Search Documents

By A. B. Cook, C. J. Walker, G. B. Spencer

Although water will displace oil from a petroleum reservoir to a greater extent than gas will, there are some reservoirs in which gas rather than water should be used for pressure maintenance. This is indicated by the high-percentage oil recovery in the case history reports on the Pickton field1 in East Texas and the Raleigh field2 in Mississippi. In gas cycling, total oil recovery includes vaporized products from the immobile oil in addition to oil produced by displacement. If a large part of the immobile oil is vaporized, total oil recovery may be higher than that obtainable from pressure maintenance by water injection. However, the amount of immobile oil vaporized may range from almost 0 to 100 percent, and no simple and reliable method has been presented in the literature for calculating oil vaporization. Development of such a method was the purpose of this study. Several papers concerning the calculation of oil vaporization have been published,3 6 and each is based on the concept dealing with K values — equilibrium constants for the various components in reservoir oils. (K for a component in a system of vapor and liquid in equilibrium is the mole fraction in the vapor phase divided by the mole fraction in the liquid phase.) This appears to be the most logical approach. Yet, the problem is too great for a perfect solution, even with modem laboratories to analyze oils and high-speed digital computers to perform calculations; the number of components in reservoir oils is too large. Because of their complexity no two reservoir oils are exactly alike. Also, K values change not only with variations in pressure and temperature but also with composition of the reservoir oil. In addition, during gas cycling, the lighter hydrocarbons tend to vaporize first. Thus, the reservoir oil becomes more dense and less volatile as gas cycling continues. Furthermore, the greatest amount of oil vaporization occurs near the injection well. Therefore, a simplified method is required for calculating oil vaporization because a rigorous method is not practical. The present methods of calculating vaporization generally require knowledge of the reservoir oil composition in which the mole fractions of the lighter components through hexanes are given; the remaining oil is described as C, + (heptanes and others of greater molecular weights). Assigning one K value for the C,+ system provides the simplest solution, but this incorrectly assumes that K for C, + does not change as gas cycling continues. This assumption can cause large errors because the K value may become less than a thousandth of the original after a large amount of oil vaporization. Another way to solve the problem is to determine changing K values for C, + according to how much of the C, + has been vaporized. To determine these values a sample of the reservoir oil is injected into a pressure-volume cell, and dry gas is batched in and out of the cell. Appropriate measurements and tests are made to determine K

Jan 1, 1970

By AIME AIME

BESIDES commanding increasing importance as an alloying element in combination with ferrous and other nonferrous metals, the variety of uses for pure nickel continues to widen. For coinage it is growing in popularity. These coins have been minted for 27 countries in 72 issues representing 69 denominations. Approximately 3,000,000,000 pieces have been struck, the aggregate weight, of which amounts to nearly 14,000 tons. . Danzig, Iraq and Japan are the most recent governments to adopt, pure nickel coinage. France is adding the denomination of five francs to its other nickel currency; they replace silver pieces. Germany is now minting a new issue of one Reichsmark coins of pure nickel. The Japanese program for 1933 called for the issue of 35,000,000 10-sen pieces and 30,000,000 5-sen pieces. In radio tube manufacture the consumption of pure nickel was approximately twice that of 1932. During 1.933 the nickel plating process by which bright deposits may be plated

Jan 1, 1934

By G. D. Monk, W. C. Krumbein

THE relation between permeability and the size parameters of unconsolidated sand is approached by considering sands as logarithmic frequency distributions having the basic parameters mean size and standard deviation. Sieve separates were mixed in accordance with the normal logarithmic probability law, so that the mean and standard deviation could be varied at will. Experiments were conducted in which one parameter was kept fixed and the other varied; in this manner the dependence of permeability on the individual parameters was evaluated. It was found that permeability can be expressed as the product of a power function of the mean size and an exponential function of the standard deviation.

Jan 1, 1942

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By M. A. Hunter

THIS paper gives the results of an investigation of the specific resistance and temperature coefficient of the electrical resistance of nickel and its important alloy, monel metal. For most of the pure metals, the temperature coefficient of resistance is approximately 0.0004 per degree centigrade at 2.0° C. Nickel and iron, however, are exceptions. This property is important as it gives us good material for the construction of thermometers and other instruments involving electrical control. A summary of information on this subject has been published by the Bureau of Standards.1 The present experiments antedate this publication by several years and as the information obtained is not contained in it, the results of the experiments are published as additional information. ELECTRICAL PROPERTIES OF PURE NICKEL It is generally conceded that the lowest values for electrical resistance are obtained in the purest metal. In the case of nickel, the best material obtainable is electrolytic nickel, which contains approximately. 99.80 per cent. nickel, 0.15 per cent. iron, and 0.05 per cent. copper. Any cobalt that may be present is included in the nickel figure. If the electrolytic sheet has been deposited without intermission, it is possible to cut a section from the sheet and roll it into wire without melting. By this means a nickel wire may be obtained that is uncontaminated by any of the impurities always taken up by nickel during melting.

Jan 5, 1922

By Will Mitchell, Ford F. Miskell, C. L. Sollenberger

THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators 1-5 have noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilities6 and by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported' to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of this portion is shown in Table I and an approximate mineralogical analysis is shown in Table II. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of -6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1952

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,' the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

By L. D. Anderson

WHEN, after years of troublous experiences in roasting sulfide ores with heavy dust and fume losses resulting from the equipment and methods first available, there appeared on the, scene of metallurgy that revolutionary process known as sintering, it was felt that at last there had been found the ideal method for preparing sulfide ores for blast-furnace reduction. Not only were the sulfides roasted but also the fine oxidized ores were bound together with them in strong porous cellular masses which were in the best possible condition for reduction. With the experiences gained in the manipulation of the Huntington-Heberlein, Carmichael-Bradford, and Dwight & Lloyd processes there developed a refinement of detail which brought the whole plan of roasting by sintering to a high plane of perfection. But that metallurgy is never stationary is revealed by the fact that changes in milling practice, particularly the development of flotation, have introduced a new set of problems in sintering itself. Inasmuch as it is felt that these problems have not yet been solved in an entirely satisfactory manner this paper is written to record the present practice of the Salt Lake Valley smelters with the hope that there will be brought forth such discussion as may perhaps lead to still better practice. By far the greater proportion of the sulfides smelted today are flotation concentrates. Usually they are high grade, sometimes as high as 70 per cent. and more in lead. They are extremely fine, many mills grinding the ore so that from 60 to 80 per cent. will pass through screens of 200 mesh. The physical condition in which many of these concentrates reach the smelters is disconcerting to the metallurgists. Some are of about the consistency of putty. Others are of a sticky, slimy nature. Others again, dried to the limit, are veritable powders. Remembering that the down-draft sintering charge for the best results must be porous enough to let air be drawn through it reasonably well, must be thoroughly mixed, and must have some coarse material in it to segregate out and form a layer on the grates, it will be understood that the advent of this extremely fine material has made necessary still further elaboration in the equipment and processes of preparing sulfides for the blast furnaces, all of which is expensive. The high metal contents of the concentrates

Jan 1, 1929

By L. D. Anderson

WHEN, after years of troublous experiences in roasting sulfide ores with heavy dust and fume losses resulting from the equipment and methods first available, there appeared on the scene of metallurgy that revolutionary process known as sintering, it was felt that at last there had been found the ideal method for preparing sulfide ores for blastfurnace reduction. Not only were the sulfides roasted but also the fine oxidized ores were bound together with them in strong porous cellular masses which were in the best possible condition for reduction. With the experiences gained in the manipulation of the Huntington-Heberlein, Carmichael-Bradford, and Dwight & Lloyd processes there developed a refinement of detail which brought the whole plan of roasting by sintering to a high plane of perfection. But that metallurgy is never stationary is revealed by the fact that changes in milling practice, particularly the development of flotation, have introduced a new set of problems in sintering itself. Inasmuch as it is felt that these problems have not yet been solved in an entirely satisfactory manner this paper is written to record the present practice of the Salt Lake Valley smelters with the hope that there will be brought forth such discussios as may perhaps lead to still better practice. By far the greater proportion of the sulfides smelted today are flotation concentrates. Usually they are high grade, sometimes as high as 70 per cent. and more in lead. They are extremely fine, many mills grinding the ore so that from 60 to 80 per cent. will pass through screens of 200 mesh. The physical condition in which many of these concentrates reach the smelters is disconcerting to the metallurgists. Some are of about the consistency of putty. Others are of a sticky, slimy nature. Others again, dried to the limit, are veritable powders. Remembering that the down-draft sintering charge for the best results must be porous enough to let air be drawn through it reasonably well, must be thoroughly mixed, and must have some coarse material in it to segregate out and form a layer on the grates, it will be understood that the advent of this extremely fine material has made necessary still further elaboration in the equipment and processes of preparing sulfides for the blast furnaces,

Jan 1, 1929

By W. P. Shinn

In a paper contributed by W. A. Goodyear, M.E., on "Water Gas as Fuel," read at the Boston Meeting, February, 1883,* the following statenlent was made: "The latest experiments on a scale of some magnitude in our citier, in the way of heating buildings and furnishing power for manufacturing purposes, have been by the distribution of high-presslire steam through pipes laid in the streets. Hilt these experiments (1) have not hitherto been very successful; and when we consider the high cost and (2) the great and unavoidable loss of heat and power, which always accompany the conveyance of high-pressnre steam to any considerable distance in pipes, to say nothing of (3) certain practical difficulties in the management of the pipes themselves, (4) it is evident that all such methods must eventually disappear before a system which can furnish a cheap gas of great heating power, easily distributed wherever wanted, without requiring pipes to stand pressures of 50 to 75 pounds per square inch, and (5) without keeping the whole mass of ground in the streets through which it passes hot, gratis, for a distance of ten or fifteen feet, in all directions around the pipes!' For the purpose of controverting Mr. Goodyear's statements in regard to steam-distribution in cities, I hare numbered the points made in his indictment, my principal object being, not a professional discussion of the technical and theoretical merits of steam vs. watergas, but a simple statement of facts, in regard to the present state of the street system of steam distribntion. Taking Mr. Goodyear's points in their order: 1. Concerning what he terms " These experiments," saying that they " have not hitherto been very successful," I propose to show, that the problem of stearn-distribution has passed beyond the experimental stage, and that its practical solution is highly successful. This will be shown by the facts hereinafter fully set forth. 2. "The great and unavoidable loss of heat and power whicn always accompany the conveyance of high-pressure steam to any con-

Jan 1, 1884

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By J. C. Bayles

Jan 1, 1886

By GEO M. FOWLER

AN appraisal of the activities of the mining geologists during 1936 clearly indicates the ever in- creasing utilization of geology in the search for ore. Few men with geo- logic training are idle at present; this is particularly true regarding recent graduates. Many have accepted employment in distant fields, such as the Philippines and South America, and greatly increased mineral production from these places reflects their activities. In North America, regions of intense mineralization formerly important are being restudied in greater de- tail and with better understanding; as a result, new mineral wealth is being found in many such districts. Much is being done by private companies and individuals, and it is to be hoped that mining companies will increasingly make available the purely scientific results of such studies by permitting their geologists to publish. On such generosity to a large extent will future advances in ore finding depend.

Jan 1, 1937

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By C. F. Nagel

This paper is written primarily for those who are familiar with the processes mentioned but who desire a further insight into some of the fundamental principles. It does not give a complete description of the various practices employed in the working of aluminum and its alloys, but presents a few illustrations of the essential respects in which aluminum differs from other common metals, and emphasizes the controlling factors of the processes under consideration. Heat Treating Certain aluminum alloys are capable of having their mechanical properties greatly altered by a heat-treatment process. The degree of this irnprovement may be illustrated by some typical properties of dura-lurnin (Table 1). It is essential that the material be in the wrought condition in order to obtain rnaximum heat-treatment effects. In the case of duralumin, the process consists of heating the metal to a prescribed temperature and then quenching it. Immediately after quenching, the material is relatively soft though not as soft as in the annealed state. If allowed to stand at room temperature, the material changes, increasing in hardness and strength without loss of elongation, but at the expense of the plasticity. This action is very rapid at first, gradually diminishing in intensity and to all practical purposes being completed in about four days. This process of hardening is termed

By A. L. Bailey, B. A. Landry

All who are even generally aware of the tremendous rate of increase in coal washing operations must realize the growing importance of the float-and-sink test. I believe it is conservative to estimate that, in the past decade, the dollar volume of float-and-sink testing has increased tenfold. It is a simple matter of economy, then, to examine the factors that determine the cost of adequate float-and-sink testing. When the Coal Preparation Section of the Bureau of Mines entered upon a greatly expanded program of such work in connection with the synthetic liquid fuels investigations, it seemed advisable to examine these factors experimentally. The principal consideration that differentiates float-and-sink test sampling from general purpose sampling, is that the original particle size must be preserved. Therefore, the total cost of the test will be directly affected by any standard that might be proposed to limit sample bulk reduction at any given particle size. For this reason, the relationship of sample size to variability of results was the first factor to be studied experimentally. Of course, the matter is rendered complex by the circumstance that the float-and-sink test, not a simple analytical measurement but a process test, comprehends a number of more-or-less independent items of fundamental data; and as shown in the report, the&apos; variability of the samples differs with respect to these different items. This condition and the wide variety of situations in which float-and-sink test data are used, in combination with other factors, to study complex process operations, indicate the difficulty of setting up fixed standards for float-and-sink sampling and testing. At this stage at least, it is the intent rather to obtain experimental data on the principal Factors involved so that the reader may arrive more intelligently at a procedure adapted to his problem. The authors of this paper have presented experimental data showing the relationship between size of sample and particle size for different variability tolerances with respect to percentage of sink. In further studies, data are being collected to appraise also the variability of the samples with respect to float-ash content and size consist. The scope of this work will be broadened to cover particle sizes up to 4 in., and a third series of tests has yielded similar data for a much cleaner type of raw coal. Thus, the further studies will make available a fairly comprehensive meas- ure of variability with respect to size consist, percentage of sink, percentage of middlings, and percentage of ash in the float, for three coals ranging from 3.87 to 17.68 pct in refuse content (heavy sink material) and from 4.18 to 17.52 pct in middlings. Introduction At present there are no published standards for float-and-sink test sampling. During the rapid expansion of float-and-sink test work, varying procedures have been based on adaptations of the ASTM standards for sampling coal for analyses. For this reason, a special study of gross sample reduction has been undertaken to determine the limits for this step in the operation where no reduction in particle size is to be made before testing. Float-and-sink tests are made whenever a thorough study of coal characteristics is desired. The tests may be made on samples from coal-cleaning units such as jigs or tables, or coal samples may be tested which are taken from a loading boom, railroad car, or the coal seam itself. The resultant gross sample may be large and pose a problem of sample reduction. The question is, then, how much can the sample be reduced and still fall within preassigned limits of accuracy of the original gross sample of coal? Coal from channel samples may be crushed to liberate impurities and then separated into various gravity fractions from which washability curves are drawn; from these curves, it is possible to determine the cleaning characteristics of the coal. However, coal samples from coal-cleaning units cannot be

Jan 1, 1950