Search Documents

By Robert F. Winkle

A detailed breakdown of mining costs, available to management on monthly and year-to-date bases, is mandatory for a controlled and efficient mining operation. A simple lump sum reporting of costs may indicate a profit or loss differential, but it does not allow an effective search for areas of possible cost reduction. Moreover, functional reporting is necessary on a timely basis so as to note trends of increasing costs In specific areas, which in turn allow possible preventive action by management. Definitive cost information helps to eliminate the tendency to overlook areas where cost Improvements can be made. A good cost control system points out salient operational weaknesses by: ( 1 ) allowing comparison of functional costs with similar costs of other mines and (2) pinpointing sudden increases over unit empirical costs within the organization. In general, the cost accounting structure is relatively uniform within large open pit mines, but surprisingly some systems will overlook the need for detailed breakout in comparatively high cost areas. In some other systems, unrelated costs will be lumped together, preventing careful analysis of cost accrual.

Jan 1, 1979

By Joseph Kuti

ROOF SUPPORT DEVELOPMENTS IN LONGWALL (1) European longwall mining technology developed towards its modern form in relatively deep mines. With increasing depth the stability of openings driven for ventilation, travel or transport becomes paramount in mine design considerations. As a result the number of roadways and entries, as well as their width must be a minimum. (1) Another important aspect of European mining is the high density of mineable seams, as opposed to the wide lateral extension of a single seam in the U. S. A. Multi-seam mining requires strict planning and near 100% extraction, since with increasing depth, the effect of remnant pillars can be devastating. As a result the face layout of a modern European longwall panel is based on single panel entries of moderate width and great height. The mode of extraction is generally a mixture of the advance and retreat system which is called a 2-system. It is obvious, therefore, that the supports developed for the entries and for the intersection areas are more complex than those in the U. S. A.

Jan 1, 1981

By John C. McDonald

CONTROLLED cold work is used between solution heat treatment and precipitation heat treatment for producing certain tempers of the commercial aluminum base alloy 2219 (designation of the Aluminum Association, U.S.A.) which contains 6.3 pet Cu as the major ingredient responsible for the age hardening. The complete composition limits for this alloy are listed in Table I. The alloy has been described in detail,' and the control of the heat treatment has also been published.2 Beneficial effects of such cold work in other alloys have also been pointed out.3'4 NO data have been published on the effects of varying amounts of cold work under fixed aging conditions. In connection with an investigation of the possibility of providing the desired cold work by explosively generated shock waves, it became desirable to investigate the effect of variable cold work, and to compare the re -sults with those obtained from explosives. The general principles of explosive hardening are well-described in the literature.' All material used was guaranteed by the supplier

Jan 1, 1968

By Harry C. Swanson

TRANSPORTING concrete from mixer to forms has always been a problem. Twenty-five years ago this task was generally accomplished by means of wheelbarrow or concrete buggy. On large dam jobs, as the number of these projects increased, the gantry crane or highline came into use. Today several methods of handling concrete are employed on smaller surface construction jobs, for example, transit-mix trucks or dumpcrete trucks, which have crawler cranes with buckets for placing concrete into forms. In 1944, during early stages of developing Mather mine A shaft, several large underground concrete jobs were necessary. At this time the Cleveland-Cliffs Iron Co. purchased the first pumpcrete machine, introduced by the Chain Belt Co. of Milwaukee. The machine was used to pour approximately 200 cu yd of concrete for a dam, or bulkhead, located 400 ft from the shaft. Concrete was mixed on surface, lowered down the shaft 1000 ft in a 2-cu yd bucket hung under one skip, spouted into the bowl of the pumpcrete machine from the bucket, and pumped directly into the forms.

Jan 4, 1954

By A. Arrott, G. S. Ansell

A model is proposed to account for the observed strengthening behazlior of ferrous martensites. me model is based upon the inheritance of carbon-rich regions by the martensite which were present in the FERROUS martensite is formed by a nucleation and shear mechanism when austenite is cooled, at a rate which is fast enough to suppress the formation of pearlite, below a critical temperature (Ms ). Although the mechanism of the transformation process appears to be well understood,1,2 the mechanism re- austenite prior to transformation. These carbon-rich regions strengthen the martensite in a manner analogous to the strengthening effect due to a finely dispersed second phase. sponsible for the observed high strengths exhibited by ferrous martensites is uncertain. In this paper, a model is proposed to account for the strengthening of ferrous martensite. MODEL The maximum solubility of carbon in austenite is 1.98 wt pct as compared with a maximum solubility of 0.025 wt pct in ferrite. Prior to transformation, the carbon in the austenite is nonuniformly dis-

Jan 1, 1963

By W. H. W. Husband

Rock salt has been solution mined for many years in many countries. Attempts have been made in the past in Canada and various other countries to produce potash by the same method. However, only Kalium Chemicals Ltd. has been successful, possibly because the conditions in Saskatchewan are the most favorable to be found so far for the development of a solution-mining method for potash. In view of the fact that few studies of solution mining of potash have been attempted, only one company has succeeded in using the method, and no information has been released by this company, the application of solution mining of potash ore bodies has to be presented on the basis of available theory, past small-scale studies, and recent patents. A simple mining method is outlined and possible methods of recovering the potash from the brine are discussed. Dissolution data pertaining to solution mining of potash, flowsheets, and material balances are presented. The available information is brought together in a cost analysis to show capital and product costs in terms of 1966 dollars.

Jan 1, 1972

By S. L. Payne, J. P. Morris, R. L. Kipp, G. R. Zellars

The activities of iron and nickel in liquid Fe-Ni alloys were determined by measuring the vapor pressures of iron and nickel above the alloys and comparing with the vapor pressures of the pure metals. Nickel was found to deviate negatively from Raoult's law over the entire composition range. Iron behaves ideally down to 0.7 mole fraction but shows negative deviations at lower concentrations. At 1600°C the activity coefficients at infinite dilution are 0.40 for iron and 0.66 for nickel. 1 HE formulation of the conditions of chemical equilibrium between liquid metals and gases or slags is an important application of thermodynamics to pro- cess metallurgy. Usually the metal and slag phases are solutions of several components; and for accurate calculations, it is often necessary to use the activities of the components in place of their concentrations. Data concerning activities, however, are quite meager. The evaluation of the activities of iron and nickel, presented in this paper, is part of a project to determine activities in iron alloys at elevated temperatures.

Jan 1, 1960

By Chauncey Berrien

THE Hawkesworth detachable drill steel shank and bit were invented by A. L. Hawkesworth; while he was a mechanical foreman for the Anaconda Copper Mining Co., at Butte, Mont. Mr. Hawkesworth died on June 16, 1925, at the time that his invention was practically a proved success. The first application for patents was made by him in November, 1918, and the bit is now being manufactured under patents issued in 1922 and 1923. The credit, for its development in the early stages belongs to A. L. Hawkesworth, Roy S. Alley, Harry A. Gallwey, E. J. Bowman and various officials of the Anaconda Copper Mining Co. Later improvements, manufacturing problems and the direct usage in the mines were originated and perfected by the mechanical department under C. D. Woodward, E. R. Borcherdt, head of the Rock Drill Equipment Department, Robert E. Kelly of the Mechanical Department, and various operating department heads of the Anaconda Copper Mining Co. The author wishes to acknowledge the assistance of these officials in the preparation of this paper.

Jan 1, 1930

By H. L. Barr

THE following report covers the history of the development of the mine, present equipment, methods and costs of mining and milling. In addition, a description of the ore deposit is given with emphasis on the origin of the fractures, mode and types of ore occurrence, and mechanics of granite emplacement. An endeavor has been made to present a complete and accurate statement of the San Mauricio mine, the highest grade gold mine in the Philippine Islands. Credit is gratefully acknowledged to the mine staff for descriptions and details regarding their particular field of work. All analyses were made by Mr. T. A. DeVore, head chemist, San Mauricio Mining Co. Messrs. Edward Wisser, J. E. Fyfe, A. F. Skerl and W. B. Meek, geol-ogists, have contributed geologic information and ideas, for which thanks are extended. The Executive Committee of Marsman and Co., Inc., Managers of the Company, has kindly given permission for publication. Mr. J. B. Stapler, Division Manager, Marsman and Co., has had the courtesy to read the manuscript and to give critical and helpful suggestions.

Jan 1, 1940

By H. L. Barr

THE following report covers the history of the development of the mine, present equipment, methods and costs of mining and milling. In addition, a description of the ore deposit is given with emphasis on the origin of the fractures, mode and types of ore occurrence, and mechanics of granite emplacement. An endeavor has been made to present a complete and accurate statement of the San Mauricio mine, the highest grade gold mine in the Philippine Islands. Credit is gratefully acknowledged to the mine staff for descriptions and details regarding their particular field of work. All analyses were made by Mr. T. A. DeVore, head chemist, San Mauricio Mining Co. Messrs. Edward Wisser, J. E. Fyfe, A. F. Skerl and W. B. Meek, geol-ogists, have contributed geologic information and ideas, for which thanks are extended. The Executive Committee of Marsman and Co., Inc., Managers of the Company, has kindly given permission for publication. Mr. J. B. Stapler, Division Manager, Marsman and Co., has had the courtesy to read the manuscript and to give critical and helpful suggestions.

Jan 1, 1940

By Ernst A. Hauser

A few years ago an Indian native of British Columbia drew the attention of white men,' to a deposit of a claylike material on King Island, at the mouth of Dean River just opposite Hunter Island in the Pacific Ocean (Fig 1 ) . The native claimed that this natural product, which is found not in solid form but either as a paste or as a thick, viscous liquid, exhibited exceptional healing properties not only for various types of skin irritation but also for internal ailments. He pointed out that the natives had been using this material very successfully for generations. Since then, systematic surveys have revealed that the deposit, covered by a humus layer of varying thickness, is far more extensive than had originally been assumed. The product as mined today is of puttylike consistency and of greenish color. If exposed to air it dries rapidly, forming a slightly gray, rather brittle product, which does not permit redispersion to its original consistency. When the natural product is rubbed on the skin, however, the presence of coarse, sandy material is revealed.

Jan 1, 1952

By Joseph E. Worthington

The present-day Northumberland gold mine is one of the deposits generally characterized as a Carlin-type occurrence. It lies at the crest of the Toquima Range in Nye County near the center of Nevada. Gold mineralization occurs in two modes, in argillaceous and in silicified limestones, and is generally very fine-grained or micron gold. The Northumberland district has had a history that is typical of many western gold districts: minor production prior to World War II and intermittent exploration thereafter until a combination of geological insight, improved economics, and the advent of heap leach technology created the Northumberland gold mine. Nye County, Nevada, was sparsely populated and little explored in the early years of the settlement of the west; the Northumberland district was not established until 1866. Initial interest was in silver and the district operated as a very small producer for the next seventy years. The disseminated gold occurrences in silicified limestones were recognized and Northumberland Mining Co. was organized to develop the property in the late 1930s. Northumberland Mining Co. actually conducted drilling operations (over 200 drill holes) and mined from small open pits in the silicified limestones. They ultimately produced almost 936 kg (33,000 oz) gold before being shut down by War Production Board Order L-208 in 1942. After World War II gold mining activities were essentially nil for over a decade due to the poor economics of gold production. The property was, however, a known gold producer and attracted recurrent exploration attention. About 45 holes were drilled under the direction of Peter Joralemon for private interests between 1959 and 1963. Next Kerr McGee drilled about 25 holes during 1963 and 1964. Some- what later, in 1968, Homestake drilled 20 holes. The property was then acquired by Idaho Mining Co. which drilled about 30 more holes between 1972 and 1974. By this time the Northumberland mine was becoming somewhat shopworn with over 300 holes drilled. Interest in gold prospects was increasing substantially in Nevada, how- ever, due to rising gold prices in late 1974, and several companies were interested in continuing exploration at Northumberland. In 1975 Cyprus Mines Corp. was successful in obtaining a joint venture arrangement with Idaho Mining Co. for further exploration and development of the property. The overall Cyprus exploration program was under the direction of James G. Hansen, Vice President Exploration. The geologist recommending acquisition of Northumberland was Peter E. Chapman who reported to Joseph E. Worthington, Manager of U.S. Exploration for Cyprus. The basis for selection of the Northumberland mine as an exploration target for Cyprus by Chapman was essentially prior knowledge of regional and 16cal geology and of the mine. Exploration for the next few years was directed by Chapman under the supervision of Worthington. During 1975 and 1976 rotary and check core drilling were conducted that indicated that a substantial Carlin-type or disseminated, low-grade gold deposit occurred in two separate bodies. Drilling was based on geologic mapping and rock chip geochemical sampling. Both ore zones were reflected at the surface as gold and arsenic anomalies in rock chips. Heap leach tests attempted in 1977 were aborted by a flash flood, but were completed in 1978. Engineering studies occupied the next couple of years until the property achieved production in the fall of 1981. It is now producing by open-pit mining with gold recovery by heap leaching and cyanide extraction at a rated capacity of approximately 2722 t/d (3000 stpd) ore. Metal recovery has been projected (probably conservatively) at 5 10 kg/a (18,000 oz per year) gold and 1.6 Mg/a (59,000 oz per year) silver. Reserves are reported to be adequate for ten to fifteen years of production. REFERENCES Anon., 1981, "Gold in Nevada," Span Magazine, Vol. 21, No. 3, Standard Oil Co., pp. 6-9. Koschman, A.H. and Bergendahl, M.H., 1968, "Principal Gold- producing Districts of the United States, Professional Paper 610, US Geological Survey, p. 193. Kral, V.E., 195 1, "Minerals Resources of Nye County, Nevada, Bulletin, Vol. 45, No. 3, Geology and Mining Series 50, Nevada University.

Jan 1, 1985

By L. Stone, H. Margolin

The Ti-C-N and Ti-C-O systems were investigated in the temperature range from 500° to 1400°C and in the composition range up to 2 pct C and 5 pct N or 0. Characteristic isothermal sections at 800°, 900°, 1000°, and 1300°C are presented. The Ti-N-0 system was studied in the temperature range from 900' to 1400°C with alloys containing up to 6 pct total alloying content. Characteristic isothermal sections at 1000° and 140O°C are presented. Melting-point data for all three systems are also included. THIS paper reports on one of a series of investi-gations which have been conducted on the phase diagrams resulting from interstitial alloying with iodide titanium. The other investigations involved delineation of the binary systems with carbon,' nitrogen and boron,h and oxygen. The Ti-0 binary system has also been investigated by Bumps et al.' In varying degrees, each of these interstitial elements has been shown to stabilize the low temperature a modification of titanium1-5 and each forms a face-centered cubic TiX compound (henceforth designated 6). In addition, the Ti-N and Ti-0 systems reveal a low temperature tetragonal phase (6) formed by a peritectoid reaction between a and TiX Experimental Procedure The development of experimental techniques for the study of titanium alloy systems has, to a large extent, become standardized. In this investigation, the equipment and procedures described in detail by Cadoff and Nielsenl have been used. Arc Melting: In general, binary alloys with carbon, nitrogen, and oxygen, prepared in the composition range of interest in this investigation, show negligible composition changes during arc melting. However, the possibility of the formation of some gaseous combination of alloying elements such as CO, CN, or NO during the preparation of these ternary alloys was considered. Calculations showed that the evolution of only 0.05 gram of such a gas would be detectable as a pressure change in the closed system used during preparation of these alloys. Such pressure changes were not observed. Consequently, nominal compositions have been used in plotting the data. The compositions of the materials used in the preparation of the alloys are shown in Table I. After melting for 3 to 5 min at 275 to 350 amp, the alloys were checked for homogeneity by microstruc-tural examination. Alloys containing up to 1 pct C were homogeneous in the presence of less than 3 pct N or 0. At higher alloying contents, some inhomo-geneities in the carbon distribution became evident. Alteration of the melting procedure toward longer times and higher currents did not improve the homogeneity of these alloys. Ti-N-0 alloys were homogeneous in the range to about 3 or 4 pct total alloying addition. Beyond this, almost all of the specimens showed as-cast microstructures consisting only of the phase. Consequently, inhomogene-ities could not be detected by examination of micro-structures. Ten alloys from each of the systems were analyzed for two of the elements present (oxygen being omitted in all cases and titanium being omitted in the Ti-C-N alloys). In all cases the analyses were found not to be sufficiently precise to serve as criteria for the total composition of these alloys. On the basis of phase distribution in heat-treated alloys, however, it appears that carbon is distributed throughout the alloys most uniformly, with oxygen and nitrogen following in that order. Heat Treatment: Specimens for heat treatment were wrapped in titanium sheet before sealing in the argon-filled quartz capsules. Heat-treatment times varied from 100 hr at 800°C to 0.5 hr at 1400 °C. After heat treatment the specimens were quenched by breaking the capsule in water. With the exception of alloys in the low composition region, heat treatment did not have an appreciable effect on the as-cast microstructures. Metallography: Following heat treatment, the specimens were prepared for metallographic examination by grinding on emery paper and electrolytic polishing. For the majority of the specimens a 10-sec etch with Remington "A" agent (25 pct HNO3, 25 pct Hf, and 50 pct glycerin) adequately

Jan 1, 1954

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By A. T. Corey, C. H. Rathjens

INTRODUCTION Although the oil industry has been aware of the directional variability of permeability in porous rock, the directional variability of relative permeability has been largely ignored. Yet it is apparent that such an effect must be present in a system in which the distribution of oil and gas within the porous matrix is controlled by capillary forces. It is easy to visualize a rock composed of layers of fine and coarse material such that gas flow across the bedding planes would take place only after the average oil saturation had been reduced to a very low value. The fine layers, because of their greater capillarity, would remain saturated and act as barriers to the flow of gas after the coarse layers had been desaturated. Flow of gas parallel to the bedding planes would obviously take place at a much greater liquid saturation. Without more complete information concerning the geology of a reservoir than is generally available, it is not possible to predict exactly how such phenomena would affect the over-all performance of an oil field. It is possible, however, to predict qualitatively the effect of stratification on relative permeability measurements made on laboratory cores. In this investigation the effect of stratification was studied analytically by assuming that two porous materials with different capillary pressure-desaturation curves (but identical relative permeability curves) were in contact and in capillary equilibrium. As a qualitative check on the analytical results, cores having various degrees of visible stratification were used for relative permeability measurements made with fluids flowing both parallel and perpendicular to the bedding planes. A quantitative check was considered impractical because of the difficulty of devising models in which two materials of predetermined properties could be joined without the plane of contact becoming a discontinuity. THEORETICAL CONSIDERATIONS AND ASSUMPTIONS The assumption of capillary equilibrium in an oil-gas system implies that the difference in pressure between oil and gas is everywhere the same. This means that the curvature of the interfaces must be everywhere the same in order to satisfy the equation where PC is the pressure difference between phases, y the interfacial tension and r, and r2 are the major and minor radii of curvature. Depending on the pore size distribution of coarse and fine layers, the volumetric percentages of oil and gas in these layers will differ when equilibrium exists. The exact relationship can only be determined by obtaining the complete capillary pressure-desaturation curves for each of the porous materials in contact. It has been pointed out elsewhere' that the capillary pressure-desaturation curves of sedimentary porous materials can often be approximated by the relation where C is a constant and Soe is the effective saturation to oil based on a percentage of the pore volume effective to flow. In the same paper it was indicated that, as a first approximation, the values of oil relative permeability are given by and the values of gas relative permeability by For this analysis Eqs. 2, 3, and 4 were assumed to apply to each of two components of a hypothetical porous rock in capillary equilibrium. It was also assumed that each of the components had a residual wetting phase saturation of 20 per cent so that 80 per cent of the total pore volume was effective to flow. The permeability of the coarse stratum was taken as 100, and its displacement pressure was such that C in Eq. 2 had the numerical value of 1. The corresponding values for the fine stratum were 10 for the permeability and 10 for C. Units are not specified because they do not enter into the final results. The choice of the permeabilities and displacement pressure ratios was made to expedite the calculations. Any reasonable rock properties could have been chosen without changing the results qualitatively. Several arrangements of the two components were studied. Table 1 summarizes the resultant permeabilities obtained for four types of arrangement. RELATIVE PERMEABILITY CALCULATIONS The first step in the computation of relative permeability for the composite cores was the plotting of the capillary pressure-desaturation curves and the relative permeability curves for the individual components according to Eqs. 2, 3, and 4. At arbitrary

Jan 1, 1957

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By H. Sigurdson, T. V. Cherian, C. H. Moore

The phenomenon of recovery of cold-worked metals is interesting not only because of its practical importance but also because of its fundamental significance in solid state reactions. Although extensive investigations1,2 have already been made in an attempt to discover the mechanics of the recovery process, many of the observations have not yet been satisfactorily correlated to provide a completely consistent model for the process. The wide differences in the recovery rates of various properties can be cited as a typical example of one of the difficulties that are encountered. Frequently, for example, the electrical resistance will have almost completely recovered before any recovery in tensile strength can be detected. Of course, such differences in the recovery rates of different properties might be explained by assuming that each property is a unique function of the work-hardened state, and consequently each property exhibits its own unique recovery rate. The assumption that different properties are uniquely related to the work-hardened state cannot be denied. On the other hand, the properties that recover at different rates often exhibit more or less parallel changes upon work-hardening. This suggests that the microstructural changes attending recovery are not exactly the reverse of the changes attending work-hardening. Several types of imperfections must be postulated in order to account for this apparent anomaly. The different recovery rates for various properties, then, are due to the different recovery rales of the type of imperfection to which each property is most sensitive as well as the unique dependence of each property on the cold- worked state. This concept assumes that a simple model of the work-hardened state consisting only of one type of imperfection, such as Taylor's type of dislocation patterns, is inadequate to cope with the diversified phenomena attending work-hardening and recovery. Although current models for the work-hardened state are not useful for describing all aspects of the recovery process, the general trends of the recovery of each postulated type of imperfection as a function of time and temperature should be at least qualitatively deducible from the rather well developed laws of kinetics of reactions in the solid state. Consequently, recovery data might prove useful for elucidating some aspects of the complexities of the work-hardened state of metals. A preliminary attempt to study work-hardening by investigating recovery rates of cold-worked metals is outlined in the following pages of this report. Experimental Procedure Many properties recover when cold-worked metals are annealed below their recrystallization temperature. Therefore, electrical resistivity, thermal electromotive force, X ray diffraction line widths, X ray diffraction line intensities, elastic spring back, density and other physical and chemical properties have been used to study the recovery process. Major interest, however, has generally been directed toward the recovery of the mechanical properties such as hardness, yield strength, and tensile strength. But a search of the literature suggests that the effect of recovery on the true stress-true strain curve has been neglected, in spite of the current recognition of the fundamental importance of such an investigation. An investigation on the effect of recovery treatment on the true stress-true strain curves in tension, therefore, was undertaken in the present study. Commercially pure aluminum (99. + pet Al) in the form of 0.100 in. thick rolled sheet of 2S-O aluminum alloy was selected as the material for this investigation because rather extensive correlatable data are already available on the recovery of some of its properties. Tensile specimens having a 6 in. long gauge section and a uniform reduced section width of 0.500 in. were machined from the sheet in accordance with a design that has previously been reported.3 All specimens were selected with their axes aligned in the rolling direction. In order to eliminate the effects of previous work-hardening and the effects of machining, the specimens were annealed for 15 min. at 750°F before testing. During tensile testing the loads were measured by means of a proving ring (sensitive to 1/2 lb) in series with the specimen.4 Strains were determined from the extension of a rack and pinion strain gauge sensitive to a strain of + 0.0001. The stress was recorded as the true stress, namely

Jan 1, 1950

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950