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By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By Edward L. Clark, Garrett A. Muilenburg

THE first record of the discovery of iron ore in Missouri was Marquette's observation in 1673 of brown iron ore, or limonite, in the Mississippi River bluffs just north of the mouth of Apple Creek in southeastern Perry County. There is no record of any attempt to mine or smelt Missouri iron ores until 1815, when the Ashebran furnace was erected at the Stouts Creek shut-in near Arcadia, Iron County. Some limonite was treated in this furnace, the first iron furnace west of Ohio, but most of the ore was hematite from Shepherd Mountain and adjacent deposits. Eight years later, in 1823, the Perry furnace five miles north of Caledonia, Washington County, was constructed to smelt limonite ore. It

Jan 1, 1955

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 Edward W. Parker

I. INTRODUCTION. AT the Seventy-sixth meeting of the Institute, held in New York, N. Y., February, 1899, I presented a, paper on this subject entitled, Coal-Cutting Machinery,' which has become somewhat out of date, in view of the decade's development in this feature of the coal-minim industry. It should be explained that the present paper is limited to the use of mining-machines in bituminous mines. Practically all of the anthracite mined is ?shot from the solid," no undercutting being done. Anthracite-mining is therefore not considered in the statistics or other references. The statistical record as compiled by the United States Geological Survey shows that in 1898, the year preceding the presentation of my former paper, there were 32,413,144 short tons of coal undercut by the use of machines. In 1907 the machine-mined coal-product amounted to 138,547,823 short tons. In sympathy with the general decrease in coal-production during 1908, the output of machine-mined coal decreased to 123,183,334 short tons, but the proportion of machine-mined coal to the total output, nevertheless, showed an increase, from 35.1 per cent in 1907 to 37 per cent in 1908. In 1898 only 19.5 per cent. of the total product was undercut by the use of machines. The number of undercutting-machines in use in the bituminous mines of the United States has increased from 2,622 in 1898 to 11,144 in 1907, and to 11,569 in 1908. The total production of bituminous coal in the United States in 1908 was almost exactly double that of 1898, while the machine- * Published by permission of the Director of the U. S. Geological Survey. 1 Trans.. xxix.. 400 to 4,59 (1899).

Sep 1, 1910

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By D. R. Parrish, F. F. Craig

In some respects, forward combustion (alias: fie-flooding, underground combustion, in-situ combustion, dry combustion) is an efficient oil recovery method. For example, its displacement efficiency (as much as 95 percent in reservoirs with high porosity and high oil saturation) is good. In its use of heat, however, forward combustion is grossly inefficient. Most of the heat generated during forward combustion is wasted. About one-fifth of the heat is picked up by the incoming air and re-used (regenerated); the remainder is left behind the combustion zone and ultimately is lost. Compressed air is expensive, and heat generated from compressed air via underground combustion is too valuable to be thrown away. Improvement is needed. Since the early 1950's, improvements in forward combustion by addition of water injection have been discussed, particularly in the patent literature, with increasing frequency.'-'' These concepts are based on the fact that relatively inexpensive water can be used to pick up much of the heat that is ordinarily wasted during forward combustion, and transport it forward to a more useful place, thereby reducing the amount of air required to move a heat front through the reservoir. Several approaches have been proposed. Merriam and Squires1 taught that a combustible (fuel) gas should be injected along with the air and water. This, however, would give at least a tendency toward reverse combustion instead of forward combustion, and would reduce the velocity of the heat bank, defeating the primary purpose of the water injection. Pelzer2 described primarily a batchwise method of forward combustion and water flooding. He advocated burning part way through a reservoir with forward combustion, then switching from air to water injection alone to push the heat toward the producing wells. Though possible, this method has serious disadvantages, the major one being that, by the time water injection is started, much of the heat has been irretrievably lost to the overlying and underlying formations. We have described what is considered a practical Combination Of Forward Combustion And Water-flooding (COFCAW).3,4 Air and water are injected simultaneously (or alternately) after a small heat bank has been formed by forward combustion. Some of the injected fluid fills up the region behind the heat bank; the rest enters the heat bank. Upon encountering heated rock, the water is converted into steam, which then flows ahead of the combustion zone and displaces much of the oil in place. Only enough air is injected to provide heat for vaporization of the water and to compensate for reservoir heat losses. Since the size of the heat bank is minimized, heat losses also are minimized. Because of more efficient oil displacement ahead of the combustion zone, fuel consumption is reduced. Too, unlike a forward combustion zone that cannot move until all fuel at a point has been consumed, COFCAW leaves some

Jan 1, 1970

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By N. A. D. Parlee, I. D. Shah

THIS communication reports the results of some work done on the effect of gold, palladium, and platinum on the liquid-gas-solid equilibrium in the Ag-O system,1,2 see Fig. 1. Recently several investigators3, 4, 5 have reported the effects of gold, palladium, platinum, and copper on the solubility of oxygen in liquid silver. This communication represents only a portion of the work done here on the solubility of oxygen in liquid silver and liquid Ag-Au, Ag-Pd, and Ag-Pt alloyss—the greater part having already been reprted. The apparatus, materials, and procedures used were similar to those of earlier work.' l The main precautions observed in obtaining these freezing points at constant temperature and PO2 = 1 atm were as follows: 1) The points were approached very slowly from higher temperatures. 2) In the very near vicinity of the L-G-S equilibrium point precautions were taken to see that the melt was in equilibrium with oxygen at one atm. Equilibrium was considered to have been attained when no more absorption of oxygen was observed in the last 15 min at a fixed temperature. 3) In the case of these alloys, the freezing point of the melt at 1 atm of oxygen and the equilibrium amount of oxygen absorbed by the liquid "infinitesimally" above this point were determined by lowering the temperature in very, very small steps, equilibrating at

Jan 1, 1969

By Joseph T. Roy

MINING revival during the last few years has brought about a considerable increase in the number of gold and silver determinations made, noticeable in all branches of the industry but especially so in the business of a custom smelter. At East Helena, solely a custom smelter the assay department found that the four assay furnaces available were inadequate to handle the increased amount of work. These furnaces were of a standard design, having duplex muffles, one superimposed on the other; each muffle was 12 1/2 in. wide, 18 1/4 in. long and 6 in. high, and could handle 72 cupels or 20 fusions. Since the heat varied considerably between the upper and lower muffles, cupellations were not ruin in both at the same time. To speed up assaying, E. A. Meale, chief chemist, had the happy idea of enlarging a muffle furnace, originally designed by the Montana Power Co., so that one muffle would acconmmodate at least as many determinations as the duplex muffles. An order was given to the Denver Fire Clay Co. for a Carbofrax muffle of the size required and the local engineering department enlarged the furnace to accommodate the muffle. Details of the

Jan 1, 1938

By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

By W. T. Ober

the hammering effect acts only to a point 3 in. back from the cutting edge, and the hardening heat extends back only 1 in. from the cutting edge. Then, as a steel is taken from the fire, the grain condition is as shown in Fig. I. After the forging operation has been performed the condition shown by Fig. 2 exists. The heating operation to harden the cutting edge produces the effect shown in Fig. 3. The questions that naturally arise are: Will the cost of the extra heat treatment necessary to change this condition (annealing) be more than the saving that may be effected in the drill steel or will the extra heating be an economical as well as a wise thing to do? Is this condition necessarily detrimental to the maximum service of the drill steel? Can this annealing action be obtained in the hardening heat by heating more of the bit, say at least 5 in., to the hardening temperature but quenching only the end of the bit by a shallow immersion? Short Rock-drill Steels Reclaimed by Welding By W. T. Ober, Lynn, Mass. Experimental tests by the Thompson Company have shown that short lengths of rock-drill steels may be reclaimed by electric butt welding. The drills used in the experiments were hollow drills l1/4-in. in diametcr containing 0.95 per cent. to 1.05 per cent. carbon. The ends to be joined must first be ground off fairly square and the greater part of the rust, scale, etc. removed for 3 or 4 in. back in order to insure good electrical contact with the dies of the welder and countersunk, with an 80° countersink, approximately 1/4 in. The steels are then clamped in the copper dies of the welder, so that a length projects from the inside edge of each pair of dies equivalent to from one-half to three-quarters the diameter of the drill. The drills should also be brought into accurate alignment. The first step is to bring the ends into close proximity and then close the primary circuit of the transformer, slowly bringing the steels together until their ends lightly touch, when they will "flash," that is, minute

Jan 1, 1922

By Donald L. Katz, Leo B. Bicher

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By Leo B. Bicher, Donald L. Katz

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By R. S. Olson

An analysis of the wash thickener-two stage filtration circuit was undertaken to quantitatively describe the circuit performance. On the basis of information developed in this study, the factors of major importance in reducing soluble loss are: filter wash, wash zone size, filter capacity, filter feed pulp dilution, blow back, filter cloth, water to repulp, water to primary wash, water to feed pulp and thickener underflow. The wash thickener-two stage filtration circuit has been used in many hydrometallurgical plants to separate solute from leach solids. As many as 20 to 30 plant operating variables determine the performance of the wash circuit and hence the soluble loss. The complex relationships of these variables, with each other and with soluble loss, make the evaluation of their effect on mill performance difficult. An analysis of this type of circuit was undertaken to quantitatively describe the circuit performance. THE CIRCUIT The diagram in Fig. 1 represents the operation of the wash thickener-two stage filter circuit. This circuit provides for counter current, cross current or for a combination of countercurrent-cross current operation. The feed pulp stream, J, is intended to include any solution or water, other than primary and secondary filtrate, which enters the wash thickener. Except for filter washing, the operations in the circuit are simple mixing operations which can be described by material balance. The concentration of solute in the filtrate and cake solution after application of wash liquor cannot be described by simple material balance. The displacement washing equation, derived by Rhodes1 and extended by Choundhury and Dahlstrom,2 appears to best describe this case of miscible displacement in porous media. In a useful form, it is

Jan 1, 1963

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957