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By E. J. Dulis, G. V. Smith

AS reported several years ago,' nitrogen may be taken up from the atmosphere by austenitic Cr-Ni steels during creep or creep-rupture tests. This was indicated by chemical analysis and by the appearance of a new microstructural phase, or phases, tentatively identified as chromium nitride (S), at the surface or at the intergranular cracks associated with fracture. The nitrogen pickup was observed to be dependent on time, temperature, and deformation. In a more recent investigation, a sample was obtained in which there was sufficient of the precipitate to suggest that it could be readily identified by X-ray diffraction. This sample had been taken from a 1/4 in. diam creep-rupture specimen of annealed, type 304L stainless steel of the following initial composition: C, 0.03 pct; Mn, 0.65; P, 0.010; S, 0.019; Si, 0.54; Cr, 19.50; Ni, 12.02; N, 0.031; and Al, 0.005. The specimen had ruptured after 10,470 hr at 1500°F (2000 psi). In this case nitrides were distributed across the whole section of the sample, Fig. 1. The precipitate occurred both at the grain boundaries and within the grains; the latter precipitate had in some cases the appearance of pearl-ite, and in others was distinctly Widmanstatten. Chemical analysis of the sample after test showed 0.64 pct "soluble" nitrogen (soluble in 1:1 hydrochloric acid: water) and 0.18 pct "insoluble7' nitrogen (insoluble in the hydrochloric acid solution but dissolved by fuming sulphuric acid). For identification of the precipitate by X-ray diffraction, the matrix in the surface layer of the specimen was dissolved by prolonged attack in an alcoholic solution of picric and hydrochloric acids. The appearance of the specimen surface after such etching is shown in Fig. 1c. The diffraction pattern of the surface-concentrated precipitate was obtained with a recording spectrometer in both the forward and back-reflection regions (the latter by adapting a special fixture to the conventional X-ray unit). The observed X-ray diffraction lines, Table I, show the presence of Cr,N and CrN; the agreement with interplanar spacings calculated from reported data2,3 is quite good. Since it has been suggested' that CrN dissolves only in concentrated sulphuric acid, whereas Cr2N dissolves in dilute hydrochloric or sulphuric acids, an effort was made to distinguish between the two nitrides. This proved possible, inasmuch as etching in a dilute solution of hydrochloric acid gave a sample in which microscopic examination showed that much of the Widmanstatten-pearlitic precipitate within the grains had been eaten out, leaving the grain boundary precipitate in relief, and which, when examined by X-ray diffrac-

Jan 1, 1953

By H. S. Rankin, E. C. Houston

OLIVINE is considered a valuable potential source of metallic magnesium in the chloride electrolytic process. Treatment of olivine with hydrochloric acid can be carried out under conditions that prevent the formation of gelatinous silicic acid, which would inhibit the reaction by forming a covering around the ore particles. It is our hypothesis that the formation of gelatinous silicic acid is avoided by the dehydrating action of the magnesium chloride, which takes up water to form a series of hydrates and leaves the silicic acid in granular condition. Leaching serves to separate the magnesium chloride from the silicic acid and unattacked ore, which can be treated with fresh acid in successive steps until extraction is essentially complete. The leach solution can be purified by the addition of caustic magnesia and the precipitated impurities removed by decantation or filtration. The resulting magnesium chloride contains: Fe, less than 0.001 per cent; Mn, 0.012 per cent; Ni, none. Chlorinationt of olivine has two major defects: (I) a large part of the chlorine goes to form silicon and iron chlorides, (2) the anhydrous magnesium chloride is held by absorption in the finely divided silica. SUPPLY It is well known that olivine, a silicate of magnesium and iron, is present in large amounts in several localities in the United States. The largest deposits occur in the southeast and on the Pacific Coast.1 The southeastern deposits were surveyed by Lewis2 in 1896 and by Hunter3 in the period 1933-1940. It is estimated that high-grade olivine, conveniently located with regard to transportation and power, is present in excess of 230 million tons above local drainage level in western North Carolina and north Georgia. PREVIOUS TECHNICAL WORK In the past few years, olivine has attracted considerable attention in the refractory field. In the chemical processing industry, however, it has long been thought axiomatic that the cost of processing silicates is an economic barrier to their utilization, especially where more reactive minerals, such as carbonates, oxides or salts, are available. This attitude is not entirely justified in connection with olivine. Unlike most silicates, olivine is readily attacked by acids, chlorine and other reagents without resorting to fusion to break down the silicate structure. Olivine has been suggested as a raw material for making epsom salt by roasting with pyrites.4 Other processes include acid treatments and digestion with calcium chloride.6 Recently a small plant was built near Webster, N. C., for making epsom salt from olivine by treatment with sulphuric acid. This plant is now in commercial operation, producing approximately two tons per day. Olivine is also receiving attention from the fertilizer industry as an inexpensive source of soluble magnesium.

Jan 1, 1942

By T. P. Meloy

The behavior of slime-sized particles in a flotation cell is neither well documented nor well understood. In general, slimes (or 'fines' as they will be alternatively called in this chapter) have been either ignored, eliminated, or treated empirically. Recently, however, some good experimental and theoretical work has been done that leads qualitatively to a clearer understanding of the problems involved. Fines are small particles that, owing to their smallness, behave differently from larger particles of the same material. The smaller the particle, the larger is its surface-to-mass ratio. The difference in the surface-to-mass ratio for a micron-sized particle and a centimeter-sized particle is 10,000 to 1. For our purposes we shall arbitrarily define any particle less than 10 µ 10-3 cm) as being a fine. This is generally considered the upper limit of colloidal-sized particles. Recently, the field of colloidal chemistry has successfully used the concept of the double layer to explain dispersion and flocculation of fine particles in a static system. Flotation, however, is a dynamic system due both to the turbulence of the liquid and to the coursing of the bubbles through the cell. Further more, a flotation system is a heterogeneous system in which there are a number of different types of particles which interact with one another. A further difficulty is that no two flotation systems are the same for minute quantities of a variety of common chemicals will alter the behavior of the system. These reasons make reproducible experimental results that can ex- plain fine-particle behavior difficult to obtain. In spite of these experimental difficulties, millions of tons of ore containing a large amount of fines are successfully floated every year. For example, at the Morning mill of American Smelting and Refining Co., a galena concentrate that was 42% -6 µ and a sphalerite concentrate that was 33% -9 µ were floated leaving a tailing that was 27% - 9 µ.l Ores that contain fines can generally be divided into two classes. In the first are those in which the valuable mineral tends to slime, such as galena and hematite. In the other class, one or more of the gangue minerals forms the slime; a typical example is barite. Though the problems due to the presence of fines are often the same in handling the two classes of ore, the method of handling them is different because of economic considerations. Nonmetallic mineral flotation is particularly affected by slimes, by either slime-coating effects or excessive reagent consumption. Though a given gangue mineral may not float under the conditions prevailing in the flotation cell, it may still be able to adsorb the collector. I£ it also slimes, a significant

Jan 1, 1962

By Wilford S. Wright

FOR the past four years the management of the Black Hawk Consolidated Mines plant at Mogollon has conscientiously kept accurate records pertaining to cost of operation and the performance of certain equipment. These records have been valuable in coordinating the work in the mine, mill and power plant. Also, as to quantity and kind of equipment and supplies most suitable from the standpoint of economy and dependable operation, they have served as a guide. Through comparison with records at other mines, where the same things are being done in a different way, they have pointed out mistakes to be avoided. No outstanding accomplishments, either in costs or performances, are revealed; in fact, some of the results are perhaps quite inferior to those obtained at similar plants, but it is with the thought that more records should be published for the benefit of the mining profession that the author presents these data. To other operators and to mining engineers who are called upon to make estimates for prospective operations, the information herein should be helpful. GENERAL CONDITIONS Mogollon is in the southern part of Catron County, southwestern New Mexico. It lies near the western border of the Mogollon Range, 14 miles east of the Arizona line. Silver City, 80 miles to the southeast, is the nearest railroad point. The connecting road, over which supplies are hauled into camp by trucks, is an improved highway for about 50 miles; the remainder consists of graveled roads and unimproved steep mountain grades. One general supply truck and one tank truck make daily round trips. Hauling of supplies to the mine has cost at the rate of $0.08 per ton-mile; or, on the basis of ore production, $0.30 per ton mined. Lumber, hauled in from local mills, has cost an average of $30.00 per 1000 board feet, $8.50 of which has been for hauling. The annual consumption averages 108,000 board feet. Lime, hauled from a plant in Arizona, is about the only other item not brought out from Silver City. Fuel oil for the generation of power is the item of greatest hauling expense, the f.o.b. Mogollon cost of approximately $0.06 per gal. being nearly twice the f.o.b. refinery price. Water for power plant, mill and camp use flows to camp storage tanks through a 4-in. pipe line from a spring and intake 3 miles up Silver Creek Canyon. A few times, particularly in the month of June, mill operations have been suspended for two or three days because of water shortage. MINING CONDITIONS During the years 1938, 1939, 1940 and 1941, the mine produced 230,059 dry tons

Jan 1, 1943

By George D. Roberts

Civil engineers are primarily interested in maximum core recovery. This is even more important in foundation work than in mining investigations where sludge samples are of some value. The soft materials, such as clay, gouge, or partially decomposed seams that are most readily ground up or washed away, are the materials that usually have the greatest influence on foundation and leakage conditions. Undisturbed samples of such materials should be obtained for detailed geological examination and laboratory tests. Therefore the attainable goal of sampling in connection with foundation investigations is the recovery of 99.9 pot of undisturbed core. Factors Causing Core Losses The principal factors contributing to core losses are: (1) coring badly fractured or very soft material; (2) Use of improperly designed coring equipment, including the use of bits of too small a diameter; (3) lack of the proper training and attitude on the part of the drillers and pertinent technical information on the part of the supervising personnel. Little can be done about the character of the material being cored but the other two factors contributing to unsatisfactory performance can be corrected. Although the title of this Paper is the improvement and standardization of core barrels, it is believed that the drillers' shortcomings and the lack of pertinent technical literature are more detrimental to good core recovery than either of the other factors. Uses For Large Diameter Core Barrels It is well known that the use of larger diameter bits and core barrels generally produce better cores, particularly when sampling soft or broken material. The use of larger and larger bit diameters and the insistence on better core recovery is well demonstrated by the change in practices of the various districts of the Corps of Engineers. Today NX core is the smallest diameter commonly permitted for investi-gational work and the more active districts are using coring bits up to 6 in. in diameter, as well as 36 and 40-in. calyx rigs. The latter size has proved to be just as economical because it provides more room for ctured removal and cleanup operations. The use of large diameter cores to replace the driving and jacking methods of obtaining soil samples is also increasing. The 57/8-in. Denison sampler, developed by H. L. Johnson to obtain samples from soft formations, is one example. The principal uses for bits larger than NX are: sampling soils and semi-consolidated rock; sampling decomposed rock or rock with soft seams; sampling concrete; obtaining samples for laboratory tests; drilling drainage holes, and other miscellaneous work. Core Drilling Practices of Several Engineer Districts Little Rock District The writer was employed in the Little Rock District from 1938 until 1942. Prior

Jan 1, 1949

By R. E. Ogilvie, N. L. Peterson

DURING the past few years there has been considerable effort devoted to the understanding of radiation effects on materials. The concept of the Frenkel defect and other lattice defects suggests that radiation may alter the rate of many metallurgical phenomena, especially those which are diffusion controlled. In 1953 R. R. Coltman and T. H. ~lewitt' found an appreciable effect on the ordering rate of Cu,Au due to fast neutron bombardment. Since then several rather comprehensive theories have been proposed on radiation enhanced diffusion in solids.2"4 If the energy of the radiation is above the threshold energy for the removal of atoms from their lattice sites, Frenkel defects will be produced. These defects can be produced uniformly throughout a relatively thick specimen by high-energy X-rays permitting bulk property studies without the limitation of sample dimensions. In this work high-purity arsenic containing 30 ppm of impurities was allowed to diffuse from the gase- ous phase at 700°C into single crystals of p-type germanium containing 0.1 ppm of indium. As the arsenic diffuses into the P-type germanium, an n-type layer will form in the diffusion zone. At the p-n junction the concentration ratio of the arsenic to the indium is constant. Experimental Procedures—The germanium specimens, 10 mm by 10 mm by 5 mm, were polished and etched to a mirror finish. The specimens were then sealed off in a vycor glass capsule at 3 x 10"5 mm Hg pressure with a sufficient amount of arsenic powder to produce a one-half atm pressure of arsenic at 700°C. Specimens were annealed at 700°C without radiation. The diffusion coefficient determined from these samples agrees within 8 pct of previous work done by Fuller.' Three specimens were given diffusion anneals at 700°C in a small tube furnace centered beneath the target of a 2-mev Van de Graaff generator. The specimens when in the furnace were 10 cm directly below the target of the generator. These specimens were irradiated continuously during the diffusion run with the Van de Graaff operating at 2 mev with a tube current of 225 to 250 pamp. The intensity of the x-radiation at the surface of the specimen inside the furnace was approximately 4.5 x l05 roentgens per hr. The temperature was controlled within m2°C by a chromel-alumel thermocouple throughout this work with no observed temperature change due to the radiation. By careful lapping, the samples were polished at an angle of 5 deg to the diffusion zone, giving a XI0 increase in the visible diffusion zone. The location

Jan 1, 1960

By Frank G. Miller

The lower cost of producing oil from naturally flowing wells compared with pro-luction costs accruing from artificial lifting methods has stimulated much research, rith the joint purpose of extending the natural flowing life of wells and of increas-ng the productivity of small wells. The iboratory investigation described herein was made to determine the effect of a lotted liner on the pressure gradient in the icinity of the wall of a flowing well. Flow estrictions caused by the liner induce nergy losses between the oil-bearing for-lation and the inside of the liner, which lay be reduced by improved liner design, nd thereby the flow capacity of wells may e increased. These losses have been evalu-ted for rectangular slots of different sizes, nd means are suggested for reducing them. The dearth of information concerning the ature of the flow of fluids from uncon-slidated sands through small openings in he walls of. pipes—as represented by the ow of oil from an oil sand into a slotted ner—is acknowledged. Although the bene-ts to be realized by operators through the se of optimum liners is just beginning to e recognized generally, Coberlyl in 1937 ointed out that the functioning of screen is is an important factor in the pro-uction of oil. From his study on the :lection of size of oil strings for wells in California, Parks2 concluded, in part, that the perforated section of the oil string deserves continued study, especially with respect to the selection of perforations. The growing use of gravel packing resulting from certain research findings lends even more significance to the problem of selecting optimum liners, as the application of these methods usually requires slotted liners or other kinds of perforated liners. The present study was made to obtain further information for the guidance of engineers and operators in selecting slotted liners and to develop a laboratory method that may be used in analyzing possible pressure conditions surrounding most types of perforated casings used in producing oil wells, so that the present inadequate fund of knowledge on this important subject may be expanded. Discussion of ProbleM At the beginning of the investigation the following assumptions were made regarding bottom-hole conditions of a producing oil well and the oil-sand reservoir it penetrates: (I) Conditions of steady-state flow exist, (') a a homogeneous liquid is being produced) (3) no contaminating material (such as drilling fluid) is present between the liner and the face of the oil-bearing sand, (4) the well is vertical and completely penetrates a horizontal sand stratum of uniform thickness occurring between two impermeable strata, and (5) the flow is wholly viscous. If the foregoing assumptions are made, with the added requirements that the sand

Jan 1, 1941

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By Frank G. Miller

The lower cost of producing oil from naturally flowing wells compared with pro-luction costs accruing from artificial lifting methods has stimulated much research, rith the joint purpose of extending the natural flowing life of wells and of increas-ng the productivity of small wells. The iboratory investigation described herein was made to determine the effect of a lotted liner on the pressure gradient in the icinity of the wall of a flowing well. Flow estrictions caused by the liner induce nergy losses between the oil-bearing for-lation and the inside of the liner, which lay be reduced by improved liner design, nd thereby the flow capacity of wells may e increased. These losses have been evalu-ted for rectangular slots of different sizes, nd means are suggested for reducing them. The dearth of information concerning the ature of the flow of fluids from uncon-slidated sands through small openings in he walls of. pipes—as represented by the ow of oil from an oil sand into a slotted ner—is acknowledged. Although the bene-ts to be realized by operators through the se of optimum liners is just beginning to e recognized generally, Coberlyl in 1937 ointed out that the functioning of screen is is an important factor in the pro-uction of oil. From his study on the :lection of size of oil strings for wells in California, Parks2 concluded, in part, that the perforated section of the oil string deserves continued study, especially with respect to the selection of perforations. The growing use of gravel packing resulting from certain research findings lends even more significance to the problem of selecting optimum liners, as the application of these methods usually requires slotted liners or other kinds of perforated liners. The present study was made to obtain further information for the guidance of engineers and operators in selecting slotted liners and to develop a laboratory method that may be used in analyzing possible pressure conditions surrounding most types of perforated casings used in producing oil wells, so that the present inadequate fund of knowledge on this important subject may be expanded. Discussion of ProbleM At the beginning of the investigation the following assumptions were made regarding bottom-hole conditions of a producing oil well and the oil-sand reservoir it penetrates: (I) Conditions of steady-state flow exist, (') a a homogeneous liquid is being produced) (3) no contaminating material (such as drilling fluid) is present between the liner and the face of the oil-bearing sand, (4) the well is vertical and completely penetrates a horizontal sand stratum of uniform thickness occurring between two impermeable strata, and (5) the flow is wholly viscous. If the foregoing assumptions are made, with the added requirements that the sand

Jan 1, 1941

By P. R. Schmidt, N. J. Themelis

A study zvas made of the deoxidation of copper at 1170°C by injecting a jet of carbon monoxide vertically upwards into the melt. The effects of submersion depth (2 to 20 cm), orifice diameter (& to 5 in.), and gas velocity (100 to 3650 ft per sec) were examined. In the oxygen range 0.1 to 1.0 pct 0, the overall rate was conlrolled by gaseoLcs mass Lransfer. The results were interpreted in terms of a rate coefficient per unit depth which was found to be constant with distance along the jet axis and nearly proportional to the orifice Reynolds number in the range 1000 < NReo < 9100. AS the gas flow rate through an orifice submerged in a liquid is progressively increased, at least three regions of bubble formation may be distinguished. At very low rates, the formation of bubbles is practically a static phenomenon, depending on the orifice diameter, the liquid surface tension, and the densities of the two phases. In this region, the bubble size is constant while the frequency of bubble formation increases with gas flow rate.&apos;-3 At higher flows (500 < NR~, < 2100), the frequency of bubble formation reaches a steady value and the bubble size increases with gas flow rate; when the bubbles issuing from the orifice become so large that they start coalescing to form larger bubbles, the turbulence induced in the liquid by the passage of previous bubbles shatters them into small bubbles of varying size. Finally, for gas velocities in the intermediate and turbulent regions of flow (NR,, > 2100) a tangential separation surface is created around the jet and momentum transfer takes place between it and the surrounding liquid medium. The entrainment of liquid and the resulting deceleration of the gas-liquid dispersion causes the jet to expand forming a characteristic jet cone. The large velocity and density differences between the jet and the liquid result in a high degree of instability and the jet envelope fluctuates rapidly.The characteristic jet cone can be observed by means of time exposure photographs such as those shown in Fig. 1 for an air jet introduced vertically upwards in a water bath. High-speed photography has showns that the gas-liquid dispersion within the cone consists of small bubbles the size of which depends mainly on the jet orifice diameter and Reynolds number. In the laminar region of flow, the following correlation was obtained by Leibson: The results of Liebson et a1.&apos; are plotted in Fig. 2. It can be seen that the region 2000 < NReo c 10,000 is not well-defined experimentally. In the entrance to the fully turbulent region of flow (NR,, = 10,000), the mean bubble diameter decreased to about 0.4 cm and varied only slightly from there on according to the correlation:

Jan 1, 1968

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By J. W. Spretnak, V. Kandarpa, G. W. Powell, R. A. Erickson

Neutron-diffraction pattens were obtained at room temperature from two austenitic manganese steels, oxc wth n carbon content of 1.23 zct PC/ and the olher 0.63 wt pct. Analysis of the data showed that the curOan atols (ions) occupy tile octaheadral site. any of the cavbon is in the tetahedral site, tile concentration is too strzall lo be detecled by tzeulr-on d$facton. AS part of a long-range investigation of eutectoid decomposition, a study of the structure of austenite has been undertaken in order to characterize as best as possible the parent phase in the Fe-C system. Austenite is a solid solution of carbon atoms in fcc iron, the carbon atoms being located in interstitial positions. Of the two kinds of interstitial sites, octahedral (0, +, +) and tetrahedral (4, a, $), in this lattice, the larger octahedral sites are usually considered as the probable position of carbon. The strain energy involved in pytting a neutral carbon atom (covalent di; ameter 1.54)&apos; into a tetrahedral site (diameter 0.56A) is considerably greater than that associated with p2tting carbon into the octahedral site (diameter 1.08A). Dayal and arkeen&apos; observed the migration of carbon in iron under the influence of an electric field indicating tha tye carbon is ionized. pe ionic radius of C&apos;4 is 0.15A and that of C" is 0.29. Consequently, it is conceivable that carbon ions could occupy the tetrahedral sites if one considers only the strain energy. Size considerations alone do not provide a complete explanation for the formation of the interstitial solid solutions, however. because metals such as copper, zinc, and cadmium do not appear to form interstitial solid solutions in spite of their large interstitial sites. Evidence which suggests partial ioni-zation of the carbon in austenite has also been obtained by Speiser, Spretnak, and alor who derived formu- lae relating the observed change in lattice parameter to the effective diameter of the solute atom. Assuming the carbon occupies the octahedral site. they computed the effective diameter of carbon to be 1.33A whereas the covalent diameter is 1.54A. petch5 concluded from powder X-ray diffraction experiments that carbon atoms occupy the octahedral sites. His conclusion was based on the general trend observed in the intensity of the diffraction lines as the carbon content of the austenite was increased. However, the major difficulty associated with application of X-ray diffraction to this particular problem is the relatively poor scattering power of carbon. Williamson and smallman&apos; utilized X-ray diffraction to study the line broadening caused by the strain field about carbon atoms inferrite: these investigators concluded that at least 85 pct of the carbon in ferrite occupies the octahedral (0: 3, B) site rather than the larger

Jan 1, 1967

By John M. Hartman

TWO systems are used for heating air in blast-furnace operations: I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100" F. as a maximum temperature of the blast. 11. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more comylex than the double surface, as it invoives the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300" F. to 1400&apos; F. is the best average temperature for economy of coal for safe working. This is equivalent to a saving of 11/2 to 2 cwt. of coal per ton of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the ralue of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxygen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800" in place of 1100°, it is obvions that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calorics lost to the hearth must be regained before good iron can be made. Take another case: A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1879

By John M. Hartman

(Read at the Wilkes-Barre Meeting, May, 1877.) Two systems are used for heating air in blast-furnace operations I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100° F. as a maximum temperature of the blast. II. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more complex than the double surface, as it involves the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300° F. to 1400° F. is the best average temperature for economy of coal for safe work¬ing. This is equivalent to a saving of 12 to 2 cwt. of coal per ton, of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the value of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxy¬gen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800° in place of 1100°, it is obvious that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calories lost to the hearth must be regained before good iron can be made. Take another case : A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1878

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By J. E. Gould, H. J. Hand

MANY independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types In maintaining quality control at the National Tube Company&apos;s plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final deoxidation In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding over-deoxidation to minimize the amount of inclusions present and to make as sound a steel as possible For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or long FeO values The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishing the state of oxidation at a given time Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors Data obtained are from actual furnace operations, the metal test being of the spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States Steel Corporation This method of taking open-hearth metal temperature was invented by Collins and Oseland,1 and was developed into its present form by L 0 Sordahl,2 of the Research Laboratory The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications 3,4,5 Slag components were obtained by chemical analysis Data were taken from four 165-net-ton furnaces during the working period of the heat Recognizing that additions of ore affect the

Jan 1, 1942

By H. R. Stahl

THE disseminated lead district of Southeast Missouri lies 70 miles south of St. Louis. The only metal of economic importance in the ore is lead, but minor amounts occur of iron, zinc, copper, cobalt, nickel, silver and cadmium. These minor metals, as might be expected, tend to concentrate in both the flotation and table middlings. In the past, some zinc has been recovered by differential flotation. The silver and cadmium tend to associate with the zinc, and some recovery is made of these two metals at the smelter. The lead occurs as galena, or lead sulphide. The minor metals are also present as sulphides. The presence of oxidized lead is suspected, but has not been definitely proved. The gangue is chiefly dolomitic limestone, with small amounts of sandstone and shaly glauconitic and chloritic minerals. The ore contains about 3.25 per cent lead, occurring as galena disseminated through the gangue. Some of the galena is very finely disseminated, and the mineral in the gravity tailings, or chat, is seldom or never in the free state. The method of treatment of the ore has been evolved over a period of 75 years; hence probably is not far from correct. The milling processes have tended toward simplification during the past 15 years, but recoveries have never been sacrificed for the sake of simplicity. In many cases, simplification of flowsheets has led to better recoveries and operating economies. A simplified flowsheet is shown in Fig. I. The St. Joseph Lead Co. operates four mills in the Flat River district, with a normal total capacity of about 21,000 tons per day, divided as follows: Federal mill, 11,000 tons; Leadwood mill, 4500 tons; Desloge mill, 3400 tons and Bonne Terre mill 2400 tons. The methods of concentration used at these plants are similar in principle; they differ mainly in details and in the type and size of the equipment used. The process of concentration may be divided into five main steps; i.e., dry crushing, wet grinding, classification with its attendant desliming, tabling and flotation. A brief description of these processes will be given, noting important differences in the various plants, and also noting the more important changes or developments of the past few years. DRY CRUSHING The run-of-mine ore is hoisted in skips, the capacity of these skips ranging from 2 ¾ tons to 8 ¼ tons. At the Desloge plant, the ore is hoisted in 2-ton mine cars on self-dumping cages. All ore is hoisted at shafts adjacent to the various crushing plants, no ore being transported on the surface. Primary breaking at all the mills is accomplished with 9E Telsmith breakers. Preliminary screening is provided ahead of most of these crushers, either by station-

Jan 1, 1943

By H. S. Rankin, E. C. Houston

OLIVINE is considered a valuable potential source of metallic magnesium in the chloride electrolytic process. Treatment of olivine with hydrochloric acid can be carried out under conditions that prevent the formation of gelatinous silicic acid, which would inhibit the reaction by forming a covering around the ore particles. It is our hypothesis that the formation of gelatinous silicic acid is avoided by the dehydrating action of the magnesium chloride, which takes up water to form a series of hydrates and leaves the silicic acid in granular condition. Leaching serves to separate the magnesium chloride from the silicic acid and unattacked ore, which can be treated with fresh acid in successive steps until extraction is essentially complete. The leach solution can be purified by the addition of caustic magnesia and the precipitated impurities removed by decantation or filtration. The resulting magnesium chloride contains: Fe, less than 0.001 per cent; Mn, 0.012 per cent; Ni, none. Chlorination[f] of olivine has two major defects: (1) a large part of the chlorine goes to form silicon and iron chlorides, (2) the anhydrous magnesium chloride is held by absorption in the finely divided silica. SUPPLY It is well known that olivine, a silicate of magnesium and iron, is present in large amounts in several localities in the United States. The largest deposits occur in the southeast and on the Pacific Coast.1 The southeastern deposits were surveyed by Lewis2 in 1896 and by Hunter3 in the period 1933-1940. It is estimated that high-grade olivine, conveniently located with regard to transportation and power, is present in excess of 230 million tons above local drainage level in western North Carolina and north Georgia. PREVIOUS TECHNICAL WORK In the past few years, olivine has attracted considerable attention in the refractory field. In the chemical processing industry, however, it has long been thought axiomatic that the cost of processing silicates is an economic barrier to their utilization, especially where more reactive minerals, such as carbonates, oxides or salts, are available. This attitude is not entirely justified in connection with olivine. Unlike most silicates, olivine is readily attacked by acids, chlorine and other reagents without resorting to fusion to break down the silicate structure. Olivine has been suggested as a raw material for making epsom salt by roasting with pyrites.4 Other processes include acid treatment5 and digestion with calcium chloride.6 Recently a small plant was built near Webster, N. C., for making epsom salt from olivine by treatment with sulphuric acid. This plant is now in commercial operation, producing approximately two tons per day. Olivine is also receiving attention from the fertilizer industry as an inexpensive source of soluble magnesium.

Jan 1, 1942

By L. B. Ticknor, M. B. Bever

An isothermal calorimeter suitable for measurements of heats of solution in liquid tin as solvent is described. Measurements of the heats of solution of gold, silver, copper, and a gold-silver alloy are reported. The heat of formation of this gold-silver alloy is also reported. HEATS of solution in liquids can be determined directly, but few such data have been published for metals as solvents. Knowledge of heats of solution is desirable because it contributes to the general understanding of energy relations in metallic solutions. Thermochemical measurements of this type also furnish answers to specific problems: For example, from the heats of solution of an alloy and of a mixture of its constituent elements in a given solvent, the heat of formation of the alloy may be found. Similarly, differences in the energy content of samples of the same metal in two different states, such as the annealed and cold worked states, may be determined. In the work reported here, gold, silver, and an alloy of gold and silver were dissolved in liquid tin at 240°C and gold, silver, and copper were dissolved in tin at 300 °C. The experiments yielded the heats of solution of these metals in tin. The heat of formation of the gold-silver alloy was also determined. The same calorimetric method is being used to measure the energy stored in metals during cold working and preliminary results have been published.&apos; Equipment and Experimental Procedure The isothermal calorimeter used in this work, Fig. 1, consisted of a Dewar flask completely immersed in a constant-temperature salt bath. A long neck provided space for thermocouple leads and a stirrer shaft and permitted the injection of solute samples. The metal bath in the calorimeter flask was stirred at about 100 rpm by a small glass impeller driven by a constant-speed motor. The shaft of the stirrer passed through a Wilson vacuum seal.2 All measurements were made under vacuum in order to eliminate temperature disturbances resulting from gas convection and to prevent the oxidation of tin. The calorimeter flask was joined by an all-glass connecting line to a gas-control system which made possible the use of a protective atmosphere of deoxidized and dried hydrogen. At the operating temperature of the calorimeter tin oxide was not reduced by hydrogen, presumably because the reaction rate was too slow. Part of the closed system was a removable side tube through which the solute sample could be introduced and in which it was held at a temperature of 0°C prior to injection into the metal bath. The salt bath containing a mixture of sodium, lithium, and potassium nitrates was similar to that described by Beattie3 and was equipped with a stir-

Jan 1, 1953