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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 R. W. Hunt

The old plan was to increase every part of a rail much in the same proportion. But each part should be in proportion to what it ha.; to do. The head should be deep in proportion to tile amount. of traffic and the lowness of the rate of interest on its cost. The body need only he strong enough to carry the head after it is well worn down, and that deperlds on the weight of the machinery, and in the case of steel has little to do with the volume of traffic, except SO far as that affects weight of machinery. Ad on most railroad systems, the same niacliinery is used on main lines with heavy traffic, and bra11ct:es with light, I suggested in 1874 that each systern adopt the same body of rail for both, and make the head deeper on the main lines, shallower on the branches. This plan was adopted on the Pennsylvania Railroad. Bandberg seems to recognize this in his patterns of 1878. E. W. HUNT, TRoy, N. Y.: Again Dr. Dudley preaents to our cousideration a series of most carefully conductetl experiments, and ~llile I fully appreciate the labor and thought this work has cost him, I must still hesitate to accept his deductiono. This paper dilliirs from the previous one in that it denls esclrieively with the wearing qualitiei. of steel rails. Dr. Dudley gives his reason for this change in the following statement: " With the improvement in maintenance of way which has characterized the Pennsylvania Railroad during the last five or six yearn, the remova1 of rails from the track from the first two of these causes (i. e., broken and crushel), has, if I am right, quite notably diminished. This certainly is true with regard to broken rails. And if, as time advances, the number of crushed rails shall diminish, both because of the continued improvement in maintenance of way before referred to, and because, owing to improved and better methods at the steel works, there are fewer crushed rails caused by physical defects in the steel, the question of the wearing capacity of steel rails obviously becomes the allimportant one." Certainly the condition of the roadhd has much to do with mils brealring, crushing, and wearing. If the Pennsylvania and other railroads have done and are doing their part, Dr. Dudley oourteously admits that the steel works have performed part of theirs. But as far as I am informed, the formulas which they have used have been and are still quite wide of the one he continues to recommend. The rails which are not breaking or crushing to so great an extent as formerly, contain higher percentages of both carbon and manganese.

Jan 1, 1881

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineracao de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60' and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Padua, Sao Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the Silo Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has beer] carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, nith nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1947

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 i 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† 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.' 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 treatment6 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 George L. Reiter, George B. Clark

Commercial strip mining of coal was first begun in the state of Illinois in 1911.l The annual tonnage of coal produced from coal strip mines in the state was very small until 1924, when the strip mines shipped 1.68 pct of the total state shipping mine tonnage. Since then, strip mines have gradually come into their own by producing a sizable percentage of the coal produced in the state. Table 1 shows the coal tonnage shipped from both underground and strip coal mines in the state of Illinois for selected years. The table illustrates the major role that strip mines play in the state's coal industry. Today, strip mining is generally conducted in areas where the coal seams lie so close to the surface of earth that a stripping method of mining the coal seam is cheaper than an underground method. Strip mining not only recovers 100 pct of the coal deposit, but may also be used as a method of mining large acreages of coal abandoned by the closing of underground mines. Open cut or strip mining is a very highly mechanized method of producing coal and is carried on in three distinct and separate operations. The first of these is uncovering or exposing the coal seam so that the coal is made available for mining. The second operation is that of actually mining the coal. The third operation is the washing, crushing and grading of the coal according to the producer's market. Description of Shovel The Marion 5560 power shovel is used in the first of these three operations. The large electric-powered shovel works forward and back across the coal deposits, removing the overburden of dirt, rock, and clay in successive cuts of 30 to 60 ft deep and 40 to 80 ft wide. The shovel has a maximum cutting height of 95 ft, but around 60 ft is considered to be the maximum economical cutting height by the operators. The smaller the depth of cut, the more economically the shovel will operate until a minimum cut of 15 ft is reached, below which the efficiency decreases rapidly. The Marion shovel may be used in tandem stripping in excessive depths of overburden. The other type of excavating equipment used in the tandem team is generally a dragline with a long boom of about 180 ft. In tandem stripping, the dragline is used to remove the upper portion of the cut and to place it at a maximum dumping radius from the place of removal. The Marion 5560 power shovel is then used to remove the overburden left above the coal seam and to deposit it at the shovel's maximum dumping radius. The Marion 5560 power shovel is of gigantic proportions. It has a 102 ft 6 in. boom and 32 cu yd dipper and is

Jan 1, 1950

By P. H. Bohart

THe answer to the title question will be found by considering the ultimate influence of the petroleum engineers on industry and by considering the tools with which petroleum engineers must be equipped. Some 2000 to 3000 petroleum engineers are being absorbed by the industry yearly, indicating the magnitude of influence which they may exert on the industry. The petroleum industry is a highly technical one and it is inevitable that management be entrusted more and more to executives with technical training. The industry, therefore, expects the petroleum engineering schools to provide a broad basic training and a social and economic orientation which goes beyond merely supplying the minimum technical qualifications necessary to discharge responsibilities for a particular job. Because of the many branches of industry, emphasis must be placed on the Student's being trained in fundamentals, as well as grounded in other engineering branches, such as mechanical, civil and electrical engineering. The petroleum engineering graduate must know how to outline and organize the material for an engineering report and should be thoroughly grounded in English, both written and spoken. Even to the end that a five-year course may be required, they should receive instructions in auxiliary cultural and social science courses, industrial relations, and public speaking. Training in the method of approach to an engineering problem is something in which industry is deeply interested. A standard of ethics, a desire to arrive at the truth, and leadership training should be stressed. Introduction The basis of an an to any ques- tion concerning the petroleum engineering schools' responsibility to the industry will be found by considering the ultimate influence of the petroleum engineers on the industry and by considering also the tools with which petroleum engineers must be equipped in order to achieve success and happiness in the role in which their training, individual talents and choice of a profession ultimately will cast them. The problem must always be considered as it relates to a large group and not as it relates to a particular individual possessing strong natural talents and destined, by virtue of them, to pursue a certain course. The question implies that petroleum engineering schools have a responsibility, and indeed they do, not only to the industry but also to the students and even to the public. Because the responsibility is concentrated in a relatively few schools whose graduates are absorbed largely by the one industry, the responsibility is more apparent and the effect of failure to discharge the responsibility fully is more serious than the effect of similar failure on the part of schools supplying a smaller portion of the industry's intake of engineering graduates. This fact is especially true with respect to an industry such as the petroleum industry whose ratio of technical to nontechnical employees is relatively high and is increasing.

Jan 1, 1948

By L. G. Graper, E. L. Ramsey

The present program of increased production of armament and lend-lease material for mechanized war has created a problem for the shops that must do the machining. They have naturally turned to the steel producers to provide them with a steel that can be accurately machined with the greatest possible speed. The adding of sulphur to steel as an aid to machinability has long been practiced; however, it may cause red shortness in rolling and may result in billets with seams and cracks, which must be removed before rolling can be continued. This conditioning of billets slows down production and adds to the cost of making steel. Experience with various grades of sulphur steel made to different specifications has shown that Bessemer sulphur steels roll better than similar grades made in the open hearth, and also that low-carbon steels that are open or semikilled as tapped roll better than completely deoxidized or killed steels. This has led to the belief that oxygen plays an important part in the rolling qualities of sulphur-bearing steels. It is generally held that the red shortness of sulphur steels is due to the low melting point of the sulphide compounds that separate out at the grain boundaries when the steel solidifies. At the rolling temperature of steel these sulphide compounds melt and cause cracking. Adding Sulphur as a Sulphite These difficulties can be avoided if sulphur is introduced into the stecl by means of an anhydrous sulphite, such as sodium sulphite or sodium bisulphite, which—upon decomposition—forms sulphur dioxide. It is assumed that, in this case, the oxygen of the sulphur dioxide forms part of the sulphide inclusions in the steel, and raises their solidification temperature enough so that the formation in the steel of a low-melting eutectic is prevented. The result is the prevention of hot shortness and a more uniform distribution of inclusions. Fig. I shows photomicrographs of steels made with sulphur, while Fig. 2 illustrates the structure of steels made with sodium bisulphite. These samples were cut from the steels as cast—that is, before rolling— and were polished and lightly etched to bring out the grain boundaries. Fig. I shows that sulphide inclusions segregate more or less at the grain boundaries, and it can be seen how the continuity of these low-melting inclusions would cause red shortness. Fig. 2 shows that the sulphide inclusions arc more or less uniformly distributed throughout the matrix. This arrangement of inclusions has no apparent effect on the rolling qualities of a steel. This statement has been substantiated by the observation of the rolling of over 6000 tons of steel made with a sulphite addition. Results As stated before, the sulphur dioxide is added to steel by means of the decomposi- 27

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN a previous study' of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is a more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about r1to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, 1 per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to 1-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudomartensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously' that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By V. Patarini, D. Kuehl, F. Galasso, M. Salkind

In recent years, a great deal of research has been directed toward the production of continuous low-density, high-strength, high-modulus boron fibers for aerospace applications. A technique which has proven to be quite successful for forming these fibers involves the reaction of boron trichloride and hydrogen on a hot tungsten wire. In this process, a boron fiber is produced which consists of a tungsten boride core covered with amorphous or crystalline boron depending on the temperature of the preparation.2,3 The purpose of this paper is to present the properties which have been obtained to date from measurements and observations on these fibers. Selected samples of boron filament produced by reacting boron trichloride and hydrogen on a 0.5 by 10-3 in. diam tungsten wire substrate using different reacting temperatures were cross-sectioned, polished, and photomicrographed with cross-polarized light. The temperature of the wire was measured using a two-color optical pyrometer. Photomicrographs of these samples are shown in Fig. 1. Three general types of boron, in addition to the tungsten borides, have been identified by means of X-ray powder diffraction techniques: a) at low temperatures (below 1400°C) the boron is deposited in the amorphous form; b) at temperatures between 1400° and 1500°C the boron is deposited in the ß tetragonal form; and, c) above 1500°C the boron is deposited in the B rhom-bohedral form. In the depositing range of 1400" to 1500°C the boron initially deposits as amorphous and becomes crystalline as evidenced by the large equi-axed grains which then merge into columnar grains in later stages of boron deposition. This can be seen in Fig. 1 and has been observed in the X-ray patterns of these fibers, which contain both halos from the amorphous boron and lines from the ß tetragonal form. Above 1500°C the only boron reflections observed in the X-ray patterns were those of the ß rhombohedral form and only columnar grains are seen in the photomicrographs. Photomicrographs of the surface in Fig. 2 show the smooth-surface kernal-type deposition which corresponds to the amorphous form and the rougher surfaces which correspond to the crystalline form. Mechanical measurements were made on amorphous boron produced at 1300°C rather than the crystalline boron because the strengths of these filaments were greater and were more consistent. A tensile tester consisting of a fixed crosshead containing a double

Jan 1, 1967

By L. C. Snider

All important industries have certain basic principles in common which govern them and give them a family resemblance. In addition, each industry has a certain individuality due to some principle or principles which govern, or are accepted as governing, that industry and which is not effective in others. The customs and practices of an industry depend on these basic principles much as the corollaries follow a proposition in geometry. After the proposition is proved or is accepted as proved, the corollaries are seen to be true almost without additional evidence or proof. In many cases, the corollaries are more important in practical affairs than the proposition on which they depend. By continued application the corollaries may come to be accepted as law and the fact that their truth depends on the correctness of the fundamental proposition is forgotten or ignored. If it is discovered that an error was made in demonstrating the proposition and that the proposition is untrue, the corollaries are, in most cases at least, equally untrue. Considerable time may be required, however, to realize the fact that the corollaries have failed, particularly if they have been embodied in custom and law. For example, in the business of government the proposition that women are intellectually inferior to men was formerly considered, by most men at least, to be duly proved if not axiomatic. This propositiot was never embodied in law, but its corollaries—that the rights of the wife in property and even in her own children were inferior to the rights of the husband, and that women had no place in governmental affairs—were duly incorporated in law or so completely approved by custom that they had the effect of law. Developments of the past few decades have proved, to the satisfaction of the majority, that woman's intellectual inferiority to man had not been satisfactorily demonstrated, and that the proposition that she was inferior, although accepted for many generations, was untrue. It was not so great a shock to men to discover that this proposition was wrong as it was to find out that its corollaries were also untrue and that the laws embodying them were not good laws and were subject to repeal. The adjustments which give women equal rights with men

Jan 1, 1932

Using 5-p Ni powder and 0.018 ,u A1203, oxide dispersion strengthened nickel alloys were prepared by mechanical mixing of powders, followed by compaction, sintering and extrusion. Processing variables such as cooling of the powder during mixing, electrostatic discharging, mixing time, amount of oxide, and so forth, were studied to determine the effects on room-temperature tensile and high-temperature creep-rupture properties and on the reproducibility of alloys. MECHANICAL mixing of metal and metal oxide powders provides one of the simplest and most inexpensive methods for preparing dispersion strengthened metal-metal oxide alloys;" however, because of large differences in specific gravity, powder particle diameters and other variables, difficulties have been encountered in reproducing alloys and alloy properties. Using 5-p Ni powder and 0.018 p A1203, the following variables were investigated: a) Blending techniques b) Blending time c) Volume fraction of oxide for the selected pow- ders d) Sintering of compacts before extrusion Cooling of Powders During Blending— Cremens and Grant had indicated that dry ball milling of the powder mixture gave superior results over other procedures. When ultra-fine metal and oxide powders became available and comminution was unnecessary or offered little gain, the use of dry mixing in a Waring Blendor gave optimum results.' In the current study, observations of the powder mixtures indicated that considerable heat was generated due to the high speed of the Waring Blendor (15,000 rpm). This heating appeared to produce some degree of clustering and pelletizing. To minimize such agglomeration, a Pyrex cooling coil was installed in the mixing vessel. A double coil, water cooled, proved to be quite satisfactory, providing a fair degree of cooling along with good erosion resistance. Discharge of Electrostatic Charge—Electron-microscopy showed that agglomeration was minimized by the cooling procedure but was not entirely eliminated. It appeared that some of the ag- glomeration had to be explained on the basis of an electrostatic attraction due to the high-speed blending operation. These charges had the effect of promoting the growth of alumina clusters. At the end of the blending procedure such clusters had an effective size which was as much as 50 times that of the individual powder particles and were very tightly bunched. Several methods were utilized to try to discharge the electrostatic forces to minimize the clustering. One successful method, utilized in alloy 17, involved continuous exposure during blending to a radium source of 50 millicuries at a distance of 1.5 ft from the container. A number of other methods were noted to work equally well. Fig. 1 shows the more open oxide structure which results from such a treatment, permitting the matrix metal to penetrate into the cluster more effectively. The combination of powder cooling and discharging led to noticeably improved structures. Fig. 2 shows a cross and a longitudinal section in alloy M-17, one of the best alloys, illustrating the marked decrease

Jan 1, 1961

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. 'The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew' suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman's' observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By Louis A. Panek

THE purpose of this paper is to present a method of designing safe and economical arch structures that are to be constructed of concrete or directly of original earth materials. The experimental data used to illustrate the design method are taken from Bucky and Fentress,1,2 and the application of the ideas presented by them is extended by obtaining an additional set of curves from which arch structures may be designed. This design method is based upon the following principles of similitude: A scalar model made of the same material as that of the full sized structure will behave similarly to its prototype if the density of the model is increased in the same proportion as its linear scale is decreased. Let R represent the scale or model ratio, namely, the ratio of a prototype linear dimension to the corresponding model linear dimension. The effect of increased density may be obtained by rotating the model in a centrifuge at a speed such that the centrifugal field exerts on the model an accelerative force R times the accelerative force of gravity. Under these conditions; (I) model unit stresses are equal to corresponding prototype unit stresses, (2) the ratio of the prototype deformation at a given point to the model deformation at a similar point is equal to the scale ratio, R, and (3) the model and the prototype will behave similarly within and beyond the elastic limits of strain. According to the above relations, such models can be used to solve the following problems: I. The dimensions of the most economical safe arch structure for a given load. 2. The maximum safe roof span underground for given geologic conditions. The procedure is described briefly as follows. Tests are made by rotating in a centrifuge a number of models that repIesent a variety of prototype loads and dimensions. From the experimental data, curves are plotted to show the relations between these loads and dimensions. The curves are used to solve directly the problems stated above. Structural design is based upon the working (safe) stress of the material of construction, which is established by applying a factor of safety to the experimentally determined ultimate strength of the material. In conformity with this principle, each model is gradually loaded until failure occurs. A safety factor is then applied to the results. If a safety factor of 4 is used, a given model at failure represents a safe prototype, the linear dimensions of which are equal to one-fourth the model ratio at failure times the corresponding model dimensions. The safe model ratio is computed from the following formula: [Safe R = (rl 47r2n2r _ 7r2n2r~r~ \4/ gg in which: n = centrifuge revolutions per second at model failure; r = radius of rotation of the model in feet; g = 32.2 ft/sect.]

Jan 1, 1947

By G. H. Matheson, J. M. W. Mackenzie

The coal concentrates studied contained clay slimes which would not flocculate on the addition of a polymer flocculent alone. The mechanism of the flocculation process is interpreted on the basis of the flocculation of lyophobic colloids. The filtration rate characteristics are shown to deviate slightly from certain basic filtration equations. Cake moisture was shown to decrease with cake drying time and vacuum, and increase with cake thickness. Filtration is a commonly accepted method of dewa-tering the fine coal concentrates produced in coal cleaning operations. Dewatering of these concentrates, using drum or disc vacuum filters, usually presents few technical difficulties and will result in the production of a filter cake containing some 20 to 25 pct moisture. In many coal cleaning operations it is common practice to add flocculants to the coal concentrates prior to filtration to increase the filtration rate. The mechanism whereby flocculation increases filtration rate has been summarized by Gaudin,4 while Geer, et a15 have compared the effectiveness of starch and synthetic flocculants as filter aids for a variety of coal concentrates. Coal concentrates, containing appreciable quantities of expanding lattice clays of the montmorillonite-illite group, sometimes prove impossible to filter without flocculation of the pulp prior to filtration. The fine coal concentrates produced at the Newcastle washery of The Broken Hill Proprietary Co. Ltd. fall into this group. Coals mined in this district contain appreciable quantities of expanding lattice clays which break down in the washery circuit waters and, by processes of mechanical inclusion, contaminate the coal concentrate thickener feed. Despite the classifying action of this thickener, the underflow which is pumped to the filters contains sufficient clay slimes to render filtration of the unflocculated pulp impossible. Filtration leaf and plant tests were carried out to develop effective and economic flocculant combinations and to determine the filtration characteristics of the flocculated coal concentrates. The determination, by leaf testing, of the filtration characteristics, and the analysis of these characteristics in the light of the equations of Brown2 resulted in the successful trial operation of the filters in the Newcastle washq. Although the filtration characteristics are not entirely in agreement with the theoretical treatment of Brown, the equations developed made it possible to predict, from leaf tests, the effect in the plant filters of pulp density, form vacuum, and form time on filtration rate and filtrate volume. EXPERIMENTAL PROCEDURES The sample used for leaf testing was the coal concentrate thickener underflow, which in plant operations would form the feed to the two 12-disk Dorr-Oliver filters. The feed to the coal concentrate thickener comprises the undersize produced by dewatering the Diester table concentrate on 5-mm dewatering screens and the overflow produced by cycloning of the froth flotation concentrate. At the time of testing these filters were inoperative because of the difficulties in filtration, arising from contamination of the

Jan 1, 1962

By George F. Comstock

IT has been reported recently1 that the hardenability and toughness of forging steels may be improved appreciably by the use of complex deoxidizers containing titanium, aluminum, and vanadium. In the light of these results, an investigation of similar deoxidizers containing various hardening and grain-refining elements was proposed. These deoxidizers included three manganese-silicon-aluminum-titanium al- [ ] loys with and without boron and calcium, three titanium-aluminum ferroalloys with vanadium, molybdenum and zirconium, respectively, an aluminum-zirconium ferro-alloy, and plain ferroboron. Their approximate compositions are given in Table I, and the results obtained so far in the investigation of their effects on steel are presented in the later parts of this paper. METHOD OF USING DEOXIDIZERS The deoxidizers listed in Table I were used in three series of 0.40 per cent carbon steels, which were melted in a small basic-lined induction furnace and cast in the form of I7-lb. ingots about 2.75 in. square. The basic charge for each heat was 10 lb. Armco iron and 6 lb. of clean low-carbon sheet-steel scrap. When melted, this charge was deoxidized with 15 grams of ferrosilicon, then about 500 grams of pig iron was added to give the desired carbon content. After the pig iron was dissolved, nickel [ ] shot and high-carbon ferrochromium were added if required, and additions of 80 per cent high-carbon ferromanganese and 50 per cent ferrosilicon were made to provide the proper amounts of those elements. Aluminum was added to every heat 2 min. after the silicon, for grain-size control and preliminary deoxidation. One minute later the special deoxidizer was added to the clean bare surface of the molten steel, and 2 min. afterward the steel was poured into the ingot mold, using a hot-top and pipe-preventing compound after pouring to decrease the depth of the shrinkage cavity. The special deoxidizers were used mostly in the form of about ½ to ¾ -in. lumps,

Jan 1, 1942

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. $ deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks. Types of Items far Consideration On the hazard, or negative, side some of the common items to be considered are: 1. Subsidence and resulting damage. 2. Flo wage of water above that anticipated. 3. Geological. (a) Decline in quality of probable ore, and/or (b) Decline in quantity of probable ore. 4. Depressed economic conditions. 5. Litigation. Similarly, on the enhancement, or positive, side common items to be considered are: 1. Flo wage of water below that estimated. 2. Geological. (a) Increase in quality of probable ore, and/or (b) Increase in quantity of probable ore. 3. Elevated economic conditions. 4. Litigation. 5. Technological advance in the art. Tn all of the above items no consideration is given to placing a value on, or giving consideration to, possibilities. For example, referring to Table 1, the estimated normal present value (Vp) of a property, exclusive of risk consideration, is taken as $100,000. If subsidence affects the usefulness of the shaft, the present value of the property will decrease to $60,000, and it is judged that there is a 1 in 4 chance that the shaft will be impaired;, consequent.ly, if subsidence took place, the present value would be reduced ($100,000-$60,000) $40,000, but since the chance is 1 in 4, the allowable reduction would be only one-fourth of $40,000, or $10,000, or a discount of 10 pct (hazard factor) of the original value; the related safety factor is taken as unity minus 0.10, or 0.90. Thus, the original Vp, $100,000, multiplied by the safety factor ($100,000 X 0.90) gives $90,000, which is the adjusted present value of the property in this single instance. Additionally, there is a water hazard, which, if encountered, will reduce the present value to $85,000. The chance is 1 in 3. Following through with the same reasoning as shown above, the derived safety factor will be 0.95. To arrive at a single multiplying factor which will express the combined risks, the two safety factors are multiplied together, 0.90 X 0.95 = 0.855. That factor when multiplied by the origirial Vp will give the adjusted, and

Jan 1, 1950

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By N. A. D. Parlee

THE gas-liquid metal diffusion cell technique1-3 has been used to study the diffusion of nitrogen in Fe-C alloys. The actual apparatus and technique were the same as employed by the authors to study the diffusion of hydrogen in liquid iron.' The diffusion cell' was formed by immersing an alumina tube in a stagnant melt contained in an alumina crucible. The tube (hereafter called absorption tube) contained nitrogen gas at 1 atm and was connected to a sensitive gas-measuring system. The change in the average concentration of nitrogen in the melt in the absorption tube was determined by measuring the rate of absorption of nitrogen in the diffusion cell. Eq. [I], 1-3 derived from the appropriate solution of Fick's second law, was used to examine the data and to calculate chemical diffusion coefficients (D) in situations where the absorption appeared to be controlled by diffusion in the liquid: where V is the stp volume in cu cm, d is the diffusion cell diameter in cm, p, is the density of the melt in g per cu cm, pg is the stp density of nitrogen in g per cu cm, C, is expressed in wt pct, D is in sq cm per sec, and t is in min. According to Eq. [I], a plot of v vs vt should yield a straight line passing through the origin if absorption is controlled by diffusion in the liquid. The slope of this line could be used to determine the value of D under appropriate conditions. As discussed in earlier reports,1,2 the initial thermal expansion of the gas upon immersing the absorption tube distorts the line in the initial stages of a diffusion experiment. However, this is not a serious problem since the slope of V vs 6 plots can be determined from the data points obtained after the initial expansion ceases. The volumes reported on the data plot presented here represent absorption after this thermal expansion ceased. Several preliminary diffusion experiments were attempted with melts of pure iron and with Fe-C alloys containing up to 0.6 pct C. In these cases, no or very little absorption was observed. The only data obtained were for an Fe-C melt which was in addition thoroughly deoxidized by successive hydrogen and vacuum-degassing treatments. These treatments introduced an appreciable amount of aluminum into the melt and reduced its omgen content. The original charge material for this melt contained 0.23 pct s and approximately 0.001 pct &. After repeated hydrogen and vacuum-degassing treatments two diffusion experiments were performed. The analysis of the melt

Jan 1, 1968

By C. E. Nelson, T. E. Leontis

THE properties and casting characteristics of sand-cast Mg-Al-Zn alloys, used commercially in this country and abroad, have been discussed in a number of articles during the past few years.'-" In addition, broad surveys of many compositions in the magnesium corner of the Mg-Al-Zn diagram between 0 and 12 pct A1 and 0 and 6 pct Zn have been presented by Busk and Marande7 and by Fox." The purpose of this paper is to furnish a comprehensive survey of the changes in tensile properties, micro-structure, and dimensional stability of two magnesium alloys, AZ92A and AZ63A,+ as a function of aging time and temperature after solution heat treatment. Rates of precipitation in Mg-Al-Zn alloys are slow enough so that a substantially homogeneous, supersaturated solid solution can be maintained even when these alloys are air-cooled from the heat-treating temperature. Consequently, even though it has been demonstrated9 10 that significantly higher strengths can be developed in some alloys in the aged condition by quenching rather than air cooling from the heat-treating temperature, general practice is to air-cool magnesium alloys. All the work discussed in this paper is based, therefore, on aging studies performed on material air-cooled from the heat-treating temperature. This investigation was intended to be a study of commercially practical aging cycles; the tensile properties were determined, therefore, up to aging times of 25-hr duration. The alloys, used in this investigation were prepared in the laboratory by remelting commercial ingots of the appropriate composition according to the procedures described in a previous paper" as the "crucible method." All melts were given the standard superheating treatment in order to insure the maintenance of a uniform grain size of 0.003 to 0.004 in. Standard test bars, 61/2 in. long with a 2½ in. long reduced section having a diameter of Y2 in., were cast from these melts in green-sand molds using a four-bar pattern. The alloys were heat treated according to the following schedules: AZ92A alloy: 500" to 780°F in 2 hr + 780°F (24 hr) AZ63Aalloy: 500" to740°Fin2 hr + 740°F (16hr) In commercial practice," AZ92A alloy is heat treated at 770°F for 18 hr and AZ63A alloy is heat treated at 730°F for 10 hr. The slightly higher temperatures and longer periods of heat treatment were used in order to obtain as homogeneous a solid solution as possible and thus to minimize inconsistencies in the

Jan 1, 1952