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By F. Kurata, A. F. Bertuzzi, P. C. Davis, T. L. Gore

The phase and volumetric properties of 10 very volatile mixtures are presented for temperatures from — 200°F to above the critical points. These mixtures consisted of natural gases and of mixtures of natural gases with methane and nitrogen. Existing correlations of compressibility factors have been extended to apply to these mixtures. Existing correlations of critical pressures and temperatures do not apply to these mixtures. Methods have been developed for estimating critical temperatures of these mixtures to ± 4°F and critical pressures to 2 5 per cent. These methods apply to other volatile and very volatile mixtures. The results of this work are particularly applicable to the separation of nitrogen from hydrocarbons by low-temperature distillation. INTRODUCTION Knowledge of the low-temperature phase and volumetric properties of natural gases and of other mixtures of the light hydrocarbons is becoming increasingly important as interest in low-temperature separation processes increases. Low-temperature distillation has been used to separate ethane and ethylene from natural gas and from refinery gases for petrochemical uses. Removal of nitrogen from natural gas by low-temperature distillation has been proposed 7,20 as a means of increasing the capacity of existing gas transmission lines and of improving the marketability of the gas. Further application of low-temperature separation processes has been retarded by lack of data on the phase and volumetric behavior of mixtures at low-temperatures and at high pressures. This paper presents the results of determination of the phase and volumetric properties of 10 very volatile mixtures at temperatures from - 200 °F to above the critical point. These mixtures consisted of natural gases with methane and nitrogen. Generalized methods are presented for estimating the critical temperatures, critical pressures, and the densities of such mixtures. EXPERIMENTAL APPARATUS AND PROCEDURES The apparatus and the experimental procedures have been described in an earlier paper13. The method consists of displacing the mixture from a reservoir which is maintained at constant temperature and pressure into an agitated glass equilibrium cell which is maintained at constant temperature. The liquid level within the glass equilibrium cell was visually observed, and the pressure was measured to within & 3 psi with a calibrated Bourdon gage. COMPOSITIONS OF MIXTURES STUDIED The compositions of the mixtures studied are summarized in Table 1. The measured properties included in Table 1 will be discussed later in this paper. The sources of these gases are described below: Gas "A-1'' was obtained from the Phillips Petroleum Co. Its composition was reported in connection with earlier work." The properties of this gas were reported in an earlier paper.13 Gases "A-2, A-3, A-4" were prepared by mixing nitrogen with gas "A-1." Gas "AB-1" was prepared by mixing methane with gas "A-1." The properties of this gas were reported in an earlier paper.'" Gases "AB-2" and "AB-3" were prepared by mixing nitrogen with gas "AB-1." Gas "B" was obtained by W. W. Bodle of J, F. Pritchard & Co. from the primary separator of a well in western Kansas. Gas "C" was obtained from a Cities Service Co. pipeline at Lawrence, Kans. Gas "D" was prepared by mixing gas "AB" with gas "C."

Jan 1, 1955

By Edward Sayre

IN shaft sinking for coal mines, the cost item greatly influences the method adopted. This holds true especially when soft material must be traversed. The average life of a coal mine is short. This is clue either to the limited area of the coal basin or to the great expense of maintenance and haulage underground when the entries are extended a considerable distance from the hoisting shaft. Therefore, the engineer in opening a coal mine is confronted with the fact that the cost must be kept within certain bounds else the venture will prove unprofitable. For this reason he may be prohibited from adopting certain safe, but expensive, methods that are used in sinking caissons for foundations, driving transportation tunnels, or other work of permanent construction. A common method of sinking through difficult ground employs the aid of a steel shoe pushed ahead of the shaft timbers. Another is the drop-shaft method. These two methods were used in sinking the main shaft and the air shaft of the Eagle No. 3 mine, at Des Moines, Ia., and the following data show the relative success and cost of the two methods of sinking under the same conditions. A drill log of the material to be penetrated was as follows (see Plate 1, Fig. .1)

Jan 9, 1916

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By S. C. Sun

Most previous work on sedimentation of coal 1 and mineral 2-3 suspensions has been conducted in graduated 1-liter glass cylinders of 6-cm diam. With this type of large container it is often difficult to see through the suspension and tedious to perform a large number of tests. Furthermore, the heavy glass walls and the graduation lines of glass cylinders cause internal and stray reflections, respectively. To obviate these difficulties, an Atlab Emulsion Viewer from Arthur H. Thomas Co. was adopted as an alternative apparatus. Equipment: The viewer," shown in Fig. 1, consists of: 1) a stainless steel frame rack holding 21 flat-bottom Nessler tubes or an ungraduated replica 1.64 cm ID and 1.80 cm OD, 2) a movable masked 150-w lumaline lamp behind the tubes, and 3) a scaled glass panel with 100 vertical divisions in front of the tubes. The tubes are snugly held by springs in slots formed by spacer bars, which also serve as shields to eliminate stray light. The lumaline lamp is mounted behind a slit in a movable housing so that it can be positioned behind the suspension to be examined. The lowest or 100-divi-sion line on the front glass plate is leveled with the upper side of the bottom of all tubes. The scaled portion of each tube, roughly 19 cm high and 40 ml in volume, is used to study coal and mineral suspensions. Procedure: The following procedure was used in many tests. A 1.6-gm sample of dry coal was mixed with 16 ml of distilled water in an ordinary test tube and allowed to stand for three days, with occasional shaking to insure thorough wetting of all particles. The slurry was transferred to a Nessler tube and diluted to 32 ml. The pH regulator and flocculating reagent were added, and the slurry was diluted to reach the uppermost or zero-division line. The tube was immediately stoppered and inverted downward and up again ten times during a period of 35 to 40 sec. The lumaline lamp was turned on during the inversion period. After inversion the tube was quickly returned to the viewer rack. The time elapsed for each 10-division drop of the demarcation line between solid and liquid was recorded by stopwatch until the 80-division line was reached in the zone of compression. Additional readings were taken at 15, 30, and 60 min after settling began. The clarity of the supernatent liquid was observed also. As the settling rate became considerably slower at the 75-division line, it was convenient at this time to start the next test in a separate Nessler tube. This was continued until the suspensions in any number of the 21 tubes were tested. An attempt was made to correlate the experimental results between the Nessler tube and a 1-liter glass cylinder. Table I shows that coal particles settle much faster in the cylinder than in the tube, which has a large wall effect.' The correction factor for the tube impedance is 1.662 2 0.145 at the 40-division line in the hindered settling zone, and 1.614 & 0.139 at the 75-division line in the compression zone. This rough correlation was established by dividing the pulp height of each container into 100 divisions and comparing the settling rates of the two containers at the same divisions. Tests were also performed to determine the accuracy of the viewer. The results, not presented, showed that error was within 10 pct.

Jan 1, 1960

By J. Phillip Neal, Kefton H. Teague, Carroll P. Rogers

Feldspars, the most abundant minerals of the igneous rocks, occur in numerous forms and mixtures. The feldspars of commercial significance are found in widely distributed pegmatites as large crystals usually free of iron-bearing impurities and thus suitable for hand-cobbing, and also in larger bodies where the ore contains various types of feldspar intermingled with quartz and relatively free of iron-bearing impurities, or at least readily unlocked from impurities present at relatively coarse mesh. The latter type of ore includes some pegmatites, and the "alaskite" bodies so common in the Spruce Pine district of North Carolina. On the west coast of the US and in Oklahoma there is-or has been-commercial recovery of natural feldspathic sand as a source of alumina in glass and ceramics. "Aplite" in commercial terminology is a light-colored igneous rock with a granitic composition and a fine sugary texture, often banded with readily removable iron impurities. Only one area in Virginia produces aplite for the glass industry; it is located near Montpelier in Hanover County. According to Deer et al. (1966) the word feldspar derives from the Swedish feldt or jolt (field) and "spath:" chunks of rock appearing in tilled ground overlying granite. Castle and Gillson (1960) indicate a Germanic origin, citing "spat," which is said to refer to any transparent or translucent material which is readily cleavable. The term "spar" has in the past been applied to minerals other than feldspar, such as barite, calcite, and fluorite. It is correct to call the latter "fluorspar." There is a true barium feldspar, but it is rare and of no present economic importance. What is recognized as feldspar or "spar" by present producers and consumers consists of three silicate minerals which, if pure, would have the formulas KA1Si3O8 (microcline or orthoclase), NaAlSi3O8 (albite), and CaAl2Si2O8 (anorthite). These are almost never found in pure form in nature, but occur together in great abundance in a three-component system. A considerable number of different combined ratios of these three exists, with the exception that isomorphism between potassium spar and calcium spar is very limited. User specifications for feldspar products are largely built around the prevalent naturally occurring ratios. Passages following will refer to "K-spar," "Naspar," or "Ca-spar." Nomenclature and Descriptive Terms Relating to both the mineralogy and the economics of feldspar are certain terms whose coverage it is useful to specify. Commercially, aplite is a feldspathic rock mined and beneficiated in one location in Virginia, in which both titanium and feldspar minerals are present-the latter now being the major, if not the only, economic product. Technically, the term aplite when applied to this rock is of questionable accuracy. But, in light of accepted commercial usage, the term will be here used to designate it. Regarding the Virginia rock, Ross (1941) is cited. Alaskite is another term requiring understanding if not precise use. A distinctive rock type customarily called by this name is found near Spruce Pine, Mitchell County, North Carolina. An important major feldspar source, it contains somewhat higher levels of plagioclase feldspar and quartz than alaskite as defined in the Glossary of Geology and Related Sciences, which states that `orthoclase, microcline, and subordinate quartz are the principal

Jan 1, 1983

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By Donald E. Cummings

Measures appropriate for the control of the silicosis hazard in mining cannot be formulated precisely, but sufficient knowledge1-l9 has accumulated during the past quarter century to permit the suggestion of useful, though partly empirical, rules for its alleviation. The industrial hygienist today recognizes that the peril incurred by the inhalation of harmful dust is a function of two variable factors—the degree of harmful exposure and the specific susceptibility of the exposed individual to pulmonary injury. Control of the danger arising out of prolonged contact with pernicious airborne particulate matter is consequently best exercised by influencing both of these recognized variables. Obviously the problem has two broad aspects—one, medical; the other within the province of the engineer. I—Factors Comprising Degree of Individual Susceptibility Thorough investigations conducted among miners who have labored for years in the presence of recognized silicosis hazards usually reveal an impressive difference in the injury incurred by men whose exposure to dust has been nearly identical. After a quarter century underground, one individual is short of breath and incapacitated with miners' complaint, while a fellow workman suffers no pulmonary embarrassment and is in good health. Physicians ascribe this oft-observed difference in reaction to individual susceptibility and express a universal regret when they deplore the fate that chose to make the predisposed youth a miner rather than a farmer. To trust the health of miners to fate at the present time is even more unfortunate, because many of the factors that influence man's susceptibility to dust are known, and can be accurately determined by competent medical methods. Among the most important factors comprising susceptibility to injury by dust are the anatomical peculiarities of the individual's respiratory mechanism, his physiological response to the inhalation of dust, his previous dust, exposure, the existence of pulmonary infections or other pathological processes in his lungs, his age,

Jan 1, 1940

By Donald E. Cummings

Measures appropriate for the control of the silicosis hazard in mining cannot be formulated precisely, but sufficient knowledge1-l9 has accumulated during the past quarter century to permit the suggestion of useful, though partly empirical, rules for its alleviation. The industrial hygienist today recognizes that the peril incurred by the inhalation of harmful dust is a function of two variable factors—the degree of harmful exposure and the specific susceptibility of the exposed individual to pulmonary injury. Control of the danger arising out of prolonged contact with pernicious airborne particulate matter is consequently best exercised by influencing both of these recognized variables. Obviously the problem has two broad aspects—one, medical; the other within the province of the engineer. I—Factors Comprising Degree of Individual Susceptibility Thorough investigations conducted among miners who have labored for years in the presence of recognized silicosis hazards usually reveal an impressive difference in the injury incurred by men whose exposure to dust has been nearly identical. After a quarter century underground, one individual is short of breath and incapacitated with miners' complaint, while a fellow workman suffers no pulmonary embarrassment and is in good health. Physicians ascribe this oft-observed difference in reaction to individual susceptibility and express a universal regret when they deplore the fate that chose to make the predisposed youth a miner rather than a farmer. To trust the health of miners to fate at the present time is even more unfortunate, because many of the factors that influence man's susceptibility to dust are known, and can be accurately determined by competent medical methods. Among the most important factors comprising susceptibility to injury by dust are the anatomical peculiarities of the individual's respiratory mechanism, his physiological response to the inhalation of dust, his previous dust, exposure, the existence of pulmonary infections or other pathological processes in his lungs, his age,

Jan 1, 1940

By M. L. Samuels

DURING the period from 1910 to 1920, there was a lively interest in. the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth-why and how it occurs-were treated in papers by Howe,1 Jeffries,2 Sauveur,3 Chappell,4 Beilby,5 Mathewson -and Phillips,6 McAdam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,10 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size specified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filaments" wherein it is important to prevent "sagging" between consecutive turns of the helix.12 This practical use of a certain knowledge as to the things that influ-ence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,13 in the harden-ing treatments of high-speed steels,14,15 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is predominant no growth at all takes place. Under conditions in which

Jan 1, 1938

By Edward Adarns Richardson

As developed up to the end of the Great War, an airplane was essentially a mechanism of wood and fabric, joined and held together by metal fittings and fastening. The engine and accessories, wire for wheel spokes and other tension members, and the occasional use of metal for inter-plane struts and the shafts of surface controls required some metal, but essentially it was a wood and fabric structure. Attempts had been made to use metal for other purposes, such as struts in the drag-trussing of wing panels and for short interplane struts, and Junkers had produced an airplane of iron in 1915. By 1917 he was using steel tubes and duralumin sheets, securing noteworthy advantages aerodynamically and from the standpoint of weight and upkeep. He was a pioneer along lines in which progress is still being made. Principles of Airplane Construction The loaded weight of airplanes ranges from 500 lb. for the light plane of which we heard so much a short time ago, to about 40,000 Ib. The great majority of planes range from 2000 to 10,000 Ib. Of this weight from 15 to 30 per cent. is for the dividend-earning load. This percentage is so low that every per cent. saved on the rest of the weight increases the pay load from 3 to 6 per cent,. The economic value of every pound that can be saved in designing or constructing a plane is sufficiently great to warrant spending money on refined methods of structural analysis, materials of superior strength properties for a given weight, methods of manufacture which may make possible the use of refinements in structural design, and the like, to an extent unknown heretofore. The weight of the airplane, without fuel, oil and crew, and pay load, ranges from 50 to 65 per cent. of the total weight loaded for planes suitable for commercial use. It is doubtful if the structural weight will ever be brought down to as low as 40 per cent. for commercial planes. The airplane may be roughly divided into: (1) Power plant, which includes engines, radiators, cooling water, oil and fuel tanks, piping, propellers, engine-starting systems, pumps, super-

By Thomas T. Read

It is natural, in reviewing the progress that has been made in mineral industry education during the three quarters of a century that has elapsed since the American Institute of Mining Engineers was organized in 1871, to seek to establish some significant correlation. Earnest endeavor along such lines, however, produces nothing more in the way of fundamental relationship than a technical economic interest in mineral production and utilization in the United States, which had been steadily increasing since 1800. This is a sound correlation, since it is unquestionable that organized and systematic mineral industry education had its origin in Germany, more than 150 years before 1871, in an economic interest in producing minerals for use with the maximum of recovery at a minimum of cost. Mineral industry became the originator* and creator of systematic technical education because of the political and economic fact that in all European (and most other) countries, prior to 1800, precious metals belonged to the ruling power, no matter upon whose land they were discovered. The practical way of working under this system was to grant to a discoverer the right to work the deposit on payment

Jan 1, 1947

By Alexander B. Morris

In a recent paper on the intermittent injection of gas in gas-lift operations as opposed to continuous injection, Morgan Walker presented a comparative table showing the effect on oil and gas production from the same wells under the two methods of operation.' This table carried a column showing the formational gas-oil ratios under each method, computed by deducting the volume of input gas from the volume of trap gas. During the entire spring and summer of 1928, the present writer had been engaged on some extensive test car tests of rich gas in Glenpool, seeking, primarily, for an explanation of the apparent loss of gasoline during the summer season between the field meters and the plant master meter. Tests at several of the field meters where the richest gas was obtained regularly failed to check with other tests on the same gas made farther along the line, and the difference was not made up by the quantity of drip gasoline collected between the points. In the course of these tests, the final outcome of which is immaterial to the present purpose, an attempt was made to construct a curve representing the relationship between gasoline content of the gas in gallons per thousand cubic feet and the shrinkage in the volume of gas treated as a result of removing the condensible fractions. Such a curve was made, expressed in units of gallons per thousand cubic feet on the abcissa and the ratio vapor volume to liquid volume on the ordinate. This curve is a rectangular hyperbola and shows that 3 gal. of gasoline taken from 1000 cu. ft. of raw gas as a vapor occupied much less space, per gallon, than did 1 gal. of gasoline taken from 1000 cu. ft. of another sample of gas. This is, in general, corroborated by converting to the same units the residue settlement curves prepared by the Tidal Oil Co. and by the Natural Gasoline Manufacturers Assn., though the three curves, when plotted together, occupy entirely different positions on the paper, as shown in Fig. 1. The bearing of all this on Mr. Walker's discussion of gas-lift is this: if the formational gas is to be computed by deducting the input gas from the trap gas, some correction must be made for the vapor volume

Jan 1, 1930

By V. I. Purcell, S. C. Sun. R. E. Snow

A study including effects of 7) pH value, 2) fatty acid collector, 3) fuel oil, 4) interfering ion, 5) particle size, and 6) operational variables. Test results indicate feasibility of fatty acid flotation under certain restrictive conditions. FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in Florida."= The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo-wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being predominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon. Experimental Procedures: After being dried to less than 1 pct surface moisture the material was dry-ground in a Hardinge conical ball mill to —6 mesh. The ground product was classified into 6/20, 20/200, and —200 mesh size fractions. On the basis of Table I, the coarse and fine size fractions were considered as phosphate concentrates, because of their high phosphorus contents. In contrast, the 20/200 mesh fraction, which was low in phosphorus, was used as the flotation feed. All the flotation tests, unless otherwise stated, were performed in a laboratory Fagergren machine under the following conditions: 1) 400 g of solid feed for each test, 2) 2000 rpm impeller speed, 3) 8.9 pH and 4-min conditioning, and 4) 3-min flotation. The procedure used for the quantitative bubble pick-up tests has been described previously.18

Jan 1, 1958

By John Chipman, K. C. McCutcheon

To a very large extent the quality of a mild steel ingot is determined by the manner in which it is poured into the ingot mold and its behavior during the first few minutes after it has been poured. The formation of the solid rim of metal around the periphery of the mold, the effervescent action of the liquid steel within this solidified rim and the upward or downward movement of the metal level are indications of what is going on beneath the surface of the liquid metal, especially at the interface at which solidification occurs. Observation of this "rimming action" enables an experienced observer to predict the thickness of the sound skin of the ingot and the location and extent of cavities or "blowholes" caused by entrapment of gases. The control of rimming action at the hands of a skillful steel pourer is a vital part of the control of quality in mild steel sheet, and the behavior of the liquid steel during the rimming period is a useful criterion of the melting and refining practices employed in the open hearth. The behavior of rimming steel during solidification depends primarily upon the evolution of gases from the molten metal and it is therefore a problem of considerable interest to determine the nature and amount of the gases evolved. A number of attempts to determine either the amount or the analysis of the evolved gases have been reported. Klinger,1 in 1925, analyzed the gases extracted from rimming, semikilled and killed steel ingots and found that the chief constituent of the rimming gas was carbon monoxide. The relatively large amounts of nitrogen reported in his first few samples may have been due to incomplete removal of air from the gas-collecting mechanism. McKune2 reported similar studies of rimming ingots from which surprisingly large proportions of nitrogen and hydrogen were evolved. Ameen and Willners3 determined both the amount and composition of gases extracted from unkilled ingots with the aid of diminished pressure. . Their ingots weighed only 80 kg. (176 lb.) and apparently were solid within two or three minutes, so that their

Jan 1, 1938

By Rudolph Gahl

RUDOLF GAIL, Miami, Ariz.-Since I wrote the paper on flotation which is in your hands, important developments have taken place, and, for this reason, I will try in a few words to bring it nearer up to date as far as the Inspiration plant is concerned. You, may have noticed that in the Inspiration concentrator, flotation is not solely relied upon for the recovery of the coarser material, but that flotation tailings are split into a sand and a slime product on drag classifiers. The sand product is treated on tables which thus supplement the work of the flotation machines. Extensive tests have shown, us that, if we wanted to, we could leave out these tables and substitute additional flotation machines, as they will make fully as good, if not a better recovery than tables on the deslimed feed, but the treatment would be more expensive, especially in view of the fact that oils are required which cost more than those which we are now using in our main flotation plant. We have, however, decided to apply flotation treatment to our table middlings. I would also like to add a few words regarding the treatment of oxidized copper ores. Although our experience shows that the addition of hydrogen sulphide and other soluble sulphides effects a very good recovery of copper carbonates with certain ores, we have not been able to prove that we could use it advantageously for the ore mixture which we are treating in our concentrator, and for this reason, have looked toward leaching for extracting the carbonate and silicate copper that we are losing now. Experiments in this direction are going on and are giving very encouraging results. It may interest you to hear that we intend to use limestone for the precipitation of the copper which goes into solution, as electrolytic precipitation seems to be out of the question on account of the diluteness of the resulting solutions, and precipitation by iron was rightly objected to on account of the unavoidable contamination of the water supply. We feel very hopeful about the success of our limestone precipitation which, if it holds what it seems to promise, will develop into a novel feature of copper metallurgy.

Jan 10, 1916

By O. D. Gonzalez, H. A. Wriedt

Alloys ranging from pure iron to pure nickel were saturated with nitrogen gas at 918°, 999°, and 1217°C and analyzed. The solubility of nitrogen at 1-atm pressure was obtained as a function of nickel content for the whole range of iron-nickel alloys and the temperature dependence of solubility is shown for the experimental alloy compositions. The heat of solution and the entropy of solution of nitrogen in the alloys as func-tiom of composition up to 41 pct Ni are given. 1 HE acquisition of more exact thermodynamic information for systems composed of iron with various alloying elements continues to interest ferrous metallurgists. The interstitial alloying elements, especially carbon, hydrogen, and nitrogen, comprise a field of particularly intense study. A recent investigation of carbon solubility in Fe-Ni alloys held at 1000°C in gases of fixed carbon activity showed an unpredicted minimum in the solubility near 72 pct Ni.1 The present investigation was undertaken to see if a similar anomaly in solubility existed for nitrogen in Fe-Ni alloys. The solubility of nitrogen in ? iron at known nitrogen activities has been measured several times.&apos;-&apos; Corresponding information for the solubility of nitrogen in solid Ni and Fe-Ni alloys is not available. Juza and sachsze9 reported that metallic nickel dissolved 0.07 pct N in equilibrium with Ni3N at 445°C. This result was regarded as dubious by Turkdogan and Ignatowicz10 who found less than 0.0004 pct N in nickel specimens equilibrated at 600°C with ammonia-hydrogen mixtures having fugacities of N2 gas up to 35,000 atm. Such fragmentary reports indicate only that nitrogen gas has a very much lower solubility in nickel than in iron. MATERIALS A purified iron from Battelle Memorial Institute was used for solubility measurements. This grade contained more than 99.95 pct Fe, the highest content of any measured individual impurity being 50 ppm for each of As, C, Cu, and Pb. The nickel and iron-nickel alloys, supplied by the International Nickel Co., contained 0.02 to 0.04 pct C, 0.17 to 0.19 pct Mn, 0.04 to 0.08 pct Si, < 0.01 pct P, <0.03 pct S, and <0.20 pct Co as principal impurities. The Fe-0.59 pct Mn alloy was of zone-melted quality, the highest concentration of any individual impurity being 15 ppm Al. The "prepurified" grade of nitrogen gas from Matheson Co. had a nominal nitrogen content of 99.996 pct. An "electrolytic" grade of hydrogen gas from National Cylinder Gas. CO. in which the principal impurity is water vapor was admixed with the nitrogen to prevent oxidation of these specimens. This grade was preferred to a purer grade because the presence of some oxygen helps in suppressing contamination of the specimens, for instance, by silicon from the porcelain furnace tube. EXPERIMENTAL PROCEDURE The specimens were equilibrated in vertical tube furnaces through which a 99 pct N2-1 pct H2 gas was passed at ambient pressure. For the 915", 918", and 999°C runs, a wound-resistance furnace was used, and for the 1217°C runs, a furnace with a tubular silicon carbide element was used. The temperature control system on both furnaces was similar: a Weston "Celectray" controller with a modulator, responding to the electromotive force of a thermocouple with its hot junction in the furnace, switched the furnace current between high and low settings. The temperature distributions in the working zones of the furnaces were determined with calibrated Pt/Pt-10 pct Rh thermocouples. The overall uncertainty in temperature was estimated to be ±3° at 915° to 999°C and ±5° at 1217°C . Consideration of the small temperature coefficients of the equilibria studied, together with the error limits in the method of analyzing for nitrogen, showed that further refinement in temperature uniformity would give no improvement in resultant accuracy. The reactive gas was generated by mixing together "prepurified" nitrogen and "electrolytic" hydrogen directly from cylinders commercially supplied. The flow rates of nitrogen and of hydrogen were fixed by setting with bleeders the pressure drops across the individual calibrated flow meters of constant resistance. For any given alloy, the solubility of nitrogen at 1-atm pressure (% N) was obtained from the analyzed nitrogen content of equilibrated specimens (% Na)according to Sieverts&apos; law, thus

Jan 1, 1962

By E. W. Stewart, G. P. Conard, J. F. Libsch

The effects of several additives upon the reduction characteristics of hydrogen-reduced ferrous formate are described. The various additives inhibit sintering of the reduced iron particles by apparently different mechanisms. The magnetic properties of the low density compacts produced from the resulting ultra-fine iron powders were improved markedly. THE permanent magnetic characteristics of ultra-fine iron powder prepared by various means have been a subject of considerable interest and experimentation in the past few years. When such particles are small enough to show single domain behavior, they possess&apos; 1—permanent saturation magnetization, and 2—high coercive force. In the absence of domain boundaries, the only magnetization changes in a particle occur through spin rotation which is opposed by relatively large anisotropy forces. With decreasing particle size, the coercive force tends to increase to a maximum and then decrease because of the instability in magnetization associated with thermal fluctuations. Kittel&apos; has calculated the critical diameter at which a spherical particle of iron can no longer sustain domain boundaries or walls to be approximately 1.5x10-&apos; cm. Stoner and Wohlfarthr in England and Neel4,6 in France have shown from purely theoretical calculations that the high coercive force expected from single domain particles is dependent upon crystal anisotropy, shape anisotropy, or strain anisotropy contributions. Further work by Weil, Bertaut,&apos; and many others has contributed much to the understanding of fine particle theory. Neel and Meikeljohn" have demonstrated that a decrease in particle size below a critical value of approximately 160A leads to a quite rapid decrease in coercive force because of the prevention of stable magnetization by thermal agitation. Lih1, working with powders prepared by the reduction of formate and oxalate salts of iron, has shown the marked influence of powder purity upon magnetic properties. Maximum coercive force was obtained in powders of approximately 65 pct metallic iron content while the maximum energy product, (BxH) occurred in powders of 85 pct metallic iron content. Careful consideration of the preceding theoretical considerations and experimental results has led to the manufacture of permanent magnets from ultra-fine ferromagnetic powders by powder metallurgy techniques. Such work has been done by Dean and Davis," the Ugine Co. of France, and Kopelman." The aforementioned work of Kopelman and the Ugine Co. was concerned somewhat with the effect of various additives upon the properties of hydrogen-reduced ferrous formate. Virtually no work, however, has been published on the effects of additives on the reduction rates of metal formates, although unpublished work by Ananthanarayanan16 howed promise of improved energy product in ultra-fine iron compacts prepared by the hydrogen reduction of a coprecipitated mixture of magnesium and ferrous formate. After consideration of the preceding information, it was hoped that a better balance between the metallic iron content and particle size of the reduced iron powder could be accomplished by a prevention of the attendant sintering of the partially reduced iron powder during the reduction reaction. It appeared possible that magnesium oxide might interpose a mechanical barrier between adjacent iron particles and prevent their sintering together, while metallic cadmium and metallic tin would interpose a liquid barrier which might accomplish the same purpose. The degree to which these materials were effective in accomplishing the foregoing objective and the experimental details associated with the work are reported in the following sections of this paper. Experimental Procedure Preparation of Formate and Oxide Mixtures: To obtain ferrous formate of reproducible reduction characteristics, a slight modification&apos; was made in the technique of Fraioli and Rhoda." A supersaturated solution of ferrous formate was mixed with an equal volume of 95 pct ethyl alcohol and the formate crystals precipitated by stirring and screened to —325 mesh. These crystals were in the shape of elongated hexagons, approximately 4x10 micron in dimension. Various preparations of such ferrous formate, designated as lot 111, were reduced for 2 hr, yielding ultra-fine iron particles of exceedingly reproducible size, metallic iron content, and magnetic properties. The magnesium and cadmium formates were prepared by the reaction of dilute formic acid with their respective carbonates, while the tin formate was prepared by the reaction of dilute formic acid with stannous hydroxide. To evaluate the effect of metallic formate additives in intimate mixture with the ferrous formate, varying amounts of magnesium, cadmium, and tin formates were coprecipitated with the latter. The designations of these materials and their chemical compositions are given in Table I. Due to the differing solubilities of the various formates in aqueous media,

Jan 1, 1956

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By George D. Graffin

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3500°C and sublimes at about 4500°C. It is combustible in the presence of oxygen between 620° and 670°C, but is stable and chemically inert at ordinary temperatures.

Jan 1, 1975

By Irving A. Palmer

During the past 15 years in this country there have been few additions to the literature of lead smelting. After the consolidation of the principal smelting companies at the beginning of this period it became the policy of the larger company not to permit the publication of details in regard to many of its metallurgical processes. This led to similar action on the part of some of its competitors. The result, of course, was a decided decrease in the number of papers written upon the practical side of the subject. Even upon the theoretical side the contributions have been few. It would seem that the industry as a whole has suffered from this general unwillingness to exchange information. While it is true that a given company is entitled to the reward that may come from its own development of a new process, it is also true that a still greater reward might be the result of a free exchange of ideas with other plants. This principle has been recognized for a long time in other metallurgical industries, notably those engaged in the smelting of iron and the manufacture of steel. It is pleasing to note that the leading lead-smelting company has very recently decided to modify its policy of secrecy, and to permit the publication of papers covering some details of its metallurgical methods. The statement has been made that there has been but little progress in lead smelting during the period just referred to. This impression is due in part, no doubt, to the scarcity of papers written on the subject. &apos;There has been, it is true, some discussion of the new sintering processes, but with little reference to detail, and to the effect that blast roasting has had upon the industry as a whole. In spite of the prevailing belief, it may be said that lead smelting, in common with other metallurgical industries, has made steady and substantial progress. It is the purpose of the present paper to discuss briefly some features of the industry as it is now conducted, with special reference to the blast-furnace practice in the larger silver-lead smelting plants of the United States and Mexico.

Jan 1, 1915