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By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By Roland D. Parks

CORUNDUM, little publicized as an industrial abrasive, has, in its small way, contributed greatly to the production of many specialized items vital to our war program and to our allies. Optical elements of the highest quality for range finders, bombsights, and scientific instruments; precision metal parts for torpedoes and airplane engines; quartz crystal plates for military radios; armorplate and malleable castings for tanks and guns; and eyeglasses for everyone; these are some of the products that corundum has helped to produce in the quantities needed and on time. Unlike metals and many other raw materials, corundum is not incorporated into any of these finished products. It is simply a grinding medium used to produce the desired finish or precision; an operating supply or tool, so to speak. With a Mohs' scale index of o, corundum ranks next to the diamond in hardness among the natural minerals and is superior to emery and garnet. The gem varieties of corundum, including the Oriental ruby and sapphire, are frequently more highly prized as jewels than the diamond. It is the intent of this paper to deal only with a description of the corundum industry, the administration of wartime control, and certain economic aspects as seen by the author. Several references are listed to assist anyone who wishes further information on the geological occurrence of the mineral. ORE PRODUCTION AND CONSUMPTION For the past two decades, South Africa has been the world's sole producer of corundum ore. A possible exception is Russia, where, it is understood, there was considerable production during the thirties for domestic consumption but for which statistics are lacking. The United States is the world's principal consumer of corundum ore; imports for the period 1934 through 1940 averaging 3000 short tons per year. The years 1935 and 1936 were close to the 5000-ton mark, and imports during 1941, the last prewar year for which statistics have been released, were approximately 6000 short tons. Again lacking statistics on Russia, the United Kingdom ranks second, but far below the United States in consumption of ore. Historically, corundum has been found in some 35 countries throughout the world, but the principal deposits are in South Africa, Canada, Madagascar, Russia and the United States. Deposits are generally small and subject to rapid exhaustion. Thus, the United States was the principal world producer for the period 1870 to 1900, when operations ceased except for two years during World War I. India was a producer of ore from 1898 through 1921, with peak output in 1916 through 1918. Canada came into production in 1901 with substantial output of ore and finished grain until 1914; the production thereafter was smaller until 1921. Madagascar has produced ore since 1910 but has had important output in only a few scattered years. South African production started in 1912,

Jan 1, 1945

By A. C. Losekamp, J. B. Conway

Thermal-expansion data for, tungsten, rhenium, tantalum, .molybdenum, niobium, W-25 pct Re, Ta-10 pct W, ant1 Mo-50 pct Re are presented covering the range from room tempature to 2500°C. In these measureMents, made in a resistively heated tungsten tube furnace operating in a helium atmosphere, data for rod and sheet specimens were found to be identical; in addition, arc-cast and sintered tungsten were found to yield essentially identical results. Optical rneasurenlents of thermal expansion .made in any atmosphere other- than vacuum are subject to a refraction error which can be quite substantial. Specimens tested in helium appear shorter than when tested in racuum and hence a special correction factor must be applied to the helium data in order to obtain accurate results. WHILE it is true that linear thermal-expansion data for many of the refractory metals have been measured to very high temperatures, it is also true that except in a few instances the data from various investigators are not in good agreement. This is particularly evident in the case of tantalum and niobium although some tungsten data have been reported which differ by as much as 40 pct from the data of other investigators. Due to the sensitivity of both tantalum and niobium with respect to impurity absorption during exposure to high temperatures, it is probable that this single factor accounts for the majority of the discrepancies in the thermal-expansion data for these metals. However, this same factor can probably not be employed to explain the existing differences in the tungsten data. In all probability, these are due to errors in the measurement technique, to material composition variations, or to changes which take place in the material during the heating process (e.g., additional densifica-tion resulting from heating a sintered specimen above the original sintering temperature). In view of the discrepancies which exist in the linear expansion data reported for many of the refractory metals, the current study was initiated in an attempt to resolve such differences. Also, no high-temperature linear thermal-expansion data were found to be available for several refractory metals. Providing such data was another objective of the current investigation. MATERIALS In this study test specimens were employed in either rod or sheet form and in several instances both arc-cast and sintered material were employed. Material compositions are presented in Table I. Helium gas was fed to the furnace at a rate of about 0.5 SCFH and no special purification procedures were employed. However, the helium contained less than 50

Jan 1, 1967

By Gregoire Gutzeit

THE development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. GENERAL OUTLINE The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties-for instance, isotropism, anisotropism, color, cleavage, reflecting power-are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1942

By Michael J. Messel

THE critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. EXAMINATION OF DEPOSITS In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesiumsilicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1947

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

By R. L. Huntington, Frank P. Vance, George F. Russell, Robert Thompson

With the advent of higher pressures in the operation of natural-gas transmission lines, the removal of water vapor from the gas has become increasingly important in order to prevent condensation or formation of gas hydrate from slowing down or stopping the flow of gas. Intelligent design of these dehydration or gas-drying plants has been hampered through the Iack of experimental data on the water vapor content of natural gas at elevated pressures. In view of this need, this present investigation was sponsored by the Southern Natural Gas Co. in the Chemical Engineering laboratories at the University of Oklahoma Research Institute. Experimental results were obtained on the water-vapor content of natural gas up to 2000 lb. per sq. in. at atmospheric temperatures. The water content at 2000 lb. is approximately two thirds as much as it is at 1000 Ib. Deviations from the ideal gas laws vary directly with pressure and indirectly with temperature. Introduction The removal of water vapor from natural gas is an important operation in connection with the production and transportation of this commodity because: I. Liquid water accelerates internal corrosion of a pipe line. 2. Accumulation of water at low points in a pipe line reduces markedly its capacity. 3. Gas hydrates, icy snowlike growths, form readily under high pressure in the presence of the lower hydrocarbons and water, often plugging up the pipe line. In order to design dehydration plants for stripping the gas of its water content, it is essential that the engineer. have a knowledge of the saturated or equilibrium water-vapor content of the gas to be processed. With the gradual increase of operating pressures around gas-producing wells and pipe lines, it was observed that the quantity of water recovered from dehydration plants or condensed in colder lines was considerably greater than had been expected from calculated contents, based on vapor-pressure data taken from steam tables. This observation prompted a number of investigators, for instance, Laulhere,3 Dea-ton,l and Hammerschmidt2 to carry out experimental work at pressures up to 600 lb. per sq. in. in order to determine quantitatively the water content of various gases. Sage, Lacey, et al.4,5 have recognized more recently the need for such data at higher pressures, but their work was done at temperatures of 100ºF, and higher. Since hydrate formation usually, if not entirely, occurs at temperatures below 100ºF., the present investigation was confined to the . lower temperature range at pressures from 600 to 2000 lb. per sq. in. gauge.

Jan 1, 1945

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 3/4 million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done' on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

By Michael J. Messel

The critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. Examination of Deposits In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesium-silicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1948

By Michael J. Messel

The critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. Examination of Deposits In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesium-silicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1948

By J. W. Walker, G. J. Heuer, E. W. Hough

An improved apparatus is described for the deterrni-nation of interfacial tension* by the pendant drop method in the pressure range from 15 to 15000 psi and the temperature range from 100º td 280°F. The chief characteristics of this apparatus are reliability and ease of operation. Temperature control was accomplished by means of an electrically heated jacket which could he completely removed while cleaning the apptrratus. The cell was designed so that the camera could he placed about I in, from the window without overheating the carnera lens. Separate "0" rings employed to seal each window and corresponding window backup plate gave very reliable window operation at 10,000 psi. An extra pistorr-cylinder combination was added so that a high compression ratio could he attained when gas was employed as one phase in the pendant drop cell. Other essential parts of the system were similar to an apparatus already described.' The interfacial tension for carbon dioxide and water varies from about 69 dynes/cm at 15 psi to about 19 dynes/cm at 1,250 psi for 100°F. For pressure.r between t,500 and 3,500 psi, the interfacial tension is between 32 and 24 dynes/cm at this temperature. The interfacial tension at 280°F varies from about 50 dynes/cm at 200 psi to about 17 dynes /cm at 10,000 psi. The maximum surface excess for carbon dioxide, assuming the surface excess of water to be zero, occurs at about 1,500 psi jor the 100°F isotherni and Itas a value of about -79 X 1014 mol/sq cm. At 160°F this maximum IS shifted to about 2,000 psi and has a value of about 10 X 1014 111ol/.sq cm. Other maxima, us well as several minima, are present at these and other temperatures. Judging from the data on the solubility of water in carbon dioxide at elevtrted pressures2,3, it appears that the principal maxinza natned are in regions of increasing solubility of the water in the carbon dioxide rich phase. INTRODUCTION AND APPARATUS A pendant drop interfacial tension apparatus which would accommodate an opaque liquid in a gas phase was constructed several ycars ago' for industrial purposes. This apparatus was used as a starting point for the present development. The objective of the present development was to enhance reliability and convenience of operation. Other articles'" have described pendant drop apparatus which could not accommodate a gaseous phase adjacent to the windows. A schematic diagram of the apparatus is shown in Fig. 1. The water used followed the path; A, intro-

By A. H. Daane, B. J. Beaudry

The yttl-irtm-nickel system has been investigated by metallo-graphic, thermal ard X-ray methods. There are nine intermetal-lic compounds present: Y3Ni, Y3Ni,, YNi,, YNi,, Y,Ni,, YNi,, and Y,Nil, which rodergo peritectic decomposition and YNi and YNi, which melt congruently. There are eutectics at 34.8, 57.5 and 93.3 at pct Ni which melt at 805°, 950 and 1285 C, respectively. Crystallographic data are given for YNi, YNi,, YNi,, YNi5and Y,Ni,. The terminal solid solubility is low. In recent work by Fisher and Fullhart' in which yttrium crucibles to be used for containers of uranium-chromium eutectic were clad with a high nickel steel, a low melting phase formed where the yttrium was in contact with the steel. To investigate the cause of this phenomenon, Daane, et al. made a survey study of yttrium systems with chromium, manganese, iron, and nickel and found an 18 wt pct Ni (weight percent) alloy to melt at approximately 950°C. voge13 in a study of the systems of cerium, lanthanum, and praseodymium with nickel found six compounds of the same formula in each system, i.e., R3Ni, RNi, RNiz, RNi3, RNi4, and RNi5. Since there is a great similarity between yttrium and the rare earths, compound formation was likely to occur also in the yttrium-nickel system. voge13 observed that the ability of transition metals to form compounds with the rare earths diminishes in the order nickel, cobalt, and iron while no compounds are formed with manganese, chromium, and titanium. Available data on yttrium systems with these elements indicate similar behavior, except that a slightly greater tendency toward compound formation is apparent. Simple eutectics with limited solid solubility have been found in the yttrium-titanium4 and yttrium-chromium5 systems, but at least one compound is present in the yttrium-manganese system.' In the case of yttrium-iron, at least three compounds are present,5 while only two are present in the cerium-iron,' and no compounds are present in the lanthanum-iron5 system. On the basis of both the trend in the alloying behavior of yttrium and rare-earth metals with the first transition series metals and the large number of compounds in the cerium-nickel system, one might expect six or more compounds to form in the nickel-yttrium system. A consideration of Hume-Rothery's rules of alloying based on size factor, electronegati-vity, and valence predicted low terminal solid solubility and possible compound formation. The present study was undertaken to confirm these predictions of

Jan 1, 1961

HeRbeRT Haas,—(communication to the Secretary*).—Fig. I plainly shows that the comparison of the steam-turbine and Diesel-engine plants was made on a basis of 6,000 kw. continuous operating load. The tabulation of costs for an 8,000-kw. load is merely done to show the relation of increased output on the unit power costs. Both plants would sacrifice their reserve capacity, which is to insure continuous operation, if operated to generate 8,000 kw. continuously; unless Mr. Hawkins advocates the operation of one of the turbines at 33.33 per cent. overload, retaining the other as a standby, which, besides overtaxing the turbine, results in a great loss of efficiency. It would be well for Mr. Hawkins to qualify certain of his statements. Thus, under the caption "Diesel Engines, Selection of Units," he says that '(two of the largest Diesel-engine builders take the position that, in the present state of the art, they would not attempt to put out units over 1,000 kw.;" he should qualify it by saying that "two of the largest American Diesel-engine builders take the position that, in the present state of the art in the United States, they would not attempt to put out units over 1,000 kw." The reason that American manufacturers restrict themselves at present to units of that size is to be found not so much in a lack of experience in building large units as in a lack of a sufficient demand for them in the United States to justify the heavy capital outlay connected with the development of such engines. There are relatively few localities in the United States where fuel prices are as high as they are in the South-, west, and regions of high fuel prices are sparsely settled and have a very limited demand for power. Where low fuel prices obtain, steam turbines are active competitors of Diesel engines for large power plants, particularly when the station load factor is low. As most of the American manufacturers of Diesel engines work under license agreements with European manufacturers, which limit their market to the United States and its possessions and Canada, a further limitation is imposed upon them, leaving to European firms practically the entire world as a market. The greater number of power plants range in size from 300 to 1,000 hp.; the average size of the central station, on a basis of all central stations in the United States, not greatly exceeding 500 kw.; in these sizes it is hard for steam engines to compete with Diesel engines, unless fuol oil prices are excessively high, and coal prices very low, or the exhaust steam is used for heating purposes.

Jan 1, 1917