patterns in terms of certain characteristic derivative functions. These functions were shown to optimize the selection of the most appropriate functional relationship between f(p) and p from the Poiseuille flow experiment. The present paper reviews the theory of the differentiation method as applied to the equally important Couette flow experiment. We will also discuss the range of variables over which the basic integral equation for Couette flow is applicable when the non-Newtonian material is of the viscoplastic type, i.e., characterized by a yield point or yield stress. THEORY Having described the application of the differentiation method to Poiseuille-type flow in the preceding papers, we now proceed to the case where the test liquid is confined to the annular space between coaxial cylinders of length L, one of which is in motion, i.e., Couette flow, formulating the basic integral equation after the method of Mooney.3 The observed kinematical and dynamical quantities are the angular velocity O and the torque T. Here, the one nonvanishing component of the shear-rate tensor is

By Mary Louise Theodore, R. G. Aspden, D. A. Colling

T RACES of sulfur have a marked influence on the physical and mechanical properties of many iron-base alloys. The commonly used combustion method for the determination of sulfur content is not accurate enough at the 50 ppm level by weight and below to be useful in determining the influence of sulfur. Kriege and Wolfe' have described a method for the determination of sulfur in iron alloys in which the sulfur is evolved as hydrogen sulfide followed by reaction with N, N-dimethyl-p-phenylenediamine, and iron (111) to form methylene blue which is measured spectrophoto-metrically. This method of determining sulfur has been used to study the activity of sulfur in Fe-Si-S alloys,' but has not been previously applied to the determination of sulfur in Fe-Ni alloys because of the insolubility of nickel in dilute hydrochloric acid. Dissolution of nickel in dilute hydrochloric acid, however, can be greatly accelerated by the addition of a small amount of platinic chloride.3 By combining these two techniques in a procedure in which 0.005 pct platinic chloride in 1:l hydrochloric acid is used as the dissolving fect on the strength of the material. However, ductility is influenced by the presence of discontinuous precipitation. In Fig. 5, percent elongation data at room temperature and 1400°F is shown for two sets of specimens of Waspalloy which were solution heat treated at 1950°F and either quenched or slow cooled to the aging temperature and then aged for 100 hr at 1292" and 1598ºF, respectively. At room temperature the existence of a discontinuous precipitation cell at grain boundaries (see data point marked by arrow) has no apparent effect on ductility. However, at elevated temperatures a pronounced lowering of ductility occurs when discontinuous precipitation has occurred in the specimen. It would appear that the morphology of discontinuous precipitation "cells" at grain boundaries would be highly conducive to the initiation of cracks which in turn lead to premature "grain boundary" failure.

Jan 1, 1970

I would like to congratulate the authors on an interesting paper and, in particular, on their justification of the use of superposition in treating gas wells. They state, however, that no theory has previously been developed lor treating the variable rate drawdown case. In a paper published a few years ago by my colleagues and myself, a method is described which allows a constant rate drawdown curve to be derived for any well. regardless of real rate variations. This method has the great advantage that it is not necessary to make any assumptions regarding the form or uniformity of the reservoir, and the derivation suggested by the present authors is simply an idealized case of our more general treatment. In the light of several years' experience in the derivation of constant rate drawdown curves: I would like to point out that the method proposed by Odeh and Jones may lead to confusing answers, particularly if applied over an appreciable time interval. The reason is that, if pressures are measured when a well is flowing, non-linearities in plots like Figs. 1 and 2 can arise due to either (1) changes in the skin factor with time and/or flow rate, or (2) an inhomogeneous reservoir. Separation of these two effects is only possible if some of the pressures used in the analysis are measured when the well flow rate is 0 or, in other words. during brief shut-in periods. REFERENCES 1. Arthur, K. B.. Metunomski, Z. G. and Ruche, Ms "Intetet ct methode d'utilisa tion des mesures de pression [)our Petude des gisemonts" Revue de T'I.F.P. (Nov., 1962) XVII, 1299. 2. Thomere, R. and Arthur, K. R.: "Analysis of the Pressure Bet~avior of a Production Well Subject to Interterence and Its Application to Reservoir Models", Paper SPE 1189 presented at SPE :Amund Fall Mecting Ireld in Denwer, Colo. (Oct. 3-6, 1965).

Jan 1, 1966

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

By R. J. Teitel

FOUR or five years ago an investigation was initiated to study and develop basic information on llquid metal fuels for future power nuclear reactors. The objective was to find fluid forms of uranium (solutions or dispersions) in low melting alloys. A summary of the different fuels was presented in a recent article by Teitel, Gurinsky, and Bryner.' The combination of uranium and bismuth, with its low thermal neutron cross section and low melting point, is of basic interest to the development of these fuels. Most of the previous effort on the U-Bi phase diagram was done under security regulation. Ahmann and Baldwin' reported their findings on the U-Bi system in 1945. Their results indicated that the phase diagram had at least two compounds and possibly one more. UBi, and UBi were established by chemical analyses of residues after high temperature centrifugation of alloys. UBi, decomposed peritectically at1980°C and there were signs of another reaction above that. UBi melted at a very high temperature, and there were also signs of a monotectic at high temperatures in high uranium alloys. The solubility of uranium in liquid bismuth has received attention by three groups of authors: Bareis,X ayes and Gordon,' and Ahmann and Baldwin.' The latest and most widely accepted data is that of Bareis, and it is included in Fig. 1 along with new data at higher temperatures. Brewer et al." and Ferro"'' have used X-ray diffraction to determine the number and crystal structure of the compounds. Brewer identified the structure of UBi to be a simple NaCl cubic structure having a cell edge of 6.364A. The density of the compound was calculated to be 11.52 g per cu cm. Two other unindexed patterns were presented as possibly belonging to two other compounds. Ferro agreed with Brewer on the crystal structure of UBi and identified the structure of UBi, and U,Bi,. The intermetallic compound UBi, has a tetragonal cell with a = 4.445A and c = 8.908A. The density of the compound was determined and the number of atoms per cell (six atoms) was calculated. The X-ray density reported was 12.35 g per cu cm. The compound UsBir was treated in a similar way and it was reported to have a cubic structure 9.35A on an edge and to contain 28 atoms per cell. The density was given as 12.59 g per cu cm. Teitel reported that there was a compound UaBi, and no UBi, compound. (The difference in the compositions is 3.3 pct U.) This conclusion was based upon the extrapolation of some 20 tie lines in the

Jan 1, 1958

By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By H. C. Stumpf, L. A. Willey, V. L. Fink

Very few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.10 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. Materials The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society. Chemical analysis of the aluminum showed the fol- lowing impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectro-graphic standard procedures5 No. IIA and No. SI I respectively. Determination of Miscibilitv The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano. As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 1/2-in. iron pipe and pipe caps. ?&apos;he space around the sides of the crucible was filled with 40 mesh crystalline alun-dum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1949

By L. Guttman

LESTER GUTTMAN* The question of whether classical thermodynamics alone imposes any lower limit to solid solubilities was raised during a discussion among various members of the Institute for the Study of Metals. Although our conclusions are not new,1 they may be worth reiterating, since confusion on this subject seems to persist. In a binary system (A,B), the conditions for equilibrium, at constant pressure and temperature, between a solid solution and a liquid solution are µAs = µAl [la] µBs = µbl [lb] Here µ denotes the chemical potential either of component A or B, as shown by the subscripts, and the superscripts s and l refer to the solid and liquid solutions, respectively. These two conditions are just sufficient to determine the compositions of both phases. Suppose, however, that the solid phase is found experimentally not to contain any of component B; then we cannot evaluate µbs, which is defined by Here nAs and nBs are the number of mols of A and B, respectively, in the solid, whose free energy is Fs. Eq lb cannot be used, but it is no longer needed: we stated at the outset that the solid has the composition "pure A," and only the liquid composition need now be determined, from Eq la. All the equilibrium properties of the system can be derived from Eq la rigorously and simply. Hence there is no purely thermodynamic reason to exclude phase diagrams which show precisely zero solid solubility. Marsh2 has objected to such diagrams as implying that even the transformation of pure A begins at the eutectic temperature. In any case, the user of the diagram must have a certain minimum knowledge of how to interpret it, and it would seem simpler to remember the general rule that eutectic temperatures have no significance for pure components, rather than to show, say, by broken lines, on a scale which will often be exaggerated, a hypothetical solid-solubility about which we know only that it is less than a certain amount. The case of an intermetallic compound in equilibrium with a binary liquid solution does not require a separate treatment since nothing in the foregoing was dependent on the nature of the components. Therefore, thermodynamics alone does not exclude the possibility that (intermetallic) compounds may exist with compositions always precisely those given by their chemical formulas. With the aid of extra-thermodynamic methods, one may conclude that the solubility of one solid in another is never exactly zero. On the other hand, one would generally expect that the solubility will be small unless the components resemble one another (as do the metals), or form weakly-bound crystals. Therefore, it is useful to know that when there is no direct evidence for solid-solubility, one may neglect it without violating thermodynamic principles.

Jan 1, 1950

By Richard M. Foose

FIVE miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. GEOLOGY Lower Cambrian Antietam quartzite and the Montalto quartzite, stratigraphically older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65° to vertical. The clay crops out at an elevation of about 1000 feet. ORIGIN AND CHARACTER The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about l00 ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: Si02, 67.05 per cent; A1203, 22.27; Fe203, 0.40; CaO, 0.00; Ti02, 1.05; MgO, 0.52; Na20, 0.04; K20, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1944

By N. A. Gokcen, J. Chipman

A revised treatment of the authors&apos; published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors&apos; found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K&apos;2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K&apos;3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur&apos;s data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.&apos; In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K&apos;1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K&apos;1 and the following average values are suggested both for K, and K&apos;, at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-&apos;. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,&apos; which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley&apos;s tables of high-temperature heat contents" and entropies and with Korber and Oelsen&apos;s&apos; heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen&apos; is an evolution of 28,500 cal per gram

Jan 1, 1954

By C. R. Sandberg, L. S. Gournay, R. F. Sippel

The effect of fluid-flow rate and fluid viscosity on oil-water relative permeability determinations was studied using the "dynamic flow technique." In this work relative per-nleability curves were obtained for homogeneous small core .samples from several sandstorle outcrop form-utions. Radio-tracers were used for the determination of fluid saturation and for the detection of saturation gradients. Cobalt-60 in the form of cobaltous chloride was used as a water-phase tracer in some of the experiments. Iodine-131 in the form of iodobenzene and Mercury-20-3 in the form of mercury diphenyl were used as oil-phase tracers in other experiments. Flow rates for each phase were varied within a range of 2.5 to 140.6 ml/hr. Oil-phase vis-cosities under flowing condition,> were varied from 0.398 to 1.683 cp. The relative permbilities ob-tained were found to he solely a function of saturation and independent of flow rare, provided there was no .Saturation gradient induced in the core sample by "boundary effect." Even though equilibrium with re-sped to flowing conditions was obtained at the lower flow rates, where a saturation gradient exists, this equilibrium is of a "contingent"-type rather than the "steady-state" equi-librium implicit in the relative per-meability concept. The only effect of increasing the oil or non-wetting phase viscosity was to decrease the flow rate required for the elimina-tion of the boundary effect. Fairly good agreement between experimentally determined and calculated values of the boundary effect was obtained when the non-wet-ring oil phase was the only Flowing phase. INTRODUCTION In the characterization of reservoir rock, as well as in the solution of reservoir production problems, it is most desirable to have reliablc rela-tive permeability measurements for the rock and fluids of interest. Many techniques have been developed for the laboratory determination of the relative permeability of both large and small core samples. In varying degree, difficulties attend the use of all of the methods. Each of the methods requires the metered flow of fluids of known viscosity through the core sample under conditions wherein the pressure drop in the individual flowing phases can be measured or closely approximated. Since the relative permeability is a function of the saturation and distribution of the flowing fluids, some means of obtaining such information is also required. The laboratory determination of the relative permeability of a sample should give the same relative permeability saturation relationship that would exist if the sample were in place in the oil reservoir. The attainment of this objective is complicated by the fact that the use of small core samples for laboratory measurements is usually necessary. As a result, errors in measuring the relative permeability arise from boundary effects at either the fluid input or output ends of the sample; no significant boundary effect is anticipated at the sides of the sample normal to direction of fluid flow. At the input end of the sample a boundary effect exists if the flow fluids are not com- mingled as they would be in the reservoir. At the output end of the sample a boundary effect exists as a result of discontinuity of the capillary properties of the system. Here the flowing fluids leave the small flow channels and enter a collecting system having much enlarged flow channels. Thus, there is a tendency for the wetting phase to be retained by the core sample because of the attraction of the core sample for the wetting fluid. No reference is made to these boundary effects in either Darcy&apos;s equation or in the relative permeability concept. As a consequence the saturation effect peculiar to the input end of the core sample may cause an error in the effective permeability measurement, since some portion of the core sample must be utilized for commingling of the flow fluids. At the output portion of the core sample a saturation gradient or a saturation change along the axis of flow results. Since relative permeability is a function of fluid saturation, this saturation gradient may cause a variable permeability measurement, especially since extent and character of the saturation gradient can vary with fluid-flow rate. The most convenient method of minimizing the boundary effect, especially at the output end of the sample, is to flow the fluids of interest through the core sample at such high rates that the capillary forces arc insignificant as compared to the viscous forces involved in the fluid flow. Since recent work of a preliminary nature has indicated that fluid dispersion in the porous medium increases with the flow rate, the high flow minimizes the boundary effect at the input end of the core sample by enhancing the mixing of the fluids.

By R. Simon

The sources of energy dissipation for concentrated loadings on rock are considered in an attempt to account for the experimentally measured magnitude of the work required to break out a unit volume of rock from the free surface of an essentially semi-infinite medium. It is concluded that most of this work probably represents the elastic strain energy developed by the loading in a much larger volume of rock beneath the loaded region than the volume of the rock fragment broken out to the side of the loaded region. This strain energy is largely dissipated in the form of stress waves generated by the high rate of unloading produced by the propagating cracks. The energies associated with the formation of the new surfaces of the cracks and with the stress waves generated directly by the loading process are computed to be negligibly small. Possibilities for improving the utilization of energy to drill rod. subject to the geometrical limitations imposed by down-hole operation, are discussed. It is pointed out that any such possible improvements would probably have to be differential ones, since each rock configuration of more favorabIe loading geometry that can be created down the hole is accompanied by a complementary configuration of less favorable loading geometry. INTRODUCTION Dislodging each cubic inch of rock from the bottom of the hole by the action of a bit requires the expenditure of an amount of energy that varies from approximately 5,000 in.-lb to approximately 100,000 in.-lb, depending on the hardness of the rock, or, more technically, upon its fragmentation strength.1 In this paper we will discuss (I) why the energy expended in drilling is so large, (2) what happens to this energy upon completion of the drilling process, and (3) what are the possibilities for reducing the magnitude of the energy required to drill rock. DETERMINATION OF ROCK DRILLING ENERGY The volume of rock removed per unit time from the bottom of a hole of diameter D is evidently (7/4)D2R, where R is the rate of penetration of the bit. If P is the rate at which work is done by the bit on the rock at the bottom of the hole, the energy required to break out a unit volume of rock is given by: Ev =(4/p) P/D2R............(i) For rotary drilling, of either the rolling-cone or drag-bit varicty, P = 2pLN, where L is the torque resistance to rotation at the bottom of the hole and N is the rate of rotation of the bit. L is essentially the same as the torque measured at the rotary table only when drilling in shallow holes. The energies expended in rotating the drill string against the frictional resistance of the walls of the hole and and against the viscous drag of the drilling fluid are extraneous to the subject under consideration, although these may be much greater in magnitude than E, when drilling in a deep hole. For percussion drilling, P = fE where f is the percussion frequency and E is the work done on the rock per impact. The latter quantity can be both computed and measured for a percussion drilling machine. 2 (Under satisfactory drilling conditions, defined in terms of ranges of numerical values of certain dimensionless parameters, E is only 30 to 50 per cent less than the impact energy of the striker.2) Alternatively, E, may be measured directly by dropping chisels shaped like bit edges, backed by rigid weights, onto the surfaces of laboratory rock samples of effectively semi-infinite extent. Under these circumstances, essentially all of the impact energy is converted to work done on the rock, and the relationships among volume of rock broken out, chisel shape, impact energy and indexing distances can be obtained.3 The values of the energy required to break out a unit volume of rock under favorable circumstances are substantially in agreement for rotary drilling, percussion drilling and drop testing at atmospheric pressure. The energy per unit volume is a quantity of the order of magnitude of roughly twice the com-pressive strength of the rock as measured by a uniaxial loading test. The phrase "order of magnitude" in this paper means from about 1/3 as much to 3 times as much; i.e., the energy per unit volume may range from roughly the same up to several times

By Tong Guangxu

INTRODUCTION Throughout the world, the caving mining methods of ore-draw under the overlying waste rock are sublevel caving in Sweden, block caving in U.S.A. and forced block caving and sublevel caving with sill-pillar in U.S.S.R. These caving methods are of high efficiency, low cost and large production (especially the block caving method) when compared to opencast mining. From the ore production of all under- ground mines, the largest annual production of underground metalliferous mines in the world is caving methods. The sublevel caving in Kiruna Iron Mine of Sweden has reached annual ore production over 20 million tons in 1974. The block caving in Climax Molybdenum Mine and San Manuel Copper Mine of U.S.A. both have produced about 40 thou- sand tons of ore per day in 1971. At the same time, the productivity of Kiruna was 12 thousand tons of ore per man-year, Climax 42.8 tons (48.3 short tons) per man-shift and San Manuel 29.01 tons (32.1 short tons) per man-shift. The main feature of this group of mining methods is the underground extraction of ore from beneath overlying caveable waste rock. Since the loss and dilution of ore are inherent (sometimes to a great extent), the control of ore-draw in these methods as com- pared with other methods is very important. Consequently, concerned Universities and Research Institutes have devoted great amounts of research on ore-draw theory and control management which has provided positive results to mine production, and has apparently promoted the development of the caving methods. During 1979 in China, metalliferous underground mines accounted for 15.22% of the total iron ore produced, while also accounting for 56% of total non-ferrous production. According to the mining methods, sub level caving in the principal underground iron mines counted for about 56.74% of total principal underground iron mine production, but only about 1% of total non-ferrous underground mine production. Relative to forced block caving and sublevel caving with sill pillar, the Chinese non-ferrous under- ground mines estimated about 35% of total non-ferrous underground mine production from these two methods, mainly from the latter. From the trend of development of underground metalliferous mines in China, the percentage of production in caving will be increased in the future, especially in block caving and forced block caving which have already been given great attention in the mining circle. In these types of mining methods the ore is drawn from the stope under a large area of overlying waste rock, which complicates the basic regulation and control of ore-draw, but provides lower loss and dilution than sublevel caving. Because of these reasons, the Kiruna Iron Mine in Sweden is intending to change its sublevel caving by testing a sublevel shrinkage caving method and considering a large area of ore-draw beneath the stope as an advantage. Therefore, the basic regulation and control management of ore-draw under a large area, as practiced in China, will be discussed in this paper. BASIC REGULATION OF ORE- DRAW FROM CAVING STOPE The aim of studying ore-draw under a large area of overlying waste rock is to se- cure a planned draw schedule that guarantees a certain plane of interface between ore and waste rock, and controls the change of its shape in spatial position for reducing ore loss and dilution during the draw process. Presently, the ellipsoid theory is comparatively near the actual attitude of ore-draw from the cave. 1. Ore Drawn Out from Single Drawpoint Laboratory testing and practical experience all show that after a certain amount of ore has been drawn out from a drawpoint, its original shape in the stope before drawing is more or less similar to an ellipsoid, hence the name "draw ellipsoid." This draw ellipsoid is cut at the bottom by a horizontal plane corresponding to the raise of the drawpoint, and its volume can be calculated by the following formula:

Jan 1, 1981