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By Shun-ichi Satoh

Studies by many authorities have proved that nitrogen exerts an injurious influence upon iron and steel, but in the casehardening of steel by carbon, nitrogen has the advantage of accelerating the process of cementation. Its influence upon special steels is quite remarkable; it can produce the hardest layer ever known in metallurgical products—a fact hit upon by A. Fry and studied and ascertained by L. Guillet. As there have been very few investigations on the influence of nitrogen on special steels, the writer has listed important articles dealing with this problem and has conducted experiments on nitrification. He also has tested the influence of nickel upon the penetration of nitrogen in electric-arc welding. Nitrogen Process for Surface Hardening In 1919, Siegmonl conducted an experiment known as "Versticken" by treating steel with ammonia gas and found that the steel thus treated has the properties of resisting corrosion. In 1922, L. E. Benson3 nitro-genized iron and steel by sodium nitrate. Fry3-"studied the nitrogen process for surface hardening and published the results of his studies in 1923, 1924 and 1926. Guillet tested special steels containing various elements with the current of ammonia at 500' to 510' C.10, 11, 12, and determined the hardness of some of them at various temperatures.13 He also conducted corrosion tests14 in 1927. Fry15 stated that tinplat-ing could prevent nitrogen from penetrating into steel in the course of nitrification. In 1927, Guillet 65 described the historical notes of the nitrification; and many applications of nitrification were published in the Kruppsche Monatshefte.51, 59, 62, 63, 64-74~75 H. K. Herschman66 conducted the wear test of the nitrified steel. Gunnar Hägg investigated

Jan 1, 1930

By John Guillermo Bartram

The oil industry continued relatively quiet in Wyoming in 1935, although production increased about 8 per cent over the previous year; 55 oil wells were completed in 1935, compared to 34 in 1934, and at the end of the year 44 wells were drilling, 33 in proven fields and 11 in wildcat locations. The total drilling a year ago was only 30. In the year 1935 Wyoming produced a total of 13,451,000 bbl. of oil, a gain of 912,000 bbl. over the 1934 figure of 12,539,000 bbl. Approxi-mately two-thirds of the increase, or 630,000 bbl., was from black oil fields and one-third, or 285,000 bbl., from light oil pools. Salt Creek, with production of 6,357,000 bbl., is still many times the largest field in Wyoming but in 1935 it made less than 50 per cent of the state's total, after producing more than all other fields in the state for 24 years; however, its decline was only 3.8 per cent from the previous year. Oregon Basin, a black oil field, held second place again with production of 1,163,-000 bbl., a good increase over 1934. Grass Creek, with increases in both its light and black oil, jumped into third place; and Lance Creek, with its new Sundance light oil production, was in fourth place in the amount of production. Frannie, which was in third place in 1934, dropped far back on the list because of lack of market. Byron and Garland, two other black oil fields in the Big Horn Basin, increased considerably. Big Muddy, a prominent light-oil field, was down with a natural decline; and Elk Basin, also light oil, produced less because of market conditions. During 1934 only three gas wells were drilled in Wyoming and 29 dry holes, 13 in proven fields and 16 at wildcat locations. Of the latter, 5 were on wildcat structures of considerable interest. Of the 55 wells completed during the year, 53 were in proven fields and of these 17 were small ones in the shallow Osage field and 10 were light-oil wells good for 1500 to 3000 bbl. each in the Lance Creek field. Discoveries Two of the oil wells were discoveries at Medicine Bow and Sheep Creek. Medicine Bow is a very large anticline with more than 3500 ft. of closure and is located in Carbon County in the south-central part of the state. In 1923 it showed some oil in the Upper Cretaceous Frontier

Jan 1, 1936

By John Guillermo Bartram

The oil industry continued relatively quiet in Wyoming in 1935, although production increased about 8 per cent over the previous year; 55 oil wells were completed in 1935, compared to 34 in 1934, and at the end of the year 44 wells were drilling, 33 in proven fields and 11 in wildcat locations. The total drilling a year ago was only 30. In the year 1935 Wyoming produced a total of 13,451,000 bbl. of oil, a gain of 912,000 bbl. over the 1934 figure of 12,539,000 bbl. Approxi-mately two-thirds of the increase, or 630,000 bbl., was from black oil fields and one-third, or 285,000 bbl., from light oil pools. Salt Creek, with production of 6,357,000 bbl., is still many times the largest field in Wyoming but in 1935 it made less than 50 per cent of the state's total, after producing more than all other fields in the state for 24 years; however, its decline was only 3.8 per cent from the previous year. Oregon Basin, a black oil field, held second place again with production of 1,163,-000 bbl., a good increase over 1934. Grass Creek, with increases in both its light and black oil, jumped into third place; and Lance Creek, with its new Sundance light oil production, was in fourth place in the amount of production. Frannie, which was in third place in 1934, dropped far back on the list because of lack of market. Byron and Garland, two other black oil fields in the Big Horn Basin, increased considerably. Big Muddy, a prominent light-oil field, was down with a natural decline; and Elk Basin, also light oil, produced less because of market conditions. During 1934 only three gas wells were drilled in Wyoming and 29 dry holes, 13 in proven fields and 16 at wildcat locations. Of the latter, 5 were on wildcat structures of considerable interest. Of the 55 wells completed during the year, 53 were in proven fields and of these 17 were small ones in the shallow Osage field and 10 were light-oil wells good for 1500 to 3000 bbl. each in the Lance Creek field. Discoveries Two of the oil wells were discoveries at Medicine Bow and Sheep Creek. Medicine Bow is a very large anticline with more than 3500 ft. of closure and is located in Carbon County in the south-central part of the state. In 1923 it showed some oil in the Upper Cretaceous Frontier

Jan 1, 1936

By Paul B. Crawford, Bobby L. Landrum

Electrical model studies have been made of the effect of unsymmetrical vertical fractures on production cnpacity. The study war restricted to the case of two vertical fractures originating at the well and extending out into the reservoir for various distances and orientations. The ratio of the short fracture length to the long fracture length was varied from 0.1 to 1.0 in successive studies. The angle separating the two fractures was varied from 0 to 180 degrees. The most effective fractured patterns were obtained when the fractures were oriented 180 degrees. It was found that when the total fracture length was equal to 0.2 of the drainage radius, the increase in production capacity may vary from approximately 1.55 to 1.95. depending upon the ratio of the short fracture length to the long fracture length and the angle separating the two fractures. If the total fracture length were 0.5 of the drainape- radius. poroduction cavacitv., increases varving 1.95 to 2.65 were observed, depending on the angle between the fractures and the ratio of the .short fracture length to the long fracture length. The fractured well production capacity decreased aPproxin?ately I to 10 per cent as the angle separating the fractures was varied from 180 to 90 degrees. It was dependent on the particular fracture. The commercial application of reservoir fracturing techniques has caused an interest to be expressed in the effect of vertical and horizontal fractures on production capacities. Some data have indicated that substantially vertical fractures may be created in some reservoirs. It is believed that the fractures are possibly unsymmetrical, that is, one fracture may extend due north 100 ft and a second fracture on the opposite side of the well may extend south or southeast only 50 ft. The total fracture length, ratios of the lengths and angles of separation may vary considerably. For this reason variations in these factors were considered. The study was restricted to the case of two vertical fractures originating at the well and extending out into the reservoir. It is not known that such will occur in a reservoir, but the results may be of value in interpreting or studying fracturing applications. PROCEDURE An electrical model was used in this study of the effect of unsymmetrical vertical fractures on production capacity, A wooden tank 30 in. in diameter and approximately 2 in deep was coated with paraffin wax. A copper band was situated at the periphery and a single wire electrode was positioned at the center of the tank. The ratio of the reservoir radius divided by the

Jan 1, 1956

By E. S. Wheeler

The conversion plant of the Clirnax Molybdenum Co. is at Langeloth, Washington . County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Co1orado.l They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. Chronology of Plant Development In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. 0.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time sa.1cium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. 0.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 193 5, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. 0.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product—molybdic oxide briquets— and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. 0.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,ooo to 190,000 Ib. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By Leo F. Reinartz

The history of steelmaking in the United States is a fascinating story of determination, sudden tragedy, exploitation, and inventive genius rolled into one gigantic plot. Mr. Reinartz' flowing interpretation of the progress made in the last one hundred years is being presented in a series of four articles. THIS is the Age of Steel. We live in a mechanized era. Our everyday lives--everything we see or do-are organized and influenced by this versatile metal. Our industries, our farms, our homes, and our transportation-yes, our vocations and avocations, or luxuries and necessities-all are dependent upon smelting iron and making steel. Take away iron and steel and soon our vaunted civilization would revert to a primitive existence. These metals, often in crude forms, have been known for thousands of years. Down through the ages, until about one hundred years ago, steel was made laboriously, and at high est, in small batches. During those years, methods of manufacture did not change very much. Over long periods of time only warriors, royalty, and wealthy people could afford to use articles made of iron or steel. History has recorded that the nations which were expert in iron and steel manufacture, and had access to rich iron-ore deposits, were the leaders in war or in peaceful pursuits. At the end of the 18th century, thirteen struggling American colonies had broken not only the political shackles that bound them to Great Britain, but also many of the economic bonds. They had showed their skill, Yankee ingenuity, and energy by making iron and steel articles for their own use. After the Revolutionary War, more and more hardy American pioneers pushed westward through the Allegheny Mountain passes and down the rivers into the fertile Ohio River and Kentucky country. Demands for articles made of iron increased. The iron industry on the east coast grew and prospered. As this trend continued, iron industrialists moved their plants westward to be near the large deposits of high-grade coal in western Pennsylvania, eastern Ohio, and nothern West Virginia. They also desired to use the local iron ores and water resources of those areas. Blast furnaces and ironworks were built in the Pittsburgh, Youngstown, southern Ohio, and northern West Virginia districts. In 1810, the United States produced 53,908 gross tons of cast iron and 917 tons of steel. Iron ore discovery A white man first discovered large deposits of iron ore in the northern Michigan and Lake Superior country in 1844. One year later, the Sault

Jan 1, 1961

By Charles S. Barrett, Robert F. Mehl, Dana W. Smith

The Widmanstatten figures found in the steels have been long recognized and in some aspects carefully studied,' especially as they occur in cast hypoeutectoid alloys. Aside from the practical importance of the structures obtained in the steels by various heat treatments, a study of the characteristics of these figures is interesting because of the rich opportunity the system affords to obtain new data on the mechanism of segregation from solid solutions. This opportunity is twofold: first, by changing composition within the austenite range the proeutectoid precipitate may be changed from that of ferrite to that of cementite, thus offering the same opportunity for changing the type of precipitate while maintaining the same basic lattice as that afforded by the Cu-Zn alloys;2 and second, the eutectoid inversion leads upon drastic quenching to the formation of martensite, a Widman-statten figure of unique interest from the crystallographic viewpoint, particularly in comparison with those formed on slow cooling.3 We have, therefore, two types of structure to study: that formed on slow cooling of hypoeutectoid and hypereutectoid alloys, and that formed on quenching hypoeutectoid, eutectoid, and hypereutectoid alloys. For each of these types of structure we require the crystallographic plane in the mother austenite along which the precipitate forms (we shall see that the precipitates in these alloys are invariably platelike in form), and also the orientation of the precipitate upon this plane. Some of these

Jan 1, 1933

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By John D. Gill

THIS paper assumes the incontrovertible nature of the statement that the validity of competition in the nonnatural resource industries is established firmly on the rate and extent of the economic development of the United States. It then demonstrates the nonexistence of any condition within the petroleum industry that would invalidate the principle of competition as applied to it. It points to the benefits that competition has effected in the oil industry and the reasons why the practice of the competitive principle should continue to keep the industry virile and progressive in meeting the requirements of future generations for the kind of products natural to it. Finally, it pleads for a clearer view of the affairs of the oil industry by seeing them against a background of the whole economy. INTRODUCTION Even a few years ago there would have been only an academic reason for presenting before this Institute a paper on the validity of competition in the oil industry or any other natural resource industry; today there is no more practical subject for this body to consider. In social importance it transcends attempted solutions of perplexing technical problems; and even the numerous legal and economic problems that grow out of administration of state regulatory measures appear to be of secondary importance because they would cease to exist if competition were abolished. The aspiration of certain elements of the Federal Government to acquire control of the oil industry has long been suspected The vital need for petroleum in the national defense ... confirms my belief in the urgent need of Federal legislation to safeguard our petroleum supply through prevention of waste and by establishment and maintenance of sound economic conditions in the oil industry... . But also it may be dismissed with this mere mention of it because it predicates government control and the abandonment or broad reduction of competition on a war emergency. Clearly, the fight for a nation's life may justify a government's control over men and resources that would be abhorrent and economically enervating under conditions of national security. More pertinent to the present matter, because it appears expressive neither of a personal ambition nor of an emergency condition but rather of the long-range view of a certain school of conservationists, is the pronouncement of no less an authority than the Attorney General of the United States, who has been repeatedly quoted by the press as saying that the American Petroleum Industry constituted a case "where the principle of conservation of an exhaustible and irreplaceable resource should replace the principle of competitive exploitation." The significance of this statement in the light of the commonly accepted meanings of the " principle of conservation" and of the "principle of competitive ex-

Jan 1, 1941

By A. E. Jenkins, L. A. Baker, N. A. Warner

The electromagnetic levitation technique has been successfully applied to rate studies of the de-carburization of liquid Fe-C alloys from 5.5 to zero pct C at 1660°C using gas mixtures containing 1 to 100 pct CO2 with CO or helium as diluents. The rate was shown to be independent of carbon concen -tration in the melt and only slightly affected by total pressure. The results were shown to be consistent with control either wholly or predominantly by gaseous diffusion. As well as avoiding side reactions with the crucible, levitation allowed precise calculation of reaction rates since the geometry of the system was accurately known. It also enabled interpretation using the established mass-transfer correlations for a gas flowing past a single sphere, The existence of gaseous-diffusion control and the extremely high rates of reaction reported for gas flowing past small spheres are of great practical significance in relation to current investigations into the use of spray-refining techniques in continzcous steelmaking. PREVIOUS work on the kinetics of carbon removal from liquid iron has generally involved the use of oxygen as the gaseous oxidant. Investigations have been made on commercial steelmaking furnaces and in addition laboratory-scale experiments have been attempted with a slag phase present. The general lack of agreement and the obvious difficulty in interpreting the results is at least partly due to the complexity of the systems used. This work has been reviewed by carter1 and more recently by Bods-worth2 and ward.3 The gas-liquid metal reactions have also been studied with slag-free melts by the conventional technique of blowing oxygen onto the melt contained in a crucible. The reaction between the oxidant and carbon could be followed by sampling either the melt or the gas phase. Side reactions with the crucible material have precluded direct interpretation of the results. Fujii, 5-7 using O-A mixtures, attempted to correct for the crucible reaction and reported that the reaction between carban and oxygen occurred at the melt surface and was controlled by gaseous diffusion for carbon contents greater than a critical value and by carbon-diffusion control in the metal for carbon contents less than the critical. The critical value was given as approximately 0.15 pct C. However, whereas this was the case for oxygen contents in the gas stream up to 10 pct, between 10 and 20 pct the rate was found to be approximately independent of oxygen content, and Fujii attempted to explain this observation by postulating the presence of an oxide "film".7 Turkdogan et a1.' have studied iron fuming during decarburizing and suggested gaseous-diffusion control of the reaction above a critical carbon concentration, given as approximately 2 pct C. Filippov9-12 reports in a similar manner to Fujii but makes no mention of the crucible reaction with the carbon in the melt, even though this would be expected with the temperature, crucible material (MgO), and carbon contents used. Both CO2 and O2 were used as oxidant gases. In the present work the decarburization of liquid Fe-C alloys was studied using an adaptation of the electromagnetic levitation technique, and thus the complexities introduced by crucible side reactions were eliminated. In this technique a single sphere of the Fe-C alloy is freely suspended and heated by electromagnetic induction in a flowing stream containing the oxidant gas. The full range of carbon levels up to saturation was studied, the temperature of the melts in this instance being held constant at 1660°C. The oxidant was CO2 which was used either pure or in association with a diluent gas, the total gas pressure being maintained either at 1 atm or at a reduced pressure. Thus the reaction under study was:

Jan 1, 1964

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By O. Chanute

all of' level atid grade curve excepting Nos. 897, 898, 899, and 900, because of the impossibility of grouping them in the same nlonner, no two Iraving the chemical composition and physical prnprtiw as tho only v:iriubles. Phosphorus ~tnits have been taken to show the relatia h:wdnes. Of these 16 groups, 10 decidedly indicate slower wear firr tile harder rail. Of the remaining 6 groups, three (groups 2, 9, and 15) come well within the limits of error (.25 pound per yard) inherent in the palculation of the data as pointed out by Dr. Dndley; they catrnot, therefore, be considered tls exceptions. Group 2 and 15 arc but little outside of the limita of error. Rail 923 of group 9 is obviously abnornlal. This is probahly due to its being overheated, which the chemical analysis shows might easily be the case, and which the physical tc~ts and its low specific gravity tend to c-nfirm. We inry say, then, thnt 13 of these 16 groups fairly indicate, if they do not definitely point out, th:kt, under the same condition% tbe harder rail gives the slower wear. Of course, these comparisons are too few to enable us to arrive at positive ~?o-nclusions; but indications thus obtained are, I believe, fir more vsluitblc and tresttvc~rthy than those fhzt averages rvottld give us, mnde up from any ~lumhr of rails under intloy difi~rcal, conditions. Finally, it, seems to me, that the conclusions arrived at earlier in my remarks, together with, and confirmed by the last, show strong evidence that, under the same conditions, the harder rail will givc the slower wear. 0. C~~anute, New York CITY: We are very much shlipl, 1 ant sure, to Mr. Sandberg for his paper upn " Rail Ryaifications and Rail Inspertion in Europe." We have in thp United States bithhrto Been inspecting mils sonlewl~at haphazard, and we ore glad to gtbt tfie results of Mr. Sandberg's long experience. We recognize that he was an)ong the first, if not the very firwt, to iipply mare rittional and scientific rules to the designing of irou rails., niora recently, to adapt tlitve rules to the clesigtting of steel I':I~]R, to conform to the oapaljilities and rqniretnento of this new n1:ttcrial. Although we have generally adopted, in this country, sectinns for hteel rails which marly of our railway men think even bottar than those of Mr. Snlldlmrg, he is neverthelees the Ieat3er in foot.iito11~ we have followed ever since it has been est~blished

Jan 1, 1881

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

UNTIL recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, pre-heating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about 1150°C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the fr6nt of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29, 1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942, and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August I942 under contract with the War production Board and under the super- vision of the War Metallurgy Committee. This paper describes the phases of the investigation that are thought to .be

Jan 1, 1944

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher' During the same period there has been a falling off in similar activities within the

Jan 1, 1947

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 H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher' During the same period there has been a falling off in similar activities within the

Jan 1, 1947

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,' detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By L. P. Teas

As sphalerite is such a common constituent of many types of ore, the present investigation was undertaken to determine what its relations are to the other minerals in the deposits, and also whether these are of any genetic significance. The data presented herewith were obtained from a mineralographic study of about 200 ore specimens from some 43 different localities, represented by suites of specimens in the Cornell University collection. These, grouped according to their genesis, were as follows: I. Contact-Metamorphic Deposits.-Silver City, N. M.; Kelly, N. M.; Silver Bell, Ariz.; Bingham, Utah; Agaguca, Michoacan, Mex.; Matehuala, Mex.; Sombreretti mine, Mex. II. Deep-Vein Zone Deposits.-Mineral, Louisa Co., Va.; Edwards, N. Y.; Chestnut Yard, Va.; Allah Cooper mine, Louisa Co., Va.; Globe, Ariz.; Moyie, B. C.; Rossland, B. C.; Broken Hill, N.S.W.; Weedon, Que.1 III. Intermediate-Vein Zone.-Park City, Utah; Leadville, Colo.; Butte, Mont.; Santa Barbara, Mex.; Red Cliff, Colo.; Burro Mountains, N. M.; Idaho Springs, Colo.; Blue River, Ore.; Rye, Colo.;1 Slocan district, B. C.; Freiberg, Ger.; Clausthal, Ger: IV. Shallow-Vein Zone.-Ouray, Colo.; Goldfield, Nev., Zacatecas, Mex.; Field, B. C.; Kapnik, Austria; Frontenac mine, Kingston, Ont. V. Meteoric Water Deposits.-Joplin, Mo.; Southwest, Wis.; Austinville, Va.; Crittenden County, Ky.; Ridgeburg, Pa.; Moresnet, Belgium. It is not supposed that the investigation of such a limited number of occurrences may warrant conclusive and universal generalizations, but the conclusions reached are believed to be reliable in so far as the specimens, that were examined are concerned.

Jan 11, 1917