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By V. F. Parry, E. O. Wagner

This paper summarizes investigations during 1949 on three pilot plants for drying low-rank fine coal by entrapment in hot gases. Detailed operating results on processing seven coals having moisture ranging from 24 to 62 pet, formulas and data for calculating performance of large units, and general conclusions on the problem of drying fine coal are presented. THIS paper presents a summary of investigations by the Coal Branch of the Bureau of Mines during 1949 on the removal of internal moisture from low-rank coals by processing them in the entrained and fluidized state. A paper on this subject, giving a summary of the early work, was presented at the 1949 AIME annual meeting1 and gave a the- oretical discussion of the time and heat required to dry various sizes of low-rank coal. The investigations on two pilot plants were presented in the foregoing paper. During 1949, three additional pilot plants were built to study phases of the drying problem and to investigate different techniques of handling fine coal in the entrained and fluidized state. The present paper gives operating data on the new units and presents detailed data on the drying of seven coals having bed moisture ranging from 62 to 24 pct. The problem of removing surface moisture from fine coal is principally one of heat exchange and dispersion of the coal particles so that heat can reach the liquid moisture to permit evaporation, and it does not involve the factors of size and time of contact to any great extent. If enough heat can reach the surface of the particles at temperatures higher than 250°F, moisture evaporates almost instantly, and the factors of time and size are of secondary importance compared with the factors of heat balance and dispersion of the coal. Therefore, it does not appear to be necessary to employ a fluidized bed when removing surface moisture, and the most efficient process would be one in which the coal particles are entrained in a hot gas stream of optimum temperature traveling at a velocity that causes the particles to disperse into a low-density phase. When low-rank coals are dried, the fluidized bed is necessary to provide control of time of contact. This is done by adjusting the superficial velocity which controls the density or dispersion of the particles. The density of beds having fluidized properties suitable for drying low-rank coals appears to range from about 5 up to about 15 lb per cu ft. When the density is below 5 lb per cu ft, which represents a low-density phase, optimum conditions for removal of surface moisture should be found, and this requires superficial velocities of about 15 fps. The problem of removing bed moisture from low-rank coals involves consideration of size of coal, temperature, mass flow, heat balance, pressure, time of contact, and method of dispersing the coal in the heating mediums. The experimental work presented here gives data on these factors. Coal sizes up to 1/2 in. x 0 were dried with hot gases having initial temperatures ranging from 1900° to 2400°F. Coal

Jan 1, 1951

By E. O. Wagner, V. F. Parry

This paper summarizes investigations during 1949 on three pilot plants for drying low-rank fine coal by entrapment in hot gases. Detailed operating results on processing seven coals having moisture ranging from 24 to 62 pet, formulas and data for calculating performance of large units, and general conclusions on the problem of drying fine coal are presented. THIS paper presents a summary of investigations by the Coal Branch of the Bureau of Mines during 1949 on the removal of internal moisture from low-rank coals by processing them in the entrained and fluidized state. A paper on this subject, giving a summary of the early work, was presented at the 1949 AIME annual meeting1 and gave a the- oretical discussion of the time and heat required to dry various sizes of low-rank coal. The investigations on two pilot plants were presented in the foregoing paper. During 1949, three additional pilot plants were built to study phases of the drying problem and to investigate different techniques of handling fine coal in the entrained and fluidized state. The present paper gives operating data on the new units and presents detailed data on the drying of seven coals having bed moisture ranging from 62 to 24 pct. The problem of removing surface moisture from fine coal is principally one of heat exchange and dispersion of the coal particles so that heat can reach the liquid moisture to permit evaporation, and it does not involve the factors of size and time of contact to any great extent. If enough heat can reach the surface of the particles at temperatures higher than 250°F, moisture evaporates almost instantly, and the factors of time and size are of secondary importance compared with the factors of heat balance and dispersion of the coal. Therefore, it does not appear to be necessary to employ a fluidized bed when removing surface moisture, and the most efficient process would be one in which the coal particles are entrained in a hot gas stream of optimum temperature traveling at a velocity that causes the particles to disperse into a low-density phase. When low-rank coals are dried, the fluidized bed is necessary to provide control of time of contact. This is done by adjusting the superficial velocity which controls the density or dispersion of the particles. The density of beds having fluidized properties suitable for drying low-rank coals appears to range from about 5 up to about 15 lb per cu ft. When the density is below 5 lb per cu ft, which represents a low-density phase, optimum conditions for removal of surface moisture should be found, and this requires superficial velocities of about 15 fps. The problem of removing bed moisture from low-rank coals involves consideration of size of coal, temperature, mass flow, heat balance, pressure, time of contact, and method of dispersing the coal in the heating mediums. The experimental work presented here gives data on these factors. Coal sizes up to 1/2 in. x 0 were dried with hot gases having initial temperatures ranging from 1900° to 2400°F. Coal

Jan 1, 1951

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet's safety rules' be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,' was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References 'P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman's arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman's paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman's work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"'. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By K. E. Starling

Phase equilibria data were used to develop an equation-of-state correlation for complex hydrocarbon mixtures, thereby circumventing difficulties associated with use of pressure-volume-temperature data. Equilibrium phase data for two condensate reservoir fluids were used to determine equation-of-state parameters for hydrocarbons as heavy as C22H46 in a modified form of the Benedict-Webb-Rubin equation of state. Comparative tests of K-values from the resultant correlation were made with data for condensate reservoir, separator and gas plant absorber mixtures. Generally, for temperatures above OF and computed liquid densities below 0.55 Ib-mole/cu ft, the modified BIVR equation predicted K-values in close agreement with the experimental data. INTRODUCTION Accurate predictions of thermodynamic behavior for complex hydrocarbon mixtures are necessary for many calculations in the petroleum industry. Because of the relatively high cost of extensive experimental data, many correlations for prediction of phase behavior have been developed. Some of these, such as the correlation of K-values presented in the NGAA Equilibrium Ratio Data Book, are totally empirical.l Others, such as the Benedict-Webb-Rubin (BWR) equation-of-state method, are semitheoretical.2-4 Unfortunately, published correlation methods often do not accurately predict the phase behavior of complex hydrocarbon mixtures, principally because of inadequate representation of the effects of components heavier than decane. This paper presents a new approach to this problem in which basic equation-of-state relations including heavy hydrocarbon effects are applied. Equilibrium phase data for two condensate reservoir fluids containing hydrocarbons as heavy as C22H46 are used to correlate component K-values. The BWR equation was chosen as the prototype equation of state for this study because of its proven capability for accurately predicting phase behavior and thermodynamic properties of light - hydrocarbon mixtures? Research was directed toward development of BWR parameters for the heavy hydrocarbons and modifications of the mathematical form of the BWR equation for application to complex hydrocarbon mixtures. The new equation-of-state approach presented differs considerably from previous methods in that phase equilibria rather than PVT data are used for determination of equation-of-state parameters. It is an explicit approach since the parameters are determined directly from mixture data. As such, it does not encounter problems inherent in the implicit method used by Benedict, Webb and Rubin 2-4 and numerous other investigators—one in which mixture parameters were postulated to be functions of the pure component parameters. The pure component BWR parameters, in turn, were determined from experimental PVT data. This method has been limited to mixtures containing components lighter than decane because of lack of vapor phase PVT data. Studies have been reported in which BWR parameters have been determined explicitly from PVT data for binary mixtures.6-8 However, since small concentrations of heavier components have only a minor effect on PVT behavior, it is doubtful that these explicit methods would yield useful results for condensate systems. Ellington and Eakin9 have shown that the accuracy of K-values predicted by an equation of state developed from mixture PVT data probably would be more than an order of magnitude lower than the accuracy of the PVT data. On the other hand, an equation of state utilizing parameters developed from phase equilibria data should predict K-values with accuracy comparable to the accuracy of the experimental phase compositions. This work applies this explicit approach with the objective of improving hydrocarbon mixture phase behavior predictions. Results are evaluated by comparing predicted and experimental K-values at reservoir, separator and gas plant

Jan 1, 1967

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.' They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger' report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

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

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By J. P. Boisseau, C. N. J. Wagner, E. N. Aqua

An analysis ulas made of powder-paltern peaks from cold-rolled polycrystalline copper and from copper powders, compacted into briquets (1 in. diameter) with pressures up to about 106 psi. Powder-pattern peaks from both contact faces were measured with a diffractometer and CuKa radiation. Laltice-parameter measurements indicate the presence of residual stresses in the bulk specimen of the order of a - -10 kg per sq mm after 93 pct reduction in thickness, and give some evidence for the occurrence of deformation stacking faults (probability a - 0.003) in both bulk and powder samples. Fourier analyses of the line profiles were carried out on the (111) - (222) and (200) - (400) Pairs of reflections. The particle sizes decrease rapidly with increasing deformation and reach asymptotic values of De (111) = 550A and D, (200) = 350A at about 25 pct reduction in thickness or 80,000 psi pressure for compaction. The anisotropy of the particle sizes indicates the presence of microtwins and stacking faults on (111) planes. The rms strains increase also with deformation and reach limiting values of 2 x 10-3 in the [100] direction and 1 x 10-3 in the [Ill] direction at a distance L = 100A normal to the reflecting planes. THE diffraction of X-rays in cold-worked, polycrystalline, fcc metals and alloys yields Debye-Scherrer patterns in which the individual (hkl) lines may show a broadening, a shift, and an asymmetric shape.' These effects can be explained by the fragmentation of the small, coherently diffracting domains, the presence of residual elastic strains in the lattice, and the formation of stacking faults. X-ray studies of stacking faults in fcc metals and alloys have been methodically performed during the last few years, but so far most of the investigators dealt with cold-worked powder specimens obtained by filing.2-8,10-19 In such specimens, the crystals are randomly oriented and the average elastic strains are assumed to be zero, so that the observed peak shifts are due to stacking faults only. The agreement between X-ray diffraction theory1,20 and experiment is generally good. On the contrary, cold-worked, polycrystalline bulk specimens (after wire drawing, rolling, plastic deformation by tension or compression, etc.) contain residual elastic strains, which may not average to zero in the surface of the specimen and show very strong preferred orientation of certain lattice planes (texture) parallel to the specimen surface. Nonzero elastic strains also produce peak shifts, the magnitudes of which depend upon the crystallographic orientation of the reflecting lattice planes in elastically anisotropic materials as well as on the type of plastic deformation and which have to be taken into account when measuring stacking-fault probabilities in deformed bulk specimens.21-23 The purpose of the present investigations was to perform a detailed X-ray analysis on a bulk specimen of a fcc metal deformed by rolling at room temperature and on powder of the same material deformed by compaction, and to compare these results with those previously obtained on cold-worked filings.18 Pure copper was chosen for this study since it is known to produce only a small quantity of stacking faults by filing at room temperature.3,16,17,19 The residual elastic strain in the surface of the bulk copper should be the predominant factor determining

Jan 1, 1965

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,' is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.' The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson's ratio, v, and Young's modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By F. V. Lenel, G. S. Ansell

The creep behavior of an aluminum -aluminum oxide alloy, A T 400, fabricated by compacting an atomized aluminum powder, extruding the compact, cold working, and recrystallizing the extrusion, was investigated. This alloy has a dispersion spacing of 1 . Previously Ansell and Weertman determined the steady-state creep rate of a recrystallized aluminum-aluminum oxide SAP-type alloy, MD 2100, with a 0.48-p dispersion. This alloy was found to have a steady-state creep rate of less than 10-6 min-1, too small to be measured accurately. By employing a more sensitive method of measuring creep rate, it was possible to determine the steady-state creep rate of AT 400 alloy, which is somewhat faster than that of MD 2100, at a series of temperature and applied stresses. Above a stress of Burger's vector, A = dispersion spacing, u = is a shear modulus) the rate follms an equation of the type: Steady-state creep rate K = A exp. where A is a constant, Q is the activation energy for sey-diffusion, and is the applied stress. At stresses lower than the steady-state creep rate drops off sharply and is no longer in agreement with this equation. This behavior is in good agreement with that predicted by the model for dispersion strengthened alloys in the stress and temperature range investigated. The absolute value of the creep rate is, however, four orders of magnitude lower than that predicted if the normal number of active dislocation sources are assumed to be present. It is concluded that in this SAP-type alloy the usual three-dimensional dislocation network is not present. Instead, short dislocation segments extending from one dispersed particle and terminating at a neighboring particle may act as dislocation sources. With this provision the creep model proposed by Ansell and Weertman reasonably accounts for the creep behavior which was observed. RECENTLY, Ansell and Weertman1 proposed a dislocation model from which they derived creep equations to describe the steady-state creep behavior of dispersion - strengthened alloys. Following Schoeck,2 they assumed that the rate controlling process for steady-state creep is the climb of dislocations over the dispersed particles. In order to verify their creep model, Ansell and Weertman determined the steady-state creep behavior of an aluminum-aluminum oxide SAP-type alloy, MD-2100, in both the fine-grained as-extruded, and coarse-grained recrystallized conditions. Since the grain size was the order of the dispersion-spacing, their model was not applicable for the as-ex- truded alloy. It should, however, be applicable to the coarse-grained recrystallized alloy. The results they obtained were rather unexpected. No meas-ureable steady-state creep was observed for the recrystallized MD-2100 alloy. If their model is correct, and if the second-phase particles act solely to hinder dislocation motion, then some measureable steady-state creep would have been expected. On this basis, they postulated that, in this SAP-type alloy, the main effect of the fine dispersion was to inactivate dislocation sources rather than to hinder the movement of dislocations. In order to understand more fully this unusual creep behavior, and to determine the validity of the model proposed,' the steady-state creep behavior of an aluminum-aluminum oxide recrystallized SAP-type alloy, with a somewhat coarser dispersion spacing, was investigated. The results of this study are presented in this paper.

Jan 1, 1962

By N. F. Schulz, H. A. Lex, J. D. Zetterstrom

A green ball of iron ore faces many perils from the time it is formed until it finally emerges from the pelletizing furnace as a hardened pellet. For instance, if the rate of heat transfer into a ball is sufficient to produce vapor from either the free or combined water more rapidly than it can escape at a tolerable pressure, the ball may split, spall, or even explode, a failure commonly known as decrepitation. To avoid such failures, one must either limit the rate of heat transfer during the drying and preheating stages, at the expense of production rates, or improve the decrepitation resistance of the green balls. The latter remedy may often be accomplished through changes in ore preparation, balling procedures, or the judicious use of binders or other additives. INTRODUCTION Pelletization has become established as an especially desirable method for the agglomeration of fine taconite concentrates and it promises to be equally satisfactory for improving the physical structures of certain natural ores. A high-quality pelletized iron ore consists of uniformly sized spheres, usually about 1/2-in. diam, which are strong enough to resist abrasion and breakage during handling and which reduce well without disintegration in the blast furnace. The unfired agglomerates, "green balls", are subject to several destructive effects that must be avoided or minimized if a high-quality product is to be obtained by pelletization. Among these are abrasion and impact deformation or breakage during handling of the wet green balls, deformation and breakage by compressive forces in the bed of ore in the pel-letizing furnace, decrepitation during drying and preheating, wind erosion, and radial cracking at firing temperatures. Moisture condensation from the warm saturated gases downstream from the drying zone on wet, cool balls may cause bed collapse if it becomes excessive. Decrepitation is defined as the sudden disintegration of green balls, usually with an audible pop, that occurs when they are heated too rapidly during the drying or preheating stages of the pelletization process. The extent of ball disintegration may vary from merely splitting off a small fragment to almost total disintegration into the original ore particles making up the ball. Such ball destruction results in a decreased yield of pellets, and the fragments, which also tend to interfere by obstructing the gas flow through the bed, must eventually be screened from the fired product and recycled. The closely related type of ball failure that sometimes occurs during the high temperature firing stage, resulting in radial cracks without fragmentation, was not considered to be decrepitation for the purpose of this investigation. Failure by decrepitation is not usually a serious problem in the pelletization of taconite concentrates. The problem is significant, however, in the pelletization of some natural ores, especially those containing hydrous iron oxides. In some instances, economicd production rates cannot be maintained if the drying and preheating rates are slowed down enough to avoid decrepitation. OBJECTIVES This investigation was undertaken to: (1) Develop a practical laboratory means for quantitatively measuring the tendency for green balls to decrepitate in iron ore pelletizing furnaces, and (2) Investigate the causes and cures of ball decrepitation. MATERIALS Two iron ores were used in the work reported here: a taconite concentrate at 90% minus 325 mesh, containing 65.0% Fe, 8.4% SiO2, and no loss-on-ignition; and a crude oxidized ore at 54% minus 325 mesh, containing 59.1% Fe, 3.6% SiO2, 1.1% A12O3, and 9.5% loss-on-ignition. For a special test of effect of particle size distribution on decrepitation, two other

Jan 1, 1967