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By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By S. Vela, R. M. McKinley, L. A. Carlton

Johnson et al. have described a new well-testing technique that measures formation flow properties between wells.' The technique, called pulse-testing, requires a sequence of rate changes in the flow at one well and measzcrement of the re.rulting pressure changes at an adjacent well with a very sensitive differential pressure gauge. This paper describes an extensive application of the technique in a producing oil field. Pulse-tests on 28 of 45 possible well pairs in the field provided a picture of the areal distribution of reservoir hydraulic diffusivity, trans-missibility and storage. The primary objective in presenting these data is to demonstrate the potential of the methcid for reservoir description. A second objective is to show in three ways the qualitative and quantitative accuracy of reservoir parameters determined from pulse-tests: (I) pulse-test data show a nonuniformity in the field, closely correlating with the oil-water distribution as given by production data: (2) pulse-test values for permeability are comparable with core va1ue.s; and (3) perhaps most important, the field responds to a conventional interference test in the manner in which pulse-test data predict it should. The pulse-testing technique by Johnson et al.' is an ideal source of data for purposes of reservoir description, for it provides a measurement of formation storage S = +ch, hydraulic diffusivity 91 = k/+cp and transmissibility T — This paper describes an application of this method in a producing oil field. Results were analyzed to give numerical values for the parameters 7, T and S. These values were compared with oil-water production data (for the effect of fluid saturation), with core data and with data from an interference test. The reservoir in which the pulse-test survey was run is the result of a structural trap formed by a fault along the east side of a north-south trending anticline. A down-structure aquifer providcs a natural flank water drive for the pool. The producing formation is a dolomitic lime- stone having mainly vugular permeability; the formation oil has a gravity of 29" API with negligible dissolved gas. The field contains 19 wells, all on pump, arranged on 40-acre spacing along the top of the anticline. Fig. 1 shows the location of all these wells except two at the south end of the field. The dashed line on the right-hand side of the figure represents the approximate location of the fault with respect to well positions. Pulse-Test Survey and Analysis of Data A pulse-test requires a pulsing well and a responding well. In the field, changes were made in the rate of flow at the pulsing well by stopping and starting the pump periodically and measuring the corresponding pressure

Jan 1, 1969

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By J. H. Swisher

An experimental study has been made of the possible mechanisms for foam stability in the system CaO-SiO2-Cr2O3, where Cr2O3is the foaming agent. The degree of lowering of surface tension by Cr2O3 was determined at 1600 "C for high -silica melts. Measurements were also made of foam stability under standardized conditions. The results of the two sets of measurements then were correlated by applying the Gibbs and Marangoni theories of film elasticity. It was demonstrated that the Marangoni elasticity effect is probably the largest single contributor to foam stability, although the high uiscosity of' silicate melts makes some contribution in controlling the rate of drainage of liquid from bubble lamellae. ThE tendency of metallurgical slags to foam has frequently been observed during steel-refining operations. In the open-hearth furnace,this tendency is considered undesirable because it slows down the rate of heat transfer from the burners to the molten-metal bath. On the other hand, it is sometimes desirable to have a "foamy" slag in the basic oxygen converter.' A more effective blanket over the steel bath is made by a "foamy" slag, and loss in yield of metal due to splashing is minimized. In addition, a flush slag can be removed more easily in this condition. Since slag-foaming problems in the field have been attacked largely on an empirical basis, it appeared desirable to obtain a better basic understanding of the mechanism of foam stability. The experimental work was directed almost entirely toward the behavior of Cr2O3 as the foaming agent in CaO-SiO,-Cr2O3 melts. In the first stage of the investigation, the degree of lowering of surface tension by Cr2O3 was determined at 1600°C. The second stage consisted of measuring foam stabilities under standardized conditions. The two sets of experimental results then were correlated by applying various theories of foam stability. For convenience in interpreting the surface-tension and foam-stability results reported here, a portion of the CaO-SiO2-Cr2O3 phase diagram2 is reproduced in Fig. 1. EXPERIMENTAL 1) Surface-Tension Measurements. Very little information is available in the literature on the lowering of surface tension of slags by foaming agents. Kozakevitch 3 mentioned that the addition of 1.5 pct Cr2O3 lowered the surface tension of FeO slightly. In another system, some data on the lowering of surface tension of foaming slags by P2O5 were reported by Cooper and Kitchener.4 The technique used for the surface-tension measurements was the maximum bubble-pressure method,' using a single tube immersed to various depths in the melt. This method has been used extensively in high-temperature systems, such as in liquid metals, slags, and glasses.6,7 It has the advantage that the contact angle between the liquid and the tube material need not be known. The equation used for calculating surface-tension values from maximum bubble-pressure measurements is the Schroedinger equatioq5 which can be written as follows:

Jan 1, 1964

By B. A. Rogers

The etching effect that is produced on a piece of polished iron or steel when it is heated in hydrogen or in a vacuum seems to have been observed first by Osmond,' who believed that he could distinguish four systems of grain boundaries on a piece of steel which had been heated in hydrogen. In a number of other investigations, samples of pure iron were found, after heating, to have complex networks in which two or three systems of grain boundaries could be detected. It was further noticed that samples that had been polished plane before being placed in the furnace were, after treatment, roughened and undulating over their entire surfaces. From a comparison of the temperature of heat treatment with that of the A3 transformation, it was concluded that the changed appearance of the samples was definitely related to the latter phenomenon. Certain other deductions were made but these are not of importance here and only observations on the appearance of the samples will be reviewed. Ewen2 heated a strip of polished iron in a vacuum in such a way that one end was maintained at a temperature of 1000" C. and the other at 580" C. On the cooler end there was outlined a simple polyhedral network, and at the hotter there appeared the complex systern of lines ant the undulating surface characteristic of iron which has passed through the A3 transformation. He found that in going from the cooler toward thc hotter end the sample maintained much the same character of surface up to the beginning of the transformed area, but that near this region doublc grain boundaries were of frequent occurrence. Rawdon and Scott concluded that the simple type of network brought out by heating a sample of pure iron in a vacuum was of the same type as that developec by ordinary etching methods. They also confirmed the observations of

Jan 1, 1929

By John B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about ½ -in. water pressure. No loss of air was evident.

Jan 7, 1958

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By Edwin Ludlow

ROUNDING out a year of improved organization, substantial accomplishment and strengthened purpose, the American Engineering Council of the Federated American Engineering Societies held its first annual meeting at the Cosmos Club, Washing-ton, Jan. 5 and 6, Dean Mortimer E. Cooley of the University of Michigan, president of, the Council, presiding. Officers were-chosen, the work of the past year was reviewed and discussed, action was taken on important matters of public and technical service, new financial arrangements were put into effect, committees were named, new policies were sanctioned and old ones reshaped, and a broad and definite program was out-lined for the next twelve months. A leading event of the meeting was a dinner in honor of Herbert Hoover, who, addressing the members of the Council and their guests at the University Club, praised the work of the Committee on Elimination of Waste in Industry as a great and lasting public service, pointed the way for new engineering effort in the public interest, and expressed renewed devotion to the ideals of the Council. Resolutions of appreciation of the service of the Secretary of Commerce were presented to Mr. Hoover.

Jan 2, 1922

By Milton Williams

IT is generally recognized that fluid is lost from rotary drilling mud s to permeable strata during normal drilling operations;1,2,3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 . The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable ent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the "tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata.

Jan 1, 1939

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By William N. Matheson

The major consideration in any management and engineering decision is the economic evaluation of factors. The right decision is the best cost decision, provided of course that it is the safest. Changes, improvements, and advances in mining technology, as in any business, come about through the pressure of economics in combination with the inventiveness and engineering abilities of efficient mine operators. Without proper economic evaluation and an appreciation of profit and loss of an operation, advances in mining methods would come about at a slow pace, if at all.

Jan 4, 1959

By Axel Hultgren

IN ingots of silicon-killed carbon steel made without addition of - aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially. In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents arid, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,10,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis17 and their amount to increase from the top downward in the axial region .2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form," by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.15 Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19,20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping' or of refractory material from various sources1,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistance to hydrofluoric acid, imparted by the alumina content. Silicate inclusions, are often referred to as. the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1948

By Dilip K. Paul, Charles H. Jacoby

The economic importance of salt domes has been recognized throughout the world, primarily because of oil and gas accumulations on their flanks, and to a lesser degree, for the value of their salt and potash. Recently they have become of value as hosts for cavities used to store hydrocarbons. In the near future we believe that their main value will be a source of geothermal energy. Although tremendous effort has been expended on the understanding of the geology and physical characteristics of the strata intruded by salt domes, relatively little energy has been exerted in the comprehension of the salt dome itself. Salt domes have long been recognized as a geological heat anomaly. With respect to other sedimentary rocks, salt is a good conductor of heat. Expressing values in 10-3cgs units, sedimentary rocks vary from 1.0 to 8.0; metamorphic rocks from 5.2 to 8.4 and igneous rocks from 3.1 to 9.8. Rock salt in its pure form has a thermal conductivity of 17. Thus a salt dome can be expected to act as a conduit bringing heat vertically from deep within the earth's crust.

Jan 5, 1974

By L. B. Berger, W. P. Yant

This paper presents evidence of the general occurrence of methane in a large number of the coal fields of the United States and substantiates the apparent unnecessary differences in the ventilation requirements and codes in the various states, as was brought to the attention of the Committee on Mine Ventilation of the American Institute of Mining and Metallurgical Engineers at its Pittsburgh meeting in October, 1925, by J. A. Garcia. The data in his report have been compiled from the files of the Gas Laboratory of the Pittsburgh Experiment Station of the Bureau of Mines and represent samples collected throughout the various states and submitted for analysis by its engineers, also by mine operators and State mining departments, since 1911. Several thousand analyses were available but most of them were rejected because they represented abnormal conditions, undefined place of sampling, special investigations, or duplications in the same mine. Only those samples were included which, without reasonable doubt, were ascertained to fall within three major classes, namely, main return, air splits, and face and rooms of live workings. In the case of air splits, and face and room samples, only the one which contained the highest percentage of methane found in a given mine was taken. OCCURHENCE OF METHANE IN COAL MINES OF THE UNITED STATES Obviously it is not feasible to present the detailed analytical data here and accordingly these data have been compiled into groups in a manner which it was thought would bring out clearly their significance. These are shown in Table 1 which includes the analyses of 310 samples of return air of approximately the same number of coal mines in 19 states. Because of changes in ownership and names the exact number could not be ascertained. The table also includes 337 samples from air splits and 263 from the face and rooms of some of the same mines represented by return air samples and from other mines in these states. A total of more than 400 mines are represented by Table 1.

Jan 1, 1927

By Winthrop P. Haynes

The symposium on production for the year 1944 includes more foreign papers than any one of the past three years, because of a partial relaxation of the censorship in many Western Hemisphere countries. The committee was not successful, however, in securing papers from Europe and the Near and Far East at this time, with the exception of Saudi Arabia and Bahrein. Where possible, these papers include summaries upon production for the missing war years, so that we shall have no permanent gap in the records. At the close of the war, we hope again to publish the usual more complete form of report for all important oil-producing countries. EXCERPTS FROM CIRCULAR TO AUTHORS In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each place in the table may represent one of three possibilities; either the proper entry is determinable and can be supplied by the author, or an approximate figure can be supplied which is the author's best guess and should be entered followed by an x, or it does not apply to the particular field and the space is left blank. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. The entry of a zero is a positive declaration, and it is an important declaration where it is in order. It is thought that the nearest whole numbers are sufficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. . Under the columns on "Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when subtracted, should give the approximate thickness of the productive zone. For fields where this is not true because of unusually high dip or for some other reasons, it is suggested that the authors indicate in their text the approximate average thickness of the productive zone. The net thickness of the producing formation should be the thickness of the producing zone, less the estimated amount to cover the portions of the zone that do not yield oil, such as dense shales, etc. It is recognized that for some fields the authors can only make rough guesses; in such cases, they should enter their best estimate followed by an x. Average production per acre-foot need not be reported as it can

Jan 1, 1945

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By B. Thomas Mansbach

INTRODUCTION The Overseas Private Investment Corporation ("OPIC") is a U.S. Government agency mandated to promote the economic development of the less developed countries ("LDCs") by assisting U.S. private investment in the Third World. Generally, investment decisions turn on the optimism or pessimism of the private sector's financial analysis of a project, with market price of product a major unknown in a very chancy set of projections. Discussions with American mineral companies, however, show that, more often than not, in developing country projects it is the political risks of investing in mineral exploration and extraction that pose the most serious deterrent to investment. In several of the projects described here, investments would not have been made if OPIC had not been involved providing support to the project sponsors and their funding sources. Clearly it is not OPIC's business to promote U.S. investment in a project which is not commercially viable, but OPIC's programs can neutralize the political uncertainties which act as disincentives to investment in otherwise commercially viable projects. That is to say, OPIC's programs are designed to reinforce market decisions and not distort them. Although OPIC is an independent agency of the U.S. Government, it is managed by a Board of Directors, the majority of whom come from the private sector. This, coupled with the statutory requirement that it be self-sustaining and operate with due regard for the principles of prudent risk management, requires that it operate on a business-like basis. Although established as a development agency, to the business public OPIC is both an insurance company and a lending institution, with two major programs which are available to U.S. investors in the minerals sector: its political risk insurance program and its finance program. Each has been specially tailored to the meet needs of the mining industry. The insurance program provides coverage against four basic types of political risk: Currency Inconvertibility, Expropriation, loss caused by War, Revolution and Insurrection and Interference with Operations as a result of an act of War, Revolution or Insurrection. Coverage against the risks of Civil Strife can be added to both War, Revolution and Insurrection coverage and Interference with Operations. Inconvertibility coverage provides protection against a deterioration in an investor's ability to convert local currency into U.S. dollars. This deterioration can be the result of either active or passive delays. Active delays consist of a change in exchange laws or regulations that leads to inconvertibility delays of 30 days or more. For example, if the exchange regulations at the time of contract execution allow an investor to transfer earnings equal to 18% of its registered capital per annum and the government of the host country later changes the law to allow conversion of only 12%, the insured would convert the 12% transferable under the new exchange regulations with the government foreign exchange authorities, delivering the remaining 6% to OPIC for conversion at 99% of the then prevailing rate of exchange. (OPIC does not cover devaluation risks.) Upon delivery of the local currency to OPIC, normally at the U.S. Embassy in the project country, the insured's account in the U.S. would be credited with dollars. Delays can also result from what is termed passive blockage, which includes administrative delays of more than 60 days (sometimes longer) caused by the bureaucratic tie-ups or pigeonholding of transfer requests, as well as delays suffered simply because the government of the host country does not have sufficient foreign exchange. The transfer procedure is the same as with active blockage - the local currency is delivered to OPIC in the project country and OPIC provides dollars in the United States at the then prevailing rate of exchange. The second coverage -- Expropriation -protects not only against the loss of the investment due to the well-known risks of expropriation, nationalization or confiscation by the host government, but also against

Jan 1, 1985

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968