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By Ulick R. Evans

I Should like to commence by saying how much I appreciate the honor which the American Institute of Mining and Metallurgical Engineers has done me in inviting me to visit your country, and to deliver this lecture before you. In choosing a subject, and in deciding what to include and what to omit, I have endeavored to discuss as far as possible work carried out recently in Europe with which you may not be unduly familiar. It would be poor return for your hospitality, and a mistaken sort of compliment indeed, if I were to load the lecture with accounts of researches carried out in your own country—researches with which you are probably better acquainted than I. Not that I have in any way excluded work done on this side of the Atlantic from my survey; one would indeed find it difficult to write on this, or on any other branch of science, without mentioning American work. But I have endeavored as far as possible to concentrate on aspects of the case which will, I hope, be comparatively fresh to you, and I feel fairly certain that this will be in accordance with your own wishes. Films Produced at Elevated Temperatures If a strip of iron is heated strongly at one end, the other end remaining cold, there is produced over the heated portion a layer of oxide scale, the thickness of which diminishes steadily with the distance from the hot end. Somewhere in the middle of the strip, the thickness of the oxidized layer will become comparable to the wave length of light, and over this region the thin films give rise to a series of beautiful interference tints, commonly known as "temper colors." The colors are caused by the fact that two trains of light waves are reflected respectively from the outer and inner surfaces of the oxide film, and the possibility arises that the "crests" of one series of waves may coincide with the "troughs" of the other, thus diminishing the intensity of the light of some particular wave length. The state of affairs in this part of the strip is shown diagrammatically in Fig. 1, in which the film thickness is enormously exaggerated, of course, in comparison with the length of the strip; the

Jan 1, 1929

By J. L. Tokich, A. R. Troiano

Since 1921, when Hull1 discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at ternperatures ranging from 400° to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allo-tropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as Occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility Of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms Of this type of Of Table 1 briefly outlines the methods and results Of previous investigators Of the transformation temperatures of cobalt. Materials and Methods The major portion of this investigatioll was performed with cobalt sheet containing a total of 0.2 pet impurities with carbon present to the extent of o,I pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon con. tent analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pet pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below (600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various ternperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per set to greater than 1,0oo°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The of of the existing phases was roughly approximated by visual examina-

Jan 1, 1949

By C.R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. D. Demond

IN reverberatory smelting, fuel is the chief item of expense, as it commonly is in processes using large percentages of it. Hence the most suitable supply is eagerly sought; that is, the supply which, in the end, yields the greatest net profit. The better grades are not infrequently bought, even at an advanced price, because they are apt to be decidedly more economical. High price, of itself, however, is no merit, for freight is generally the largest part of the cost of fuel, and the nearby supply may yield as high efficiency as that from a greater distance. If a poorer grade is reasonably good, and if its cost is low enough to more than offset the decreased technical efficiency, it is of course the more suitable. Any smelting, operation depends for both efficiency and economy on raising the furnace atmosphere considerably above the "critical" temperature; that is, above the temperature at which smelting is completed. If this temperature is not exceeded, smelting stops, no matter how much coal is burned; and the real value of a fuel depends on the number of degrees that the temperature is continuously kept above this point. For example, if one fuel maintains 2,500° F. and another only 2,100° F., while the "critical" temperature is 2,000° F., the first is worth at least five times as much as the second, although the increase above atmospheric temperature is only one-fifth more in one case than in the other. This "margin of temperature" above the smelting point is much more significant than the total number of heat units developed from the fuel. The case is parallel to that of water flowing from a pipe. The reservoir may contain a billion gallons of water; but, even though the fluid has come to the nozzle, not a drop will run out, where it can be of practical use, unless the level in the reservoir is higher than the nozzle; and the speed and volume of flow depend on how much higher the level is in the reservoir than at this point. If the temperature inn a furnace is not above the critical level there will be no slag to flow over the skimming plate, even though there are enough heat units to bring an unlimited quantity of charge up to the point of slag formation; and just as the value of a water supply for the purpose of putting out a fire depends largely on the effective head, so the difficulties of furnace management

Jan 8, 1914

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

Eighty-four quaternary titanium-base alloys from the following systems were investigated: 1. Titanium-chromium-carbon-nitrogen. 2. Titanium-chromium-carbon with copper, vanadium, molybdenum, manganese, iron, or nickel. 3. Titanium-chromium-nitrogen with vanadium, molybdenum, or nickel. The tensile properties, minimum bend radii, hardnesses, response to heat treatment and aging treatment, and phase relationships of these alloys are reported. HIS paper is the third in a series describing J- titanium-base alloys. The first paper describingdescribed titanium binary alloys, and the second contained data on a large number of titanium ternary alloys. Eighty-four heats, comprising three groups of quaternary titanium-base alloys, are described in this paper as follows: 1. Titanium-chromium-carbon-nitrogen alloys. 2. Titanium-chromium-carbon alloys containing copper, vanadium, molybdenum, manganese, iron, or nickel. 3. Titanium-chromium-nitrogen alloys containing vanadium, molybdenum, or nickel. The methods of preparing, fabricating, and testing the alloys are described in the paper Binary Titanium Alloys. Quaternary Titanium - Chromiurn - Carbon -Nitrogen Alloys The properties of titanium-chromium-nitrogen and titanium-chromium-carbon ternary alloys have been described in the paper Ternary Alloys of Titanium. Because small amounts of nitrogen and carbon both appear to be somewhat beneficial, these additions have been investigated fairly completely in quaternary alloys containing chromium at the following levels of composition: 2.5, 3.5, and 5.0 pct chromium 0.25 and 0.5 pct carbon 0.1 and 0.2 pct nitrogen Mechanical Properties: The mechanical properties of these alloys are listed in table I. Fig. 1 and 2 show graphically a comparison of the tensile properties and hardnesses of quaternary alloys with those of the titanium-chromium binary alloys. Fig. 1 shows the comparison at 0.25 pct carbon, whereas fig. 2 shows the comparison at 0.5 pct carbon. It is concluded from these data that 0.25 pct carbon and 0.1 pct nitrogen are desirable additions to the 5 pct chromium-titanium base. It is further concluded that most of this improvement is produced by the nitrogen and that carbon is either harmless or mildly beneficial, at least up to 0.25 pct. Structure and Transformation Range: The effects of carbon and nitrogen on the transformation range of the titanium-chromium alloys were determined as part of the routine investigation. Additions of 0.25 pct carbon and 0.1 pct nitrogen had no appreciable effect upon the transformation range. However, the addition of 0.25 pct carbon and 0.2 pct nitrogen definitely raised the beta solvus temperature, as shown by fig. 3.

Jan 1, 1951

By C. R. Taylor, John Chipman

THE study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8: I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. EXPERIMENTAL METHOD Furnace The furnace used in this investigation differed from previous designs and may be considered a fourth modification of the original rotating furnace. Its essential features are shown in Fig. I. The outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base C are alberene stone. The coil supports D are of "Formica," a material formed from phe-

Jan 1, 1942

By John H. Walthall, Raymond L. Copson, Travis P. Hignett

In October 1942, the War Production Board requested the Tennessee Valley Authority to undertake investigations to determine the feasibility of producing alumina suitable for reduction in aluminum cells, from clays and other domestic materials, by a lime-sintering, soda-ash leaching process. The work was undertaken by the chemical engineering staff of the Authority under the general direction of the War Metallurgy Committee of the National Academy of Sciences. The investigation included small-scale tests to determine the most suitable conditions for the process, and construction and operation of a pilot plant to obtain data for evaluation of the process and for design of a plant. The results of this investigation are described in the present paper. Sources of Alumina Alumina for the commercial production of aluminum is obtained from bauxite by the Bayer process. The tremendous demand for aluminum for wartime uses is causing rapid exhaustion of the high-grade bauxite deposits in the United States. On the other hand, there is an abundance of aluminous materials such as clay and lower grades of bauxite, which are not suitable for treatment by the Bayer process because of their high silica content. The Tennessee Valley Authority has conducted research and pilot-plant work for more than 5 years on methods for the production of alumina from clay and low-grade bauxite. Particular attention has been given to the high-grade white kaolin found in Carroll County, Tennessee. Exploratory drilling has demonstrated that at least 4 1/2 million tons of kaolin containing in excess of 34 per cent AlzOI is available in this area by strip-mining methods. It has been estimated that hundreds of millions of tons of clay of similar quality occur in the Tennessee Valley region. The Process The process is illustrated in the flowsheet (Fig. I), and consists essentially of the following steps: I. Heating a mixture of clay and limestone to form a sinter containing calcium aluminate and dicalcium silicate. z. Leaching this sinter with a dilute sodium carbonate solution, to form a sodium aluminate solution and a calcium carbonate, calcium silicate residue, which is discarded. 3. Treating the sodium aluminate solution with carbon dioxide to precipitate aluminum trihydrate and regenerate the sodium carbonate solution, which is recycled. 4. Heating the aluminum trihydrate to produce alumina. The process was considered promising because of the abundance and cheapness of the two raw materials, clay and limestone; and because, as compared with an acid process, smaller amounts of critical

Jan 1, 1944

By C. D. Demond

In reverberatory smelting, fuel is the chief item of expense, as it commonly is in processes using large percentages of it. Hence the most suitable supply is eagerly sought; that is, the supply which, in the end, yields the greatest net profit. The better grades are not infrequently bought, even at an advanced price, because they are apt to be decidedly more economical. High price, of itself, however, is no merit, for freight is generally the largest part of the cost of fuel, and the nearby supply may yield as high efficiency as that from a greater distance. If a poorer grade is reasonably good, and if its cost is low enough to more than offset the decreased technical efficiency, it is of course the more suitable. Any smelting operation depends for both efficiency and economy on raising the furnace atmosphere considerably above the "critical" temperature; that is, above the temperature at which smelting is completed. If this temperature is not exceeded, smelting stops, no matter how much coal is burned; and the real value of a fuel depends on the number of degrees that the temperature is continuously kept above this point. For example, if one fuel maintains 2,500" F. and another only 2,100 F., while the "critical" temperature is 2,000" F., the first is worth at least five times as much as the second, although the increase above atmospheric temperature is only one-fifth more in one case than in the other. This "margin of temperature" above the smelting point is much more significant than the total number of heat units developed from the fuel. The case is parallel to that of water flowing from a pipe. The reservoir may contain a billion gallons of water; but, even though the fluid has come to the nozzle, not a drop will run out, where it can be of practical use, unless the level in the reservoir is higher than the nozzle; and the speed and volume of flow depend on how much higher the level is in the reservoir than at this point. If the temperature in a furnace is not above the critical level there will be no slag to flow over the skimming plate, even though there are enough heat units to bring an unlimited quantity of charge up to the point of slag formation; and just as the value of a water supply for the purpose of putting out a fire depends largely on the effective head, so the difficulties of furnace management

Jan 1, 1915

By B. F. Giyani, D. Rahal

"Stirred media mills have proved to be more energy-efficient than the conventional ball milling for fine grinding applications. The mill performance is governed by a number of operating variables including mill stirrer speed, feed particle size, solids content and slurry rheology. A study was conducted to assess effects of mill speed, media size and density, and slurry density on the Stress Intensity (SI) in a VXPmill and thereby the relationship to mill performance. For the mill speeds tested, it was found that the optimum tip speed is 7 m/s. If the speed is too high (12 m/s) energy losses result due to mechanical friction losses and heat generation. If the speed is too low (3 m/s), the kinetic energy is not sufficient to promote breakage. The size reduction ratio increases with the increase in mill speed and the decrease in solids content especially in the coarse fraction particle sizes. The effect of slurry rheology on mill performance was shown by assessing the effects of increasing solids concentration and decreasing particle size. Rheological effects seemed to interact with mill speed such that the mill was less energy-efficient at higher solids content and at higher mill speeds particularly for grinding to fine particle sizes. There is an opti"

Jan 1, 2017

By I. Raheb, M. Y. Debili

"A set of Al-Co binary alloys (with respectively in weight percent 10%, 20%, 30%, 40%, 50% and 60% Co) have been studied by X-ray diffraction at the as compacted state. The structural evolution according to cobalt addition shows special features as the apparition of fcc cobalt and hcp cobalt beside aluminium in some cobalt compositions of the Al-Co mixtures using only cold compaction without sintering at high temperature. Figure 1 Cobalt is not a common alloying element in aluminium because its solubility is very low [1]. According to the pressure-temperature phase diagram, Co is known to exist in two allotropic forms: a low-temperature hcp phase and a high-temperature fcc phase [2-3]. At room temperature, Co is stable in the hcp form but it transforms to the fcc form when it is heated to above the transition temperature 695K. Powder aluminium and cobalt (99.999 %) were used in the proportions defined according to the required compositions. The total mass of the samples to be elaborated was between 8 g and 10 g. Cold compaction of mixed powder (Al-Co) under an uniaxial load of 10 MPa has been achieved to obtain a dense product (60%)."

Jan 1, 2015

By Z. H. Zhou

It is difficult to remove cadmium from raw indium using only electrolytic refining because their standard potentials are similar. In this paper, physical and chemical methods were used to remove Cd from raw indium. Indium metal is vacuum refined for two hours at 400°C with a vacuum pressure of 20 Pa. In this process, 99.70% of the Cd can be removed. The removal rate of Cd reaches 90% to 95% when indium is further smelted for 10 minutes in a 20% glycerin solution of KI and I2 at 180°C. When pre-indium is electrolytic refined in an In2(SO4)3-H2SO4 system, in which the indium content is 80 to 100 g/L, the pH is 2.0-3.0 and the current density is 80 to 100 A/m2, the contents of the impurities decrease and the purity of the indium product reaches 99.99%.

Jan 1, 2007

By W. C. Knoblaugh

Rotary kilns are adaptable to many fuels, but this paper deals principally with the use of powdered coal. The observations and conclusions presented are based on rotary kilns used in the manufacture of basic refractories for steel furnaces. Solid fuels are pulverized for two principal reasons: (I) ease of control, and (2) rapidity of combustion. By the use of pulverized coal, the operator can increase or decrease the fuel supply by small increments and with very little time lag between the change of control and the resultant change in the flame. This is extremely important in this type of furnace, as the temperature range for maturing the clinker is very narrow. By fine grinding, it is possible to increase the rate of burning of the coal, thereby liberating great quantities of heat within a small space in a short time. Under given conditions, temperature is a measure of the heat liberated per unit of time. To attain the temperatures of 2950° to 3150ºF., which are encountered in the manufacture of various steel-furnace refractories, it is estimated that it is necessary to liberate 125,000 to 175,000 B.t.u. per cubic foot of the burning zone per hour. The manufacture of dolomitic refractories is a ceramic process and, as is true in most such processes, the material must be subjected to a certain critical temperature for a certain length of time in order to complete the reaction. If the time of reaction is reduced, the temperature must be increased; in other words, if the rate at which the material flows through the hot zone of the kiln is increased, the temperature of the hot zone must be increased to compensate for this shorter exposure to the flame. Firing with Pulverized Coal Fig. I is a line drawing of a rotary kiln with the attendant equipment indicated in their relative positions. The kiln proper consists of a sloping, refractory-lined steel tube rotating slowly about its longitudinal axis (0.75 r.p.m.), and is countercurrent in operation in that the raw feed is introduced at the stack end and gradually approaches the zone of highest temperature at the lower end, where the fuel is introduced. Before 1930, the usual method of firing a rotary kiln was to store the coal in the pulverized form and then feed from this storage to the kiln as needed. This proved unsatisfactory and dangerous because of dust explosions and the inability to obtain an even feed to the kiln caused by arching of the coal in storage and flooding of the coal feeders. In later years the practice has been to store the raw coal and grind it as it is needed. Such a layout is indicated in Fig. I. The coal is stored in bins, charged from the top and drawn from the bottom into recording scales and then into some type of unit pulverizer. There are a number of good pulverizers .on the market, each incorporating features that the manufacturer considers outstanding.

Jan 1, 1948

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

By W. C. Knoblaugh

ROTARY kilns are adaptable to many fuels, but this paper deals principally with the use of powdered coal. The observations and conclusions presented are based on rotary kilns used in the manufacture of basic refractories for steel furnaces. Solid fuels are pulverized for two principal reasons: (I) ease of control, and (2) rapidity of combustion. By the use of pulverized coal, the operator can increase or decrease the fuel supply by small increments and with very little time lag between the change of control and the resultant change in the flame. This is extremely important in this type of furnace, as the temperature range for maturing the clinker is very narrow. By fine grinding, it is possible to increase the rate of burning of the coal, thereby liberating great quantities of heat within a small space in a short time. Under given conditions, temperature is a measure of the heat liberated per unit of time. To attain the temperatures of 2950° to 3150°F., which are encountered in the manufacture of various steel-furnace refractories, it is estimated that it is necessary to liberate 125,000 to I75,000 B.t.u. per cubic foot of the burning zone per hour. The manufacture of dolomitic refractories is a ceramic process and, as is true in most such processes, the material must be subjected to a certain critical temperature for a certain length of time in order to complete the reaction. If the time of reaction is reduced, the temperature must be increased; in other words, if the rate at which the material flows through the hot zone of the kiln is increased, the temperature of the hot zone must be increased to compensate for this shorter exposure to the flame. FIRING WITH PULVERIZED COAL Fig. I is a line drawing of a rotary kiln with the attendant equipment indicated in their relative positions. The kiln proper consists of a sloping, refractory-lined steel tube rotating slowly about its longitudinal axis (0.75 r.p.m.), and is countercurrent in operation in that the raw feed is introduced at the stack end and gradually approaches the zone of highest temperature at the lower end, where the fuel is introduced. Before 1930, the usual method of firing a rotary kiln was to store the coal in the pulverized form and then feed from this storage to the kiln as needed. This proved unsatisfactory and dangerous because of dust explosions and the inability to obtain an even feed to the kiln caused by arching of the coal in storage and flooding of the coal feeders. In later years the practice has been to store the raw coal and grind it as it is needed. Such a layout is indicated in Fig. I. The coal is stored in bins, charged from the top and drawn from the bottom into recording scales and then into some type of unit pulverizer. There are a number of good pulverizers on the market, each incorporating features that the manufacturer considers outstanding.

Jan 1, 1946

By E. Maxwell, C. J. Bechtoldt, H. C. Vacher

IN the course of an investigation of the properties of metals at low temperature there was occasion to determine the constitution of four iridium-osmium alloys. There is very little information in the literature1 on the constitution of synthetic Ir-0s alloys. Zvyagintzev' s has made a comprehensive study of different natural Ir-0s alloys and concludes that alloys containing more than 32 pct 0s have the close-packed hexagonal structure of osmium, whereas those containing less than 32 pct 0s have the face-centered cubic structure of iridium. The alloys studied in this work were prepared by the American Platinum Works, Newark, N. J., and were received in the form of fragments approximately 1.5 mm average diameter. The fragments had been obtained by crushing ingots made by fusing charges of iridium and osmium under an arc and air cooling. The ingots were not given a homogenizing heat treatment. Sample fragments Table I. Results of X-Roy Diffraction and Microscopic Examinations Phases Present as Determined by X-ray Diffraction Osmium Alloy Close- Iridium Face- Packed Centered Osmium, Iridium, Hexagonal Cubic Mlcro- WtPot Wt Pct Structure Structure scope 0 99.9 None Present 1 23.6 76.4 None Present 1 38.7 61.3 Present Present 2 59.4 40.6 Present Present 2 79.0 21.0 Present Not detected 2 99.9 0 Present None 1 Note: Chemical analyses of the iridium, osmium, and alloys were furnished by the American Platinum Works. of the iridium and osmium used in making the alloys also were included. Several fragments of each metal and alloy were examined microscopically and by X-ray diffraction. For the X-ray method the fragments were crushed further to pass a 270-mesh screen, then sealed in evacuated fused-silica tubes, heated to 1100°C for 18 hr, and allowed to cool in the furnace. Powder X-ray diffraction patterns were obtained from the annealed fragments by means of a Norelco camera having a diameter of 114 mm, and unfiltered cobaIt radiation. For the microscopic examination several fragments in the as-received condition were mounted in Melmac, (American Cyanamid Co.) and ground using the conventional series of abrasive papers. The polishing was done with 0-2 diamond abrasive on a Microcloth (Buehler Ltd.) lap, wet with xylene. After polishing, the surface was etched electrolytically in a 10 pct solution of chromic acid or in a 10 pct solution of potassium cyanide. Both reagents attacked the osmium-rich constituent, whereas the iridium constituent was attacked slightly by the chromic acid reagent and not noticeably by the potassium cyanide reagent. The results of the X-ray diffraction and microscopic examinations are summarized in Table I. Fig. 1 shows the microstructure of a 21 pct Ir-79 pct 0s alloy. The results indicate an appreciable solid-solu-bility range of osmium in iridium as was reported by Zvyagintzev.' The solid-solubility range of iridium in osmium is more restricted, apparently less than 21 pct Ir. This implies a large range of composition in which two phases can coexist that was not reported by Zvyagintzev.

Jan 1, 1955

By W. C. Knoblaugh

Rotary kilns are adaptable to many fuels, but this paper deals principally with the use of powdered coal. The observations and conclusions presented are based on rotary kilns used in the manufacture of basic refractories for steel furnaces. Solid fuels are pulverized for two principal reasons: (I) ease of control, and (2) rapidity of combustion. By the use of pulverized coal, the operator can increase or decrease the fuel supply by small increments and with very little time lag between the change of control and the resultant change in the flame. This is extremely important in this type of furnace, as the temperature range for maturing the clinker is very narrow. By fine grinding, it is possible to increase the rate of burning of the coal, thereby liberating great quantities of heat within a small space in a short time. Under given conditions, temperature is a measure of the heat liberated per unit of time. To attain the temperatures of 2950° to 3150ºF., which are encountered in the manufacture of various steel-furnace refractories, it is estimated that it is necessary to liberate 125,000 to 175,000 B.t.u. per cubic foot of the burning zone per hour. The manufacture of dolomitic refractories is a ceramic process and, as is true in most such processes, the material must be subjected to a certain critical temperature for a certain length of time in order to complete the reaction. If the time of reaction is reduced, the temperature must be increased; in other words, if the rate at which the material flows through the hot zone of the kiln is increased, the temperature of the hot zone must be increased to compensate for this shorter exposure to the flame. Firing with Pulverized Coal Fig. I is a line drawing of a rotary kiln with the attendant equipment indicated in their relative positions. The kiln proper consists of a sloping, refractory-lined steel tube rotating slowly about its longitudinal axis (0.75 r.p.m.), and is countercurrent in operation in that the raw feed is introduced at the stack end and gradually approaches the zone of highest temperature at the lower end, where the fuel is introduced. Before 1930, the usual method of firing a rotary kiln was to store the coal in the pulverized form and then feed from this storage to the kiln as needed. This proved unsatisfactory and dangerous because of dust explosions and the inability to obtain an even feed to the kiln caused by arching of the coal in storage and flooding of the coal feeders. In later years the practice has been to store the raw coal and grind it as it is needed. Such a layout is indicated in Fig. I. The coal is stored in bins, charged from the top and drawn from the bottom into recording scales and then into some type of unit pulverizer. There are a number of good pulverizers .on the market, each incorporating features that the manufacturer considers outstanding.

Jan 1, 1948

By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot's reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.'' The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964