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By AIME AIME

THIS year the Petroleum Division holds its fall meeting at Houston, Texas, Oct. 2 and 3, with head- quarters at the Lamar Hotel. Technical sessions will be held in the morning and afternoon of both days. A smoker on Friday afternoon will afford an opportunity to get together socially. Saturday evening is left free for private parties to the beach at Galveston, where a wide variety of entertainment is available. On Oct. 4 there will be an excursion to Sugarland oil field, with luncheon at Boling and a visit to Boling sulfur mine and plant in the afternoon. There are nine technical papers on the program for Friday. Saturday morning will be devoted to oil production control and it is planned to make the discussion more

Jan 1, 1931

By S. H. Chauvenet

THE binding of the boshes and in walls of blast furnaces has always been an expensive piece of work. When the old stone stack was replaced by the iron shell, the brickwork was kept at a thickness of five feet or more. These five-foot walls were still too thick, and the practice now is to have as thin walls as possible and to have a free circulation of air about the brickwork of the furnace. The "basket," or lattice-work binding, accomplishes this object, but it is expensive, as to first cost, and, if any change in the diameter of a furnace has to be made, it necessitates an alteration of the binding or of the thickness of the walls.

Jan 1, 1882

By Martin F. Milligan

THIS short discussion of the effects of deoxidation on the mechanical properties of cast steels is intended to serve as general introduction to the subject of this afternoon's session. The subject is covered in detail in Mr. Carter's excellent paper. My material has been collected from the works of various investigators, several of whom are present today. For a definition of deoxidation, as applied to steel-furnace melting practice, we can best go to Briggs' book, "The Metallurgy of Steel Castings." Briggs says that deoxidation "includes all the phenomena in the final preparation of steel that would permit it to solidify free from gas cavities and from dissolved oxygen of all kinds." Various practices are used by welters to produce these end results.

Jan 1, 1947

By S. H. Chauvenet

The binding of the boshes and inwalls of blast furnaces has always been an expensive piece of work. When the old stone stack was replaced by the iron shell, the brickwork was kept at a thickness of five feet or more. These five-foot walls were still too thick, and the practice now is to have as thin walls as possible and to have a free circulation of air about the brickwork of the furnace. The " basket," or lattice-work biuding, accomplishes this object, but it is expensive, m to first cost, and, if any change in the diameter of a furnace has to be made, it necessitates an alteration of the binding or of the thickness of the walls.

Jan 1, 1882

By J. F. Labuz

Fracture tests were conducted on subsize specimens of Charcoal granite to demonstrate that the extent of the nonlinear region at the crack tip can be significant. The model of the fracture process considers an effective crack length as a traction free portion plus a process zone where closing stresses act; this zone is identified by microcracking and interlocking. A singularity is allowed at the effective crack tip. The effective stress intensity factor is the superposition of the stress intensities due to the effective crack and the process zone. By assuming that the closing stress is a linear function, it is shown that a process zone length of approximately one-third the effective crack is needed to match the compliance-determined crack length.

Jan 1, 1984

By Edward Sampson

Despite the many industrial uses, the world market for silver as a commodity is far from free, being dominated by the U.S. Government both through acts of Congress and by policy of the Treasury Department. This discussion will consider aspects of supply, demand, and price with a view to the future. Changes in Sources of Supply: The world's peak production of silver, 278 million oz, was in 1937. In the 1850's world production was about 30 million oz, having risen from a yearly average of 11 million oz for the first half of the century. From 1860 to 1940 there was a steady rise, broken only by World War I and the depression of the early 1930's.

Jan 7, 1960

ARIZONA Tucson University of AriZona, Mining Engineering Society. B CALIFORNIA Berkeley University of California, Mining Asso. B University of California, Library. B & T Los Angeles Chamber of Mines and Oil. B Southern California Local Section. T Public Library. B & T Oakland Oakland Free Library. T San Francisco California State Mining Bureau. T Mechanic's Merchantile Library. B Mining and Scientific Press. B Stanford University Stanford University Geological and Mining Society. B San Diego Public Library. B COLORADO Boulder University of Colorado, Library. T Denver Bureau of Mines. B Colorado Scientific Society. B Mining American. B Denver Public Library. B & T Golden Colorado School of Mines Magazine. B Colorado School of Mines Library. T Colorado School of Mines Scientific Society. B

Jan 1, 1923

By Leon O. Hart

The nickel-chromium alloys of importance are those containing iron and those free from iron. The most important alloys containing iron, with regard to high tonnage, are the nickel-chromium steels. Straight nickel steel was introduced about the year 1889, but it was not until 1895, when it was found that the addition of chromium greatly increased the strength and resistance to shock, that nickel-chromium steels came into use. The three types of nickel-chromium steels developed at this time were: Type 1, containing 3.,50 per cent. nickel and 1.50 per cent. chromium; type 2, containing 2.00 per cent. nickel and 1.00 per cent. chromium; and type 3, containing 1.50 per cent. nickel and 0.50 per cent. chromium.

Jan 1, 1921

By L. A. Morley, W. T. Parry

Laboratory prepared clay-quartz sand samples and fault gouge from an open pit slope undergoing plane-type failure were tested in the laboratory to determine potential mining applications of electroosmotic stabilization and to provide a better understanding of electrochemical hardening. Experiments with very low current densities and free access of electrolytes to both anode and cathode showed an increase in cohesion. Cohesion in a fault gouge increased by 9.3 to 113%, depending on location with respect to the electrodes. For this, power consumption was equivalent to 0.727 watt-hr per cu ft (25.69 watt-hr per cu m). Regions of electrochemical hardening were determined by pH and the anolyte used. Electroosmotic stabilization appears as a reasonable solution to some types of mining problems.

Jan 1, 1975

Robert H. Richards, Boston, Mass.: Mr. Goodale calls attention to the difficulty of obtaining clean tailings from the jigs which are fed by the spigots of the hydraulic separator. This difficulty is universally encountered. The Lake Superior copper mills practically overcome it by running the beds of those jigs loose, carrying into the hutch all of the available copper and some sand. These hutches are again jigged upon threesieve Collom jigs, where the treatment is very slow and gentle; and on the successive jigs lighter and lighter bedding is used. The last sieve is run thin enough to let some sand into the hutch. With these precautions most of the free copper is extracted, as well as a fair proportion of the included copper.

Jan 1, 1897

By Robert H. Richards

Very little has been published recently on this subject in the mining journals or proceedings of societies. The attention of experts has been diverted perhaps by the demands for pan amalgamation of refractory ores. Yet free milling ores occur in many localities, and it may be interesting to have on record some data as to details of running a small test-mill, especially as details of results do not seem to be accessible to stndents and investigators. Küstel, in 1863, under battery amalgamation, dismisses the subject by stating that "amalgamation on copper-plated platforms, troughs, and other copper fixings" is " very imperfect, and mostly abandoned." J. Arthur Phillips says, in 1867, under placer mining : " A well-amalgamated copper plate is considered as effective for

Jan 1, 1880

By Robert H. Richards

VERY little has been published recently on this subject in the mining journals or proceedings of societies. The attention of experts has been diverted perhaps by the demands for pan amalgamation of refractory ores. Yet free milling ores occur in many localities, and it may be interesting to have on record some data as to details of running a small test-mill, especially as details of results do not seem to be accessible to students and investigators. Küstel, in 1863, under battery amalgamation, dismisses the subject by stating that "amalgamation on copper-plated platforms, troughs, and other copper fixings" is " very imperfect, and mostly abandoned." J. Arthur Phillips says, in 1867, under placer mining : A well-amalgamated copper plate is considered as effective for

Jan 1, 1880

By R. L. Loofbourow

Trends in the metal mining industry were definitely down in 1954. With a record in 1953 of $1.8 billion output, the last year dropped to $1.5 billion, the lowest value since 1950. The decrease in iron ore production alone accounted for at least 10 pct of the decline. PROBABLY more than any previous year, political debates of 1954 marked a new high for the mining industry. Lead and zinc prices gave forth with minor rallies producing no real improvements. An anticipated drop in copper prices never came to be. Early in the year arguments for more free trade versus tariffs to restrict imports were voiced eloquently by Charles P. Taft, president, Committee for a National Trade Policy, and Andrew Fletcher, president, St. Joseph Lead Co.

Jan 3, 1955

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10'3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey' to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N's are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen's computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.' The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By Lawrence A. Roe

The magnetic reflux classifier, which utilizes the combined effects of magnetic fields and a hindered settling classifier, is a new tool for determining the quantity and quality of middlings in fine-sized magnetite concentrates. Results are given for processing a typical taconite ore, and a sketch of the apparatus is included. IN examining magnetite ores and beneficiated products it often becomes necessary to make critical studies of the amount of grinding necessary to produce the desired degree of magnetite liberation. In the past this has been accomplished by laboratory heavy-liquid tests, which provide a method for selectively removing middling particles and free magnetite from various-sized fractions. Examination of the various products under the microscope results in fairly accurate determination of the degree of liberation. The method is quite efficient on sizes coarser than 325 mesh. Thus the heavy-liquid method of middling separation was satisfactory until the advent of present day magnetic taconite studies. When magnetite concentrates ranging from 70 to 100 pct —325 mesh are studied it becomes apparent that older methods of determining liberation size are not satisfactory and that there is need for a new method. For example, some of the low-grade magnetite ores of the Wisconsin and Michigan iron ranges require grinding to 100 pct —325 mesh to produce a magnetic concentrate containing less than 12 pct silica. Examination of concentrates from such ores often reveals that many of the middling particles consist of only very minor proportions of iron mineral. Thus it becomes important to be able to determine the degree of grinding necessary not only for complete liberation, but also for liberation of only 80, 85, or 90 pct of the total iron mineral content. Actually, complete liberation is never attained, but is often used to designate that degree of liberation necessary for production of high-grade concentrates. A rougher concentrate, produced after elimination of a coarse-sized tailing, can usually be subjected to a second grinding stage and concentrated into a higher grade product than could be produced from the same crude ore with one stage of grinding resulting in the same overall size reduction. This fact adds to the importance of being able to determine partial degrees of liberation on any magnetite ore. Standard laboratory methods such as heavy-liquid separation, microscopic grain counts, Davis tube magnetic separation, magnetic flocculation, classification, flotation, and others often are not applicable, or are prohibitive because of time requirements when large numbers of fine-sized magnetite samples are investigated. The Davis tube magnetic separator is an efficient tool to use in rejecting the non-magnetic mineral particles from an ore sample. The middlings discarded by the tube separator usually are so low in iron content that they can be considered relatively unimportant in liberation studies. This condition is caused by the extremely high flux density used in the Davis tube. This flux density ranges from four to eight times the flux density produced by most of the powerful commercial machines in use today. Thus the problem resolves itself into a search for a method of selectively removing middlings from Davis tube magnetic concentrates which will be both rapid and efficient. Those methods showing most promise in the development of a process for isolating middlings from extremely fine-sized magnetic concentrates were flotation and magnetic flocculation. The use of flotation to remove middlings from magnetic concentrates is reported in the literature.'.' The flotation process is effective in removing middlings from a magnetite concentrate, but physical entrapment of fine-sized free magnetite in the silica-bearing froth is an undesirable feature. The flotation method of removing middlings requires time, effort, and precise control of many variables, and does not meet the required degree of middling isolation. Magnetic Flocculation Magnetic flocculation has long been resorted to"-" in efforts to upgrade magnetite concentrates. One of the new magnetic taconite plants now under construction on the Mesabi Range includes magnetic flocculation in the flowsheet' as an accessory process to remove high-silica middlings and free silica which has been mechanically entrapped in magnetite flocs. The use of magnetic flocculation as a laboratory method of making precise separation of middlings was further investigated, since it offered a rapid, simple method of accomplishing the desired result. Magnetic flocculation involves the subjection of a magnetic concentrate to a strong magnetic field, passing the concentrate in a highly flocculated condition to a hydroseparator or other classifiers of various types, and removing free silica and middlings as overflow products. In an attempt to utilize simple

Jan 1, 1954

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 C. R. Sandberg, C. A. Connally, N. Stein

This paper describes the results of volumetric efficiency tests on oil well pumps handling gas oil mixtures. The work was performed in a large scale, above ground unit wherein test conditions could be accurately controlled and measured. The main variables studied were gas/oil ratio (including gas from solution and free gas mixed with oil), pump compression ratio, pump stroke length, pump speed, and clearance volume between the valves at their closest approach. Results are presented for two different pumps and for oils of two viscosities. Relatively small amounts of gas entering the pump resulted in large decreases in volumetric efficiency. Under conditions where the pump was operating at reduced efficiency because of the presence of gas, it was found that variation in the clearance volume between the standing and traveling valves had a considerable effect on pump efficiency level. This effect of the valve clearance volume was found to be significantly altered by the viscosity of the oil used in the tests. The effects on pump efficiency of the other variables studied were found to be relatively small over the range of conditions utilized. INTRODUCTION The production of oil by pumping is often hampered by low volumetric efficiency. A direct increase in lifting costs results from low volumetric efficiency. An indirect increase in lifting costs, probably greater than the direct increase, results from additional wear and tear on pumping equipment and from the down-time necessary for the repairs which can be traced to low-efficiency operation. Both increases in lifting costs tend to reduce economically recoverable oil. A number of different factors can contribute to low pump efficiency. A known basic cause of low efficiency is the presence of free gas in the pumped fluid. Pump volumetric efficiency is calculated only on the basis of liquid pumped and because any free gas pumped is discounted, this volume of free gas would represent a loss of pump efficiency. However, gas also causes a reduction in pump efficiency because it is a highly compressible fluid. It is known that pumps some- times "gas lock" because of excessive gas-to-liquid ratios in the pump barrel. Little is known of the role of gas compressibility in the intermediate case where the pump is operating at low efficiency. The opinion exists, however, that oil-well pumps tend to operate at higher efficiency with long stroke lengths at low speeds, but no quantitative studies of these pumping variables have been reported. It was believed that a much better understanding of the variables which control pump volumetric efficiency could be obtained and that possibly some suggestions as to the methods for increasing efficiency might be found from a study of the operation of pumps handling gas under closely controlled conditions. Previous investigators have studied the effects on pump efficiency of such factors as oil viscosity, oil temperature, slippage of oil. past pump plungers, pump submergence, valve size and spacing, pressure above pump plunger and fluid vapor pressure. However, none of these published investigations were conducted with pumps being subjected to large amounts of gas such as might be the case in a pumping well, nor did any of the investigations study the effect of variation in stroke length or pump speed. A large-scale teat unit was therefore constructed for studying the operation of pumps handling gas and for evaluating effects of such variables as pump stroke length and pump speed. PROCEDURE AND EQUIPMENT A schematic diagram of the pump testing equipment is given in Fig. 1. A 45-ft length of 6-in. casing is mounted vertically in a 65-ft tower. Sight ports are mounted in the casing at intervals near the location of the pump intake and the liquid level in the casing. These sight ports are fitted with Lucite windows sealed by neoprene "0" rings. The Lucite windows are machined to conform to the I.D. of the casing so that no obstruction to flow is present along the casing wall. The casing is fitted with a tubing head and 2-in. tubing is hung inside the casing. Pumps are seated in a shoe attached to the 2-in. tubing. A 1-in. polish rod is attacked directly to the pump without any intervening sucker rods. The top of the polish rod is attached to the weight carrier, which contains a number of weights to be used to force the polish rod in against tubing pressure on the down-stroke. This is necessary because a long string of sucker

Jan 1, 1953

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963