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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 Thomas Chance

ALL gravity methods for the separation of ore from gangue, or of slate and other refuse from coal, are based upon differences in the falling velocities, in some fluid medium such as air or water, of the materials to be separated. As all materials falling in a vacuum have the same velocity, independent of the size, shape, weight or specific gravity of their individual particles, it would be more accurate to describe the operation of these methods as depending upon the. retardation of falling velocities effected by the resistance of a fluid medium, this retardation being greater for small or light particles than for large or heavy particles. This generalization is true also of those appliances utilizing centrifugal force to replace or to supplement the action of gravity. The separation of materials of different specific gravities by means of a fluid having a specific gravity greater than that of the lighter particles and less than that of the heavier particles has not been applied commercially, or on a large scale, to the separation of ores or to the washing of coal, the method being limited to laboratory experimental work or to laboratory determinations for the purpose of checking up the work of jigs, classifiers, and other types of concentrating appliances. A solution of zinc chloride has thus come into general use inn the laboratory to separate coal, bony coal and slate, both to check up the work of coal-washing plants and for the purpose of making tests preliminary to the designing of coal-washing plants. The use of a heavy solution of some chemical in water has often been proposed for making such separations, especially in connection with the washing or preparation of coal. Practically insuperable difficulties, however, have prevented the commercial development of any such process, the difficulties being both physical and financial. The cost of the chemical used to make high-gravity solutions is usually prohibitive, and the freeing of the coal from all traces of the chemical is found to be practically impossible. Such solutions inevitably penetrate the individual lumps and particles of coal, transfusing into the pores and saturating the joint-planes, and very large quantities of wash water

Jan 2, 1918

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

By Edward Saibel

THE various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure, no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3,4 or on the energy required to form new surface.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agreement between calculation and experiment. It has been pointed out by several observers7 that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so - nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory Of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermo- dynamic theory of the tensile strength of isotropic bodies based on work of Born9 relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melt- ing phenomenon, Fürth obtains an expression for the rupture stress u, in the form [ ] where Q is the melting energy per unit mass, ? is the density, and µ is Poissons’ ratio. Fürth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Stephen G. Dardaganian

Pore volume compresibilitieu measured in the laborutory on core .samples are reported for typical reservoir .sarrrl.rtorres at reservoir pressure. These cornpressibilities ore different for each reseriloir sample and cannot be correlated to porosity. The compressihilities are a1so functions of presslire. In recent years several authors have pointed out the importance of including pore volume compressibility of the reservoir rock in certain reservoir engineering calculations. Hall' showed that in calculating the hydrocarbon volume of an undersaturated reservoir from the production per unit change in reservoir pressure, the neglect of rock compressibility could, in the extreme case of low porosity rock, lead to results in error by a factor of two. Hawkinsl' and Hobson and Mrosovsky showed that both rock and interstitial water compressibilities must be included to achieve satisfactory accuracy in this calculation. Although rock compressibility is an important reservoir property in these calculations, very few data are available. Hall' made compressibility measurements on a few samples in a small pressure range. No other direct pore volume compressibility measurements have been reported. Geertsma' discussed the elasticity of reservoir rock but did not present any new data. In this paper, rock compressibilities suitable for reservoir calculations are reported for a variety of sandstones typical of U. S. reservoirs. The measurements were made through a range of pressures which is also typical of reservoirs. EXPERIMENTAL PROCEDURE Plugs 1 in. in diameter and 2- to 3-in. long were diamond drilled, 14 from cores from seven oil-bearing or potentially oil-bearing sandstone, one from a quarried sandstone, and another from a shallow, oil-free, pure orthoquartzite. The plugs were extracted in toluene, vacuum dried, and then weighed. The plugs were then saturated with kerosene and reweighed. This gave pore volume. They were then again extracted in toluene. vacuum dried, and jacketed in 0.004-in. thick copper foil. A short length of -in high pressure tubing led from the jacket. The jacketed sample was then saturated with kerosene and placed in the hydraulic pressure cell as shown in Fig. 1. Movement of the mercury slug showed the change in pore volume of the sample under a given pressure change. Temperature was about 72" F for all measurements. Before taking any measurements, the external pressure on the sample was raised to 10,000 psig and kept there for several hours. This formed the thin copper jacket around the plug. 7-he pressure was then removed and the sample left at least overnight, during which time it recovered its original pore volume. An external pressure of 12,000 psig was then applied and held constant. The change in pore volume was noted as the internal pressure was raised in 1,000 psig increments to 10,000 psig. The internal pressure was then reduced to zero, again noting pore volume changes,

By Harry L. McNeill

THE Selective Media Process was developed by the author in a laboratory provided by The Steårns-Roger Manufacturing Co. It is the outcome of an [ ] investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Cliffs Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7 ½ -hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼ -hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7 ½ -hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). When treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is fed to the washing plant the coarse

Jan 1, 1946

By S. W. Parr, T. E. Layng

The low-temperature carbonization of coal involves the carrying out of the coking process under conditions wherein neither the coal mass nor any of the passageways through which the volatile products pass are heated above 700" or 800" C. For convenience in this discussion, the single number 750" will be used to designate the maximum range. This temperature is not selected arbitrarily; it is the result of certain natural conditions that are inherent in the substances involved. Two of these conditions arc sufficiently pronounced to suggest a line of demarcation at this point as follows: (1) Below 750°, all the heavy hydrocarbons are expelled, which means that, at these lower temperatures, the illuminants, the gases of high calorific value, and the condensible oils are discharged; above 750") there are given off the lean, non-illuminating gases consisting for the most part of hydrogen and marsh gas and having no condensible constituents present. (2) Below 750") there is substantially no secondary decomposition; above 750") the volatile products are readily decomposed, forming tars, naphthalene, free carbon, etc. It is not intended to maintain that no secondary decompositions occur below 750". Many recent studies have demonstrated the practicability, especially in the presence of catalytic substances, of cracking certain of the hydrocarbon compounds; but at these lower temperatures the step is a moderate one, as, for- example, from xylene to toluene or from toluene to an anthracene. These changes are moderate in amount. Not only do the reactions proceed slowly but they are subjected to the decomposing . conditions for only a short time. This is evident when it is recalled that at these initial temperatures the decomposition of the coal is very rapid and, if anywhere near a neutral pressure is maintained, the movement of the evolved gases is lively and reduces, correspondingly, the time for the retention of the gases in the passageways where these milder decomposing conditions exist. It is acknowledged that the maintenance of these temperature conditions at the present time has only an ideal and not a practical status. Actual operations under these conditions, as a? industrial accomplish-

Jan 1, 1920

By T. D. Murphy

This chapter deals with those types of silica raw materials that have been segregated and refined by natural processes into nearly monomineralic deposits and hence, by virtue of their high degree of purity, have become the sources of commodities having special and somewhat restricted commercial uses. In some instances, these raw materials occur in nature as unconsolidated quartzose sand or gravel and can be exploited and used with very little preparation and expense. More often, they occur as sandstone, conglomerate, quartzite, quartz mica schist, or massive igneous quartz which must be crushed, washed, screened, and sometimes chemically treated before commodities of suitable compositional and textural characteristics can be successfully prepared. The occurrence and distribution of silica raw materials is summarized and an effort has been made to bring commodity definitions, critical properties, and specifications up to date. Presentation of mining and processing methods is considered beyond the scope of this article; they are, for the most part, conventional and well known. New production techniques are currently reported in the trade journals and are later adequately described in technical publications as promptly as competitive restrictions allow. Discussion on Basis of Use ABRASIVE USES Industrial silica used for abrasive purposes falls into three main categories: (a) blasting sand; (b) glass-grinding sand; and (c) stone-sawing and rubbing sand. Blasting sand is a sound closely-sized quartz sand which, when propelled at high velocity by air, water, or controlled centrifugal force, is effective for such uses as cleaning metal castings, removing paint and rust, or renovating stone veneer. It is commonly referred to as Sand Blast sand. Multicycle quartz sand is an efficient blasting agent by merit of its survival characteristics which are soundness, toughness, and hardness. Steel grit and shot have supplanted it to a large extent but owing to their higher cost and tendency toward deterioration in storage, are still not universally used. It is conceded that angularity promotes faster cutting but this is offset by a higher loss in fines. The peening action of a rounded grain is a desirable feature in achieving a satin finish for certain light metal castings but a subangular grain is unsurpassed for fast heavy cutting. Specifications are chiefly based on size frequency distribution but it is mandatory that the grain be free of adhering clay or irony coatings. Material that dusts upon handling will not be tolerated. There is no uniform trade designation for the many blasting sand grades. Most producers sell on the basis of numbered grades; that is, No. 1, No. 2 and so on, this generally connoting fine to coarser grades. Designation of grade by the two sieve sizes between which most of the material lies, is practiced in some areas. Thus, in a No. 1220 grade, 98 pct of the material passes a 12 mesh sieve and is retained on a 20 mesh sieve. Blasting sand specifications vary according to use. Coarse grades range from 4 mesh to 12 mesh, medium grades range from 12 mesh to 30 mesh, finer grades may range from 20 mesh to 100 mesh or finer. Specifications generally call for narrow limits of gradation, requiring precise sizing methods. The fact that most blasting sands are retained

Jan 1, 1960

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

H. Schwartzbart and W. F. Brown, Jr.—The authors have divided the effects of recovery on the true stress-true strain curve into two types; metarecovery, which effects only the first part of the curve or the yield strength, and orthorecovery, which effects the flow stress at any strain. Both of these are said to be true recovery effects, involve no recrystallization, and are explained by the removal of two different types of imperfections caused by work hardening. However, there seems to be some question as to whether the data are sufficiently conclusive to exclude, as an explanation of the authors' results, a mechanism based on the relief of residual stresses between the grains or slip bands and recrystallization. It appears that metarecovery could be interpreted in the same fashion as a customary interpretation of the Bausch-inger effect. The balanced system of internal stresses which exists between grains in a strained specimen due to varying orientation and, hence, yield strengths, of the different grains is responsible for a reduced yield strength in compression following pre-tension, and, similarly, for an elevated yield strength in tension following pre-tension. If the specimen is now heated so that the internal stresses are relieved by creep, then the yield strength in tension following tension will have been reduced and in compression following tension will have been raised. There seems to be a very strong case for the lack of recrystallization in the aluminum investigated by the authors, if one defines recrystallization as the presence of visually detectable new grains or accepts the X-ray evidence as conclusive. One must remember, however, that the appearance of spots on the back-reflection X-ray patterns cannot be taken as the time when recrystallization first started. The areas of recrystallized strain-free material must first have grown to a size large enough to give distinct spots on the patterns and this may take some time. Averbachl7 in an investigation of brass has shown that recrystallization can be detected by extinction measurements at temperatures lower than those based on hardness or X-ray line width determinations. It can be seen from fig. 10 that the rate of recrystallization is extremely low over a considerable time period at the onset of the process. Observations on the rate at which small amounts of recrystallization effect the flow stress would have given further insight as to whether undetectably small amounts of recrystallization might have been responsible for orthorecovery. Also, the question arises as to whether the effects observed in fig. 6 for various times and temperatures could not have been obtained if the time at 212°F were sufficiently long. In addition, the argument that the curve in fig. 10 is not sigmoidal seems weak in view of the scattering of the points. It is conceivable that an accurate determination of the curve for the first 100 hr would exhibit a relationship other than the one drawn. There is one point we would like to raise about the condition of the starting material. The authors annealed their material at 750°F for 15 min to remove the effects of any previous work hardening or machining strains. Reference to the work by Anderson and Mehl shows that this treatment may not have completely recrystallized the aluminum, so that the starting material may have had some strained areas. Higher temperatures or longer times may have been required to remove the effects of any small strains. We would like to mention some results of tests being conducted at the Lewis laboratory of the National Advisory Committee for Aeronautics in an investigation of the Bauschinger effect in relation to fatigue. Tests were performed on annealed electrolytic copper and several annealed brasses. Specimens were pre-strained 1 pct in tension and then tested in compression or tension with and without intermediate stress-relieving annealing treatments at 500°F for various times. Specimens heated at 500°F for 10 1/2 hr showed an elevation of the flow curve in compression and an approximately equal lowering of the flow curve in tension when compared with the curves for the un-heat treated specimens. After approximately 0.8 pct strain, all flow stresses coincided and were equal to the flow stress of the virgin material at this strain. This behavior is consistent with the metarecovery observed for aluminum by the authors and for which a residual stress model can be used. On the other hand, increas-

Jan 1, 1951

By Louis B. Slichter

Prospecting is certainly the world's biggest and best gambling business. It is a game where the chips cost many thousands and where many millions, even billions, can be won. An attractive feature of this gamble is the fact that the players are free to rig the odds as favorably as possible. Only the limited bounty of nature, the restrictions of the laws of the land, the competition from other players, the limited sagacity of the player himself- only these, and other factors, restrict the possibilities for large winnings. Today probably about half the land surface of the earth remains to be searched for signs of ore visible at the surface. It is fortunate that so much land still remains for exploration by relatively economical methods. Looking to the future, it is a good guess that the costs of finding ore will increase in response to increasing technical difficulties. To continue to achieve profits from prospecting, it will become necessary to analyze the business more skillfully, in a more and more sophisticated manner. Whenever feasible, qualitative concepts must be replaced by their quantitative equivalents, improvements, and extensions.

Jan 6, 1960

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By I. Tamura, J. O. Brittain, T. Mura

Plain carbon steel in the cold worked or marten-sitic conditions has an internal friction peak at about 250 oC at a frequency of I cps. The influence of substitutional alloying elements on this peak was examined experimentally. The alloys were vacuum melted Co-, Cr-, Mo-, Ni-, and Si-iron (about 3 pct alloying elements), and carburized Si-iron. The internal friction of the alloys in the temperature range 30o to 500 OC was determined by means of a torsion pendulum. The 250 oC peak of the cold-worked alloys was lower in height than that observed in plain C-iron and steel. Carburized Si-iron in the quenched condition had a peak which occurred at a slightly lower temperature than in quenched plain C-steel, but the height of the peak was substantially greater than that found for the same alloy in the cold-worked condition. The activation energy of this peak for martensitic Si-steel was about 35 kcal per mol. ANNEALED a iron has two internal friction peaks due to nitrogen and carbon at 20o and 40o C respectively, at a frequency of 1 cps. If a iron is cold worked, these diffusion peaks become smaller and a new peak appears at about 250o C. The activation energy for the 250o C peak is in the range of 32 to 44 kcal per mol and has an average value of 38 kcal per mo1. It has been experimentally verified that both interstitial solute atoms and dislocations are necessary for the 250o C peak. 3 Wert has also shown that an incubation period precedes the appearance of the 250 C peak.4 With regard to quenched martensitic steel, Ke et al.596 observed two peaks at around 130o and 250o C. They conjectured that the 250o C peak in martensite was due to the same mechanism as the 250°C peak in cold worked a iron, and the 130°C peak was due to the nature of tempered martensite. They did not report the activation energy for these peaks. Chernikova7 found only one peak at about 200° C in tempered martensite. In a previous paperS we reported an activation energy of approximately 40 kcal per mol for the 250° C peak in plain carbon martensitic steels. Ichiyama8 found the activation energy to be about 36 kcal per mol for the 250° C internal friction peak in steels in the martensitic condition. The present authors proposed a theory for the 250°C peak for cold worked and quenched iron and steel.= The theory for the peak is based upon the addition of a strain-energy term to the free energy for the formation of a carbide precipitate due to the presence of a disclocation. The model employed for the relaxation process consists of the growth and solution of a carbide precipitate of critical size as a consequence of an oscillating dislocation. In this report, the influence of substitutional alloy ing elements on the 250° C peak is examined and the experimental results are discussed in terms of our theory for the peak. Most of the experimental work on the alloy steels was confined to the Fe-Si-C alloys.

Jan 1, 1962

By J. Charles Miller

NATURAL carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxide. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercial production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mexico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid carbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended, The Farnham anticline is used as an example and cornputationa are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. INTRODUCTION Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1937

By L. Hartsell Cash

INTRODUCTION Created in 1944 to help rebuild those economies, principally in Europe, which were seriously damaged or destroyed during the Second World War, the World Bank--or to use its correct name, the International Bank for Reconstruction and Development-began its operational phase by making a loan to the Government of France to accomplish two tasks: (i) to import coal for space heating purposes; and (ii) to buy new machinery and equipment to help rehabilitate its coal mines. Once the thrust of reconstruction in postwar Europe was largely accomplished, the World Bank Group (for today the World Bank has three separate lending windows) turned to mobilizing funds to improve living standards in developing countries, which remains its primary goal today. Over this period of time, the World Bank Group has continued to assist the world mining industry in various ways and, since 1955 the World Bank Group has financed mining or mineral processing projects with loans/credits totalling $1.5 billion. The World Bank Group consists of two institutions--the World Bank itself and the International Finance Corporation (IFC), which was founded as a separate institution in 1956 and three separate lending windows--the World Bank, the International Development Association (IDA), and IFC. The World Bank loans are provided at commercially-related interest rates but have grace periods usually of up to 3 to 5 years and repayment periods ranging from around 15 to 20 years. Since the World Bank raises its operating funds on the international capital markets in varying currencies and in varying interest rates, it relends a basket of currencies at floating interest rates which are fixed every six months to reflect the Bank's own borrowing cost. At the present time, the interest rate is just below 10% per year and in addition, a one-time front-end fee of 1/4 of 1% is charged. Also, a commitment fee of 3/4% per year is charged on the undisbursed amount of the loan itself. For loans to industrial and mining projects, it is normal to charge an additional guarantee fee of 1 to 1.5% in addition to the annual interest rate. This guarantee fee is payable to the government of the country in which the project is carried out since, by its charter, the World Bank is required to have the guarantee of the host government for each loan made in a specific country. By far the greatest source of lending funds within the World Bank Group is that of the World Bank itself and for the fiscal year ending June 30, 1984, the World Bank approved loans totalling $12 billion. The second lending window within the World Bank Group is IDA which performs the same functions as the Bank itself and has the same staff. Nevertheless, its loans (called credits) are made on much softer terms and are made to the poorest nations only. IDA funds are subscribed by the wealthier countries, usually as grants, and these are relent as credits to those countries with the lowest per capita income. IDA credits are made for 50 year periods, including 10 years of grace, to the government itself. The credits are interest free, but there is a service charge of 3/4% per year on the amount withdrawn and outstanding to defray the administrative costs of IDA. Credits approved during fiscal 1984 totalled $3.5 billion. The third lending window is IFC. While IFC is a separate corporation and operates quite separately from the World Bank and has its own staff and regulations, it works very closely with the World Bank on its overall approach to the mining sector and to a particular country. IFC's mission is essentially to supply venture capital and to stimulate development of the local private sector in capital markets as well as to promote the international flow of private capital to developing countries. Unlike the World Bank and IDA, the IFC does not lend directly to governments

Jan 1, 1985

By J. D. Price, W. M. Bertholf

Making maximum possible use of available equipment and material, CF&I placed a high-efficiency, high-capacity washery unit in the existing buildings to gain simplified operation, reduced manpower requirements, raised efficiency, and boosted production. THE central washing plant of the Colorado Fuel & Iron Corp. was first operated in 1918 to furnish coal for two 60-oven batteries of Koppers design. Prior to that time the coke for the blast furnaces had been secured from a number of beehive operations, some with their own washeries. The original washery had four Elmore jigs, which did not do as well as had been expected. In 1923 the jigs were taken out and replaced by Deister Plat-O tables, with various changes in auxiliary equipment. In 1936 the throughput of the plant was considerably increased by the installation of vibrating filters for recovery and drying of fine coal, thereby reducing a large recirculating load of fine coal which passed through the screens of the Carpenter driers. In the late 1940's it became evident that something would have to be done to keep the washery abreast of progress at Pueblo and other washeries. Coal requirements were nearly two and one-half times the original requirements of the 120 small ovens, as additional ovens had been built in 1930, 1938, and 1945, whereas no additional coal washing capacity had been added since the 1936 modifications. Much of the equipment, moreover, had seen better days. One answer to the problem was to build a new and completely up-to-the-minute plant, with sep- arate sections for coarse, medium fine, fine, and very fine coal. On the other hand, it might be financially more profitable to place a high-efficiency, high-capacity unit in the existing buildings. The washing problem at Pueblo is not unique, but it is approached differently. There are no established specifications for coke ash and sulphur. The plant is operated on the principle that if it is more economical to wash it out than to slag it out, wash it out; otherwise, send it on to the blast furnaces. With coals at the Pueblo plant costing what they do, the benefits of washing at a low gravity are questionable. Hence the primary problem is to eliminate the high-ash components and retain all the low and medium-ash components. Sulphur is no problem at all, averaging 0.6 pct in the coke. Since a good proportion of the free impurity in the coals is as large as the coal or bone or larger, it appeared that it would be safe to go to jig washing and discontinue crushing the coal before washing, as had been the practice with the tables. This would boost the throughput. It might also decrease manpower requirements and washing costs considerably. It was assumed at the start and has been demonstrated in the first year of operation that a jig will do as well on the fines as the tables had been doing. It would not be necessary to discount any gains due to increased efficiency in washing the coarse material because of incapacity to wash the fines. By washing at —2+0 mesh it would be possible to dewater, by screening, a considerable tonnage satisfactorily, for example, at —2 + % or —2 + l/4, and then crush it in a hammer mill. The —?+20 could be dewatered in centrifugal driers and the remain-

Jan 1, 1955

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,' and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.'-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton ('Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously' in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957