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THIS chapter and the one following deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the simplification of the first two ' laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the "heat balance" of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced, and we assume that the cause lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities of flow distribution, air leakage, etc., present in any real, open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained- by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot-metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million B.t.u. per net ton. of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million B.t.u., and the sensible heat in the preheated air at the port ends is 117 million B.t.u. so that the total heat input at the ports is 477 million B.t.u. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million B.t.u., but 120 million of this is supplied by the heat in the hot metal and by various heat--evolving reactions in the bath, so that only 75 million B.t.u. need be supplied to the bath by the flame.

Jan 1, 1944

ATHOUGH the open-hearth charge contributes CO, CO2, and water vapor to the combustion gases and absorbs oxygen from them, in the main the thermal effects in the melting charge and molten bath can be considered independently of those in fuel combustion, the latter being regarded simply as the source of any extra heat required to finish a heat of steel. First of all, it should be remembered that a large percentage of the heat supplied to the bath is furnished by oxidation of the various elements in the charge itself. If this charge consisted of 80 to 100 per cent of hot metal and the oxidation were obtained by blowing in air or oxygen, as is the case in the Bessemer converter, then the net heat absorption would be negative, that is, the bath would contribute part of the heat required to keep the melting chamber hot, in addition to that contained in the finished steel and slag. In actual open-hearth practices, probably the nearest approach to this is in the duplex furnace, charged with Bessemer-blown metal and some hot metal, where very little heat is required to complete the refining and nearly all the heat energy from fuel combustion is used to keep the roof and walls of the melting chamber up to around 2900 to 3000°F. (1600 to 1650°C.) so that the bath will not cool off during the refining. The other extreme is with all-cold charges containing around 80 per cent steel scrap and 20 per cent cast iron or cold pig iron, in which case a very large proportion of the heat in the bath at tap is supplied from the fuel combustion. THERMAL EFFECTS IN MELTTNG In the previous chapter it was pointed out that in a typical heat, the fuel furnishes about four million B.t.u. per ton of steel produced. The heat required for the metallurgical processes is not easily defined in useful manner (as is shown later), but it ranges downward from about one million B.t.u., depending not only on the charge but on the manner of calculation. In any event this requirement appears quite small in comparison with the heat furnished by the fuel and invites

Jan 1, 1944

By E. D. Williamson

DURING the wartime rush to prepare the glass necessary for the needs of our army and navy, the problem of the temperature control of the annealing kilns became most serious. The narrow limits of strain allowable (all the specifications called for less internal strain than the average of the previously used German glass) made necessary a very exact procedure and the methods had to be used on a much larger scale than theretofore. At the Charleroi plant of the Pittsburgh Plate Glass Co., the members of the staff of the Geophysical Laboratory, which was cooperating with the company, had occasion to study the methods available, and reached a number of conclusions (many of them by no means new except in their application) that may interest and assist those who have to meet similar problems in other fields. The following is a short account of the essential features of the system of temperature control evolved, along with a rather abridged statement of the reasons that led to the adoption or rejection of various schemes.

Jan 8, 1919

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds ;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2 : I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium. some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17, 32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established .R3 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resinsmay serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2:I for the combined effect of both factors, as compared to the exclusive effect of either one. if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium, some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate. l7,32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

By Paul Foote

SEEBECK discovered, in 1821, that if, in a closed circuit of two metals the two junctions are at different temperatures, an electric current will flow in the circuit. In the case of an iron and a copper wire, for example, current will flow from copper to iron at the hot junction, or from iron to copper at the cold junction. Two factors combine to cause the current. An electromotive force exists between the two metals, the magnitude of which, depends upon the temperature and upon the metals; this is called the Peltier e.m.f. If a single wire of homogeneous material is heated at one end, an electromotive force is developed between the ends of the wire, the magnitude of which depends upon the metal and upon the difference in temperature; this is known as the Thomson e.m.f: The total e.m.f. acting in the circuit is the sum of the Peltier e.m.f. at the two junctions and the Thomson e.m.f. in each wire, consideration being given, of course, to the algebraic signs of the four e.m.f.'s. The total electromotive force thus depends upon the difference in temperature of the two

Jan 9, 1919

J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919

C. H. WILSON,* New York, N. Y. (written discussion?).-On page 2680, under the heading Junction Box and Zone Box, the authors say, with reference to the zone-box principle of connections between primary couple, compensator couple, and copper leads, which method in its appli-cation to a single couple is shown in Fig. 34, that if this principle is adopted for a multiple installation, so as to save compensating leads; a selective switch may be (and the inference is that it must be) inserted between the zone box and the different couples, putting the switch at an inconvenient point, or putting up with some complicated interlacing of connections.. Wilson-Maeulen Co. has employed the zone-box method extensively for several years and in none of the many multiple installa-tions has either of those alternatives been resorted to. Instead there has been used a method of wiring with the switch at the indicator and involv-ing no more complications than the junction-box method shown III

Jan 11, 1919

By I. Iwasaki, R. Titi-Manyaka

Thermogravimetric analyses were used to formulate the chlorination and chloridization behaviors of such metals as iron, manganese, copper, tin, nickel, and zinc and their oxides; of lime and magnesia; and of such minerals as calcite, siderite, rhodochrosite, rhodonite, and apatite- all commonly encountered in ironmaking raw materials. Complexities of the reaction steps involved were indicated by plotting thermogravimetric analysis curves and the possible mechanisms were discussed based on the theoretical weight changes and thermodynamic considerations. The relative effectiveness of chlorine and hydrogen chloride as chloridizing agents was considered in the light of the experimental results.

Jan 1, 1973

By I. Iwasaki, K. Adam

The oxidation behaviors of simple and complex chloride systems of copper, iron, nickel, cobalt, and manganese in a stream of oxygen were investigated using a thermogravimetric analysis technique. Their reaction mechanisms are discussed from stoichiometry, thermodynamic feasibility, and X-ray diffraction analysis of reaction products. The results are used to determine an optimum operating temperature of the selective oxidation step in a chlorination process for producing nonferrous metal chlorides, elemental sulfur, and ferric oxide from copper-nickel sulfide flotation concentrates.

Jan 1, 1985

By S. C. Lee

An uncoupled thermoviscoelastic finite element formulation with an application to Underground Coal Conversion (UCC) is presented. An incremental solution procedure with an implicit time stepping scheme is used under the thermorheologically simple material (TSM) postulate. The presented formulation, for a homogeneous and isotropic medium, is employed in the simulation of the UCC post-burn phase. Temperature, displacement, stress, and failure responses under thermomechanical loading are predicted. The solutions for the selected field problem indicate potential roof collapse, stress relaxation, and modest surface subsidence with a progressive thermal and failure front. The corresponding thermoelastic responses with temperature- dependent elastic properties are also presented and compared with the thermoviscoelastic results.

Jan 1, 1984

By Robert Roberts

(Butte Meeting, August, 1913.) In order to obtain data on the thermal effect of the blast-furnace jacket and on the water consumption in these jackets a series of tests were run on the 56 by 180 in. blast furnaces at the Great Falls Reduction Department of the Anaconda Copper Mining Co., at Great Falls, Mont. The arrangement of the jacket is shown in the transverse section of one of the furnaces (Fig. 1) on which the tests were made. The nose, spout, and breast jackets have independent water supplies and discharges. The end and side jackets are connected in pairs, as regards water supply, the feed water entering at the bottom of the lower jacket and overflowing into the bottom of the jacket immediately above it, and discharging into an independent overflow pipe for each pair of jackets. Tests were run on the main side and end jackets, the breast jacket, the spout, and the nose. Measurements were taken of the quantity of water discharged, per minute and the rise in temperature of the water in its passage through the jacket. The product of these two results, expressed in the proper units, evidently gives the number of units of heat removed per minute by the water. Sufficient work was done on each type of jacket to determine its behavior under different conditions, and the results from each set of conditions were checked by repeating the work from three to six times. The method used was as follows : The overflow from the jacket to be tested was arranged to discharge at will into a barrel, mounted upon platform scales. The discharge temperature was read just before turning the water into the barrel, and just before turning it back to the sluice; if the test lasted more than a minute, additional temperature readings were taken at 1-min. intervals from start to finish. The elapsed time of running the water into the barrel was, determined with a stop-watch, and this figure, combined with the in-

Jan 7, 1913

By Donald L. King

This paper has been prepared with the objective of providing basic information on thickening equipment as applied to mineral processing plant design. Thus, by design, the content is elementary, yet sufficiently informative to advise the reader concerning the thickening and clarifying process, equipment configurations, installation and operation. Practical considerations are provided for slurry samples for testing, evaluation of testing, preliminary sizing, duty classification, and thickener selection to enhance operation, see icing and control. Illustrations are provided to both inform and demonstrate present state of the art features and capability.

Jan 1, 1978

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thickners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter.

Jan 1, 1949

By W. Julian Patron

TREATMENT of the breaker wash-water discharges to remove the suspended particles of finely divided material is usually most efficiently and economically accomplished in settling or thickening tanks. The purpose of these tanks is to separate the excess water from the solids by sedimentation whereby the solid particles suspended in the water are thickened by the force of gravity. The water overflowing these tanks is either reused for coal cleaning or discharged directly to the streams. The settled solids, which are in a relatively concentrated condition, forming a sludge or thick pulp, can be disposed of by pumping to a storage dam, by slushing into mine workings, by processing for recovery of coal, or filtering by vacuum or centrifugal means and discharging with the breaker refuse. The scope of this paper will be limited to the discussion of settling and thickening equipment, the factors that influence the settlement of solids, and a brief description of tests that can be made to determine the size of settling facilities required for any particular condition. The practical application of sedimentation to the treatment of coal falls into two groups, one of classification or hydro- separation, and the other of clarification and thickening. Classification may be employed to prepare a relatively low- grade fuel, which can be used as is or can be further processed separately. Clarification and thickening is employed where the primary objective is to recover a relatively dewatered solid and return a satisfactorily clear water to breaker or streams. When a stream of water flows across a tank, the time required for a particle to travel from the feed inlet to the overflow must be a little greater than that required for the finest particles or flocs in the feed to settle out of the stream. OPERATION AND TYPES OF SETTLING EQUIPMENT Theoretically, the liquid in a settling tank should rise at a more or less constant rate throughout the area of the tank Under these conditions the rising velocity of the water must be less than the settling rate of the finest particles if clarification is to be obtained. When classification of particles is to be made in the tank, the overflow velocity must be greater than the settling velocity of the particles that are to be removed with the tank overflow. The performance of a settling tank, then, depends on the settling rate of the solids and the current velocities in the tank. The oldest types of sedimentation employ intermittent types of settling tanks of any convenient shape. Means are provided for filling the tank with pulp and allowing it to settle until quiet, for moving the clean liquor and for removing the thickened sludge. The operation is necessarily intermittent but a sufficient number of tanks is employed so that a continuous flow of clear water is maintained. Continuous methods for the sedimentation of slurries were developed in the metallurgical industry. Cones from which settled solids were discharged by gravity

Jan 1, 1946

By S. C. Lindsay, D. J. I. Evans

With each year that passes hydrometallurgical processes are being more widely used to recover base metals from ores and concentrates. Generally these processes involve liquid-solid separation of metal-bearing liquors from barren residues. This may be done by countercurrent decantation, thickening and filtration, or filtration or centrifuging only. Choice of method is governed by chemical and physical characteristics of the pulps; cost of labor, power, materials, and waste disposal; and even by the amount of capital available when building plans are under way. Since all these controlling factors change with time and location and with technological advances, the separation method must be re-evaluated when new plants or expansion programs are contemplated. At the Sherritt Gordon refinery in Fort Saskatchewan, Alberta, an ammonia pressure leaching process recovers nickel, copper, and cobalt from the nickel concentrate produced at Lynn Lake, Manitoba.' Pregnant liquors are separated from the barren leach residues in a thickener-filter liquid-solids circuit. The decision to use this type of separation was based on a summation of economic factors during the pilot plant and design stages. Although countercurrent decantation was not incorporated in the refinery flowsheet, the problems solved in thickening the leach residues and the experience gained in operating the commercial plant are pertinent to countercurrent decantation, particularly where it is applied to slow-settling leach slurries or slurries having a relatively high vapor pressure of a valuable, obnoxious, or poisonous vapor.

Jan 1, 1960

By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947