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By L. S. Darken, H. A. Wriedt

The equilibria at 1 atm total pressure and 600° to 1300°C (1112° to 2372°F) between gas mixtures with various partial pressures of the reactive constituents (principally sulfur dioxide, carbon dioxide, water vapor, oxygen or carbon monoxide, and hydrogen) and coexisting solid phases (groups variously including calcium oxide, calcium carbonate, calcium sulfide, calcium sulfate, iron, ferrous sulfide, and the iron oxides) are examined. Tables and charts show the combinations of temperature, oxygen activity, and carbon dioxide partial pressure under which the various groups of the solid phases coexist and the corresponding sulfur dioxide pressures. In the presence of calcium sulfide, calcium sulfate, and calcium oxide, the partial pressure of sulfur dioxide has a peak value at each temperature which increases from 101 atm at about 800°C (1472°F) to 1 atm at about 1200°C (2192°F). With water vapor present, hydrogen sulfide may predominate among gaseous sulfur compounds, particularly at low temperatures and oxygen activities; under all other circumstances considered, sulfur dioxide is the dominant gaseous sulfur-bearing species.

Jan 1, 1974

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md'ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,'-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-' Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.'-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By F. M. Yans, A. D. Donaldson, A. R. Kaufmann

Beryllium was mixed by powder. metallurgical techniques with copper, nickel, iron, and chromium, respectively, to form beryllium -rich binary alloys which Mere then extyuded and rolled transtverse to the extrusion direction. The effect of each alloying element was determined by tensile testing. In solid solution, small amounts of iron and nickel had an embrittling effect, while copper in solution increased the strength but had no effect on ductility. The effect of chromium was complicated and not readily explainable. Observations concerning the planes and modes of fracture were made. BERYLLIUM possesses some very attractive properties for general design applications, especially its strength to weight ratio which is approximately twice that of aluminum and three times that of stainless steel. Equally significant, however, is its combination of high moduli , high strength (approximately 70,000 psi tension and 40,000 psi shear), and low density (0.0658 Ib per in.3), which has made it a potentially important structural material for use in high-speed aircraft and missiles. The main attractions of beryllium are most marked when compared to other constructional alloys now in use. For example, while its density is approximateiy that of magnesium, its modulus of elasticity is approximately seven times that of magnesium, three times that of titanium, four times that of aluminum, and 1 1/3 times that of steel. Furthermore, its relatively high strength and high melting temperature permit design for service temperatures to about 1100°F. It is felt by the aircraft industry in general,' that the high cost of beryllium can easily be amortized by the savings in fuel costs, and increases in aircraft payload and range. The only factor which has prevented the use of the metal in structural applications is its lack of sufficient ductility. It is this property that has retarded the development and utilization of beryllium. Beryllium's modes of deformation, Fig. 1 indicate that the main fracture planes at room temperature in a randomly oriented sample are the (0001) basal planes; the (1150) prism planes are the planes of secondary fracture.' Klein, Macres, Woodard, and Greenspan3 obtained elongations of up to 40 pct in beryllium sheet rolled above 700°C when the (0001) basal planes were oriented parallel to the plane of the sheet (see Fig. 2).

Jan 1, 1962

By C. Chiou, M. E. Fine

While Gunier-Preston zones are growing in Al-4.2 pct Cu at room temperature, Young's modulus, measured dynamically, increases about 0.4 pct. From the change in modulus with time the exponent of time in the rate equation for growth of the zones was deduced to be %. From a comparison of the rates of increase of modulus at 1, 28, and 42°C an activation energy of 12 to 14 Kcal per mole is computed. These findings support the idea that copper atoms are supplied along dislocation channels to growing zones. In alloys the elastic constants will be functions of the distributions of the atoms. If the degree of ordering or clustering is changed, one expects a corresponding change in the elastic constants. During age-hardening of aluminum-copper alloys at room temperature, the copper atoms cluster on 100-type planes in the aluminum lattice forming

Jan 1, 1959

By J. Clair, H. Mirabel

The determination of the temperature and electrical potential distributicms in the cathodes of aluminum electrolytic cells is difficult. The reascms come from the various nature and the intricate three-dimensional geometry of the materials; besides thermal and electrical phenomena react upon each other. A method of calculation using a computer program applied to a mathematical model, figuring the cathode, is developed. Both of the thermal and electrical phenomena are simultaneously considered. Temperature and electrical potential distributions are finally obtained by successive iterations. Results are compared with measurements on industrial cells. Theoretical and practical applications of these studies are given. Up to the present time the study of the distribution of the temperatures and electric potentials in the electrodes, anode and cathode, of the electrolytic cells used for the production of aluminum was limited to one of the two aspects of the phenomena because of lack of a simultaneous method of calculation. For example, the anode or cathode drop was studied assuming that the temperatures in the iron and carbon are known, a method that obviously is very approximate since iron resistivity, in particular, greatly varies with temperature, which in turn depends on current density. Consequently we tried to find a method of calculation simultaneously taking into account both thermal and electrical phenomena. We proceeded to the study of the cathodes as an initial approach to the problem. Although the cathode and surrounding materials may have varied forms and particularly very heterogeneous characteristics, their structures are simpler than that of the Sijderberg anode and boundary conditions are more easily represented than in the case of anodes even though they are prebaked. The study was in two parts: a) development of a model schematizing the true geometry of a cathode and defining the thermal and electrical boundary conditions, and b) working out a method of calculation of the temperatures and potentials by means of an electronic computer. To facilitate solution of the problem, a model was used initially much simplified in comparison with an actual cathode. This model permitted development of the method of calculation. In a second phase, this model was adjusted to the study of actual cathodes and applied to different types of cells: low- or high-intensity cells, cells set up at ground level or above ground level, cells with cathodes more or less heat-insulated. Simultaneously measurements were made with cells equipped with cathodes of the types studied to compare the values resulting from calculation. The initial model was also used for general studies, in particular for studying the effects of current density in the carbon and iron. The results were confirmed or made precise by the model of the true cathodes. This report successively describes: a) the manner in which the model representing a cathode was worked out, with the simplifications and/or the hypotheses used, b) the method of solution of the problem by means of the electronic computer, and c) an example, stating the extent to which the results obtained may be realistic. Further the possibilities offered by such a study are examined. 1) CATHODE REPRESENTATION The purpose of this phase is to represent the cathode in the form of a so-called "mathematical model", that is with a simplified geometrical configuration, in order to meet the subsequent calculation requirements, while keeping to the true facts as closely as possible. This model further includes the thermal and electric conductivities with regard to temperature for the varied materials composing the cathode, as well as the thermal and electrical conditions at the model boundaries. 1.1) Guiding Principles. For calculating the temperatures and potentials the model is divided by trior-thogonal planes into a network of small elementary parallelepipeds. At the summit of these parallelepipeds' so-called mesh points, the temperatures and potentials are computed. The number of mesh points is of course limited by the capabilities of the computer, since 1) the number of equations to be solved depends on the number of mesh points selected, and 2) the amount of time spent by the computer considerably increases with increasing this number. These conditions call for the following requirements as concerns the model: a) Dimensional requirements: the calculation will be all the more accurate as the network is more closely meshed. Since the number of mesh points is limited in practice, it is necessary to restrict the dimensions of the model. b) Geometrical requirements: so as to make things easier in working out the network, the model must be given a simple geometry. In particular, it will be convenient to have the cathode so constituted that the surfaces limiting the cathode and the surfaces within the cathodes separating the different materials consist of triorthogonal planes. 1.2) Schematization of the Cathodes. After the tech-

Jan 1, 1968

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By L. W. McKeehan

IT is no longer necessary, if it ever was, for your annual lecturer to apologize for including in his remarks frequent references to the arrange-ment of metal atoms in crystals and for basing his arguments that metals behave as they do upon their crystal structure. Neither will any objec-tion be raised because the large metallic crystals of which we will speak are hard to prepare and of negligible commercial interest. The particular set of physical properties we propose to discuss-ferromagnetic proper-ties-may require more justification. Very few in this audience are primarily, or even remotely, interested in the ferromagnetic behavior of the metals they handle. By no means all of you ever deal, by choice or by necessity, with metals which display any ferromagnetism at all, and even those who study or control ferrous metallurgy must usually depend upon electrical engineers for assistance in ferromagnetic applications. My excuse for talking about such an obvious specialty is, like all Gaul, divided into three parts. In the first place, the members of the com-mittee who select the annual lecturer must wish the speaker to confine himself to matters he has at least thought about before he prepares his speech. In the second place, the study of ferromagnetism in crystals has, as you will soon realize, suffered in the not-too-distant past from inade-quate metallurgy. Further progress probably depends upon proper use being made of the skill and knowledge of some members of the Institute of Metals Division who have not, before today, been asked to think about the problems presented here. Finally, there is at least a sporting chance that the ferromagnetic properties of a few metal crystals will give some insight into the more generally interesting properties which they share with nonferromagnetic metal crystals.

Jan 1, 1934

By James T. Kemp

SOME interesting and, to American eyes, rather unusual processes for refining impure aluminum derived from scraps were found by American and British investigators who went into Germany in 1945 for the Technical Industrial Intelligence Committee Of the Joint Chiefs of Staff. What was found was recorded in a series of reports (see page 14), many of which have been released for general reading. This paper gathers under one title and summarizes the German work in refining light metal scrap. Reference must be made to the original reports for greater detail. Basically, the occasion and stimulus for the German developments in treating light metal scrap were hard necessity. Germany needed the metal for a rapacious war industry. Adequate supplies of new aluminum from reduction works were not assured. Great quantities of airplane and other light metal war scraps were forecast. It was evident that the scrap metal would have to be reabsorbed by the producing industry and would have to be kept of good quality. The normal current production of manufacturing scrap was being and could be consumed as generated. It offered no technical problem. The mixed scraps, especially those arising from crashed and decommissioned airplanes, however, presented problems of another kind. AIRPLANE SCRAP The recovery of usable aluminum alloy from the mixed assemblies that made up the piles of airplane scrap was attacked in different ways by different groups and with differing degrees of success. Three procedures actually were used On a commercial scale, one was in pilot-plant stage and another had come to a halt in the laboratory a year before Germany collapsed. Four of these five processes actually involved "refining"; that is, some measure of purification of the metal after melting. SORTING AND SEPARATION ON A SLOPING HEARTH The simplest procedure for utilizing airplane scrap involved no refining in the strict sense of the word. This was the practice adopted by two representative plants visited by the author, the Leipziger Leichtmetalle Werke, Rackwitz, Saxony, and the Vereinigte Leichtmetalle Werke, Hanover. These firms did essentially the same thing that was done in England but not with equal success, to judge by their shorter experience, the smaller tonnage handled and by the number and quality of alloys produced. The two German firms named rough-sorted scraps by their easily recognizable alloys, essentially by part and shape. They used hand labor to chop and hack and tear apart. The easily separated heavy metal and nonmetallic scraps were discarded as they were found. Steel and the higher-melting-point metal parts riveted to aluminum or built into

Jan 1, 1947

NEW MEMBERS The following list comprises the names of those persons who became members during the period Jan. 10 to Feb. 10, 1915: Members AGASSIZ, RUDOLPH Louis, Vice-Pres.,Calumet & Hecla Mining Co., Boston, Mass. AMIDON, RICHARD G., Min. Engr 3659 Girard Ave. N., Minneapolis, Minn. ANDERSON, HECTOR G. S., Min. Engr 323 N. 13th St., Muskogee, Okla. ANDERSON, JOHN CARTER, Petroleum Engr 2307 S. 33d St., Omaha, Neb. CLARKE, ALEXANDER FIELDER, Works Mgr., Firth-Sterling Steel Co., McKeesport, Pa. CROSS, CARLOS GARCIA, Min. Engr Calle Valparaiso 194, Vina del Mar, Chile. DAWSON, THOMAS WILLIAM, Min. Engr., Asst. Chief Engr., H. C. Frick Coke Co., Scottdale, Pa.

Jan 3, 1915

By O?Harra B. M.

THE work here described had for its purpose the procuring of data from which some quantitative estimate might be made of the results obtainable by using oxygen-enriched air in roasting zinc ores on a commercial scale. The principal metallurgical advantages of using enriched air in roasting zinc ores would be: 1. The rate of roasting would be increased, with consequent gain in the capacity of the roasting furnace. 2. As less air would be required for roasting, the volume of hot gases leaving the furnace and the heat carried out of the furnace as sensible heat in these gases would be less per ton of ore roasted; partly for this reason and partly because of the increased quantity of heat generated in the furnace by the larger amount of ore that could be roasted, the consumption of fuel by the furnace would be lessened; and by the use of air sufficiently enriched with oxygen the necessity of using fuel might be entirely obviated. 3. Roaster gas having a higher SO2 content could be produced; this would make possible greater capacity and more economical operation of the sulfuric-acid plant. Certain phases of the application of enriched air to roasting can be worked out only by experimenting with a furnace of commercial, or at least semicommercial, size. Thus the precautions necessary to secure proper. distribution of heat in the furnace;1 the volume of enriched air; and the proportion of oxygen in this air, necessary to give the desired increase in roasting capacity of the furnace and in SO2 content of the roaster gases;; and the most desirable frequency of raking, thickness of

Jan 11, 1924

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970

By P. L. Hendricks, J. W. Spretnak

The interstitial atom principally responsible for the yield point and strain aging in electron-beam-melted tantalum is identified by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Two sets of specimens contained two levels of oxygen with very low hydrogen contents and the third set had comparable oxygen and hydrogen contents. The activation energy for the return of the yield point agrees well with that for diffusion of oxygen for the first two sets of specimens. For the third set of specimens, the activation-energy value lies between those for diffusion of hydrogen and for diffusion of oxygen. The advent of the dislocation model of plastic deformation in metals has revitalized interest in the yield point and strain aging in bcc metals containing a certain minimum content of interstitial solute elements. Much theoretical and experimental work has been performed in recent years to elucidate the detailed mechanism of these phenomena. The purpose of this investigation is to attempt to identify the principal interstitial element responsible for the yield-point phenomenon in electron-beam-melted tantalum by analysis of the kinetics of the return of the yield point after an increment of plastic deformation. Some of the earlier theories of the yield-point phenomenon proposed a grain boundary film of iron carbide. Such models could not satisfactorily explain all features of strain aging and the yield-point phenomena. The most widely accepted explanation is that of Cottrell,1 later extended by Cottrell and Bilby.2 Strain aging is ascribed to "locking" of dislocations by interstitial solute "atmospheres". The yield-point phenomenon results when the dislocations are torn away from their atmospheres. The strain-aged condition is re-established after sufficient time to allow the interstitial atoms to diffuse to the dislocation lines and re-establish the locking atmospheres. Clearly, the Cottrell-Bilby model is concerned with the bulk of the grain and does not specifically involve the grain boundary. The recent modification of the Cottrell-Bilby model is a redirection of attention to the role of the grain boundary and the possibility of multiplication of a limited number of free dislocations rather than unlocking all of the dislocations. Theories have been advanced by Hahn3 and conrad4 which are modifications of the Cottrell-Bilby theory. The model proposed by Hahn indicates that, although the possibility of un- locking anchored dislocations is not excluded, it implies that unlocking is not necessarily required to explain yield drop. Locking of dislocations during the aging treatment is a necessary part of the theory; however, it assumes that dislocations once locked remain locked. It is suggested that the yield drop observed is a result of the following factors: 1) the presence of a small number of mobile dislocations initially, 2) rapid dislocation multiplication, 3) the stress dependence of dislocation velocity. In the case of bcc metals, locking is considered to be the means by which dislocations are immobilized. Cold working of the metal results in the generation of larger numbers of new dislocations and the stress dependence of the dislocation velocity accounts for yield drop observed. Conrad' has proposed a model similar to the one just described which applies to strain aging of iron and steel and which logically could be extended to other bcc metals. This model also does not require large-scale unlocking of dislocations. It is proposed that, during initial loading of a specimen below the upper yield stress, a few dislocations are torn free of their Cottrell atmospheres at regions of stress concentrations. With an increasing stress, some multiplication of dislocations occurs by a double cross slip mechanism, thus giving a preyield microstrain. At some critical stress represented by the upper yield stress, sudden profuse multiplication of dislocations occurs, enabling plastic flow to proceed at a lower stress. In this model, microstrain, preyielding, and flow represent the movement of free dislocations. It should be noted that this model also requires the locking of dislocations by interstitial solute atoms for the occurrence of a yield point; however, unlocking of large numbers of dislocations is not required. If it is assumed that the yield point will return when some fraction of free dislocations produced during pre-straining are pinned, the number of solute atoms required to pin unit length of a dislocation line can be calculated when prestrain and reloading are done at the same temperature and strain rate. Since the migration of solute atoms back to the stress fields of dislocation lines is controlled by the diffusion rate of interstitial solute atoms, it is to be expected that the activation energy for strain aging would be identical to the activation energy for diffusion. It would also be expected that the strain aging observed will be controlled by the fastest diffusing species capable of producing locking over the temperature range investigated. The rate of yield-point return has been found to be adequately expressed by an empirical rate equation of the form: rate=Ae-Q/RT [1] where A = constant, Q = activation energy, R = gas constant, and T = absolute temperature. Cottrell and Bilby2 have expressed the number of atoms per unit length of dislocation line which arrive

Jan 1, 1967

By Russell G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses.

Jan 2, 1951

By B. C. Craft, Murray F. Hawkins, John R. Rayne

A reservoir mechanism of sulfur recovery by the Frasch process is presented. Improving the economic, of recovery appears to be largely a well, rather than a reservoir problem. A most important factor is the limitation of the lateral extraction of .sulfur about the wells due to the almost vertical .flow of the injected hot water. Model studies are described which confirin the mechanism of sulfur recovery by presently used methods. Studies on a five-spot system indicate improved econo171ics regarding recovery, recovery rate, therinal efficiency, and well spacing. INTRODUCTION Sulfur mining by the Frasch process is one of the most important methods of sulfur production. Developed by Herman Frasch in 1894, it enjoyed a rapid growth and presently supplies 40 per cent of the world's sulfur and about 80 per cent of the U. S. sulfur." The Frasch process of mining the underground native sulfur deposits involves melting the sulfur in place by introducing super-heated water into the sulfur bearing formations, and producing the sulfur as a liquid. Many problems are encountered in mining these native sulfur deposits, and sulfur production depends chiefly upon the nature of the sulfur deposit and the underground thermal efficiency of the heat transfer system. THE RECOVERY MECHANISM Sulfur is typically found in salt dome cap rock as crystal aggregates occurring within the cavities, seams, and pores of limestone and gypsum formations.' Sulfur-bearing limestone is typically cavernous, vugular, and fractured. Porosity averages about 20 per cent and sulfur saturation averages approximately 25 per cent by weight.1,15 Vhe sulfur bearing formations are very heterogeneous in nature and physical characteristics vary widely within small distances. Total cap rock thickness may vary from 50 to more than 1,000 ft, and net productive thicknesses from a few feet to a few hundred feet. In most cases the upper portion of the limestone formation is barren of sulfur, varying from 5 to 200 ft in thickness.1,15,33 The immediately overlying sediments and the underlying dense anhydrite formation provide permeability barriers to the flow of water from the cap rock section.'" Sulfur wells are drilled with conventional oilfield drilling rigs. Fig. 1 illustrates the casing program of a completed sulfur well. The cap rock sections are drilled with core bits and continuous core logs are recorded. After coring, the cap rock section is underreamed to a diameter of 9 7/8 in. The bottom of the 8-in. casing is welded closed and rests on the bottom of the drill hole, which extends through the cap rock to a few feet above the bottom of the sulfur-bearing formation. The 8-in. pipe contains 5 ft of 3/4-in. perforations on 6-in. centers and 15 ft of 1-in. perforations on 1-ft centers. The 20-ft perforated section is set opposite the lower 20 ft of the sulfur-bearing formation. The 4-in. sulfur pipe is set inside the 8-in. water line on a seat ring at the top of the 5-ft section of 3/4-in. perforations. The mining water, heated to about 330°F under a pressure of 250 psi, is forced down the annulus between the 8-in. and 441-1. pipes and through the 1-in. perforations to the sulfur-bearing formation. Compressed air, at 400 psi pressure, is supplied through a 1-in. air line near the bottom of the well to provide air-lift of the liquid

Jan 1, 1957

By Horace V. Winchell

The laws here referred to are those which define the status of the prospector for mineral deposits in the soil or beneath it, establish his methods of procedure, protect him in his possession while searching for the subterranean treasures, and give him assurance of title when all required conditions have been fulfilled and valuable minerals discovered. Regulations for the operation of mines and the safety and health of mine employees are likewise subjects of Federal and State legislation, but are not within the scope of the present program. Various features of our present laws will be discussed in detail by able students of the subject, and specific remedies will be proposed for the most glaring defects. It is my purpose to present in this paper a summary review of the reasons why revision is needed and demanded by the great majority of those in daily contact with the industry. Reason Number One The first objection to the continuance of the present law is that it was not planned by its framers and the Congress which passed it to apply to many of the kinds of mineral deposits, nor to the mining conditions, which are controlled by it to-day. In 1866, under the title, "An Act granting the right of way to ditch and canal owners over the public lands, and for other purposes," was surreptitiously smuggled into existence our first mining law (14 Stats. at Large, Chap. 262, p. 251). This law provided that "whenever any person or association of persons claim a vein or lode of quartz or other rock in place, bearing gold, silver, cinnabar or copper, having previously occupied and improved the same according to the local customs or rules of miners in the district where the same is situated," etc., a patent might be granted an certain conditions. This was evidently an Act intended to validate claims already initiated, and to accord Federal recognition to mining locations made in

Jan 1, 1915

By John Rogers

The goal of a detailed quantitative understanding of the variables insulfide flotation in terms of established, or new, scientific principles is still distant, although there has been a good beginning in the past 50 years with more rapid progress since 1930. Advances have paralleled closely those in other branches of surface chemistry and the development of a series of experimental techniques such as contact angle, surface area measurement, radioactive tracers, infrared spectra, electron diffraction, monolayer, and electro- chemical methods of investigation. The second editions of books by Sutherland and Warkl ( 1955) and Gaudin2 ( 19571, are detailed accounts of this progress. The complexity of sulfide mineral flotation systems is indicated by Sutherland and Warkl who list 32 variables of flotation, of which only 22 can usually be controlled by the metallurgist. A consequence of this multiplicity of variables, many of which may be specific to each particular ore, is that ways of floating sulfide minerals from new ores are still developed empirically. How- ever, this review will try to show how the chemistry of the function of frothers, collectors, depressants, and activators in sulfide flotation is being steadily unravelled. Chiefly, it will be concerned with the interaction of pure soluble compounds with individual sulfide minerals, the surfaces of which are often not stoichiometric for several reasons discussed by Plaksin.3 As a result, for example, a freshly cleaved galena surface has cathodic and anodic areas which have different degrees of oxidation and different reactivity to- wards collectors like xanthate. Such complicating considerations should be remembered in the subsequent discussion of pure minerals. THE NEED FOR FLOTATION REAGENTS After considerable controversy it has been established with a few exceptions that unoxidized, uncontaminated sulfides will not float. Moreover all flotation plants recovering sulfide minerals use collectors which are removed from the circuit with the sulfides. Gaudin, Miaw, and Spedden4 have discussed the relation between the crystal structure of solids and the native floatability of the exceptions mentioned above. A second question which has been much explored is the nature of the surface on which a collector like xanthate is adsorbed or reacts. Is this the un- changed surface of the sulfide mineral, or does the adsorption depend on the initial oxidation of the sulfide surface ? Sutherland and Warkl and Gaudin2 discuss the work of Taggart5 and others on this question without reaching any other conclusion than that oxygen was important.

Jan 1, 1962

By F. W. McQuiston

Teamwork is the key to an efficient organization. Cooperation among mining staff members is an obligation owed to the company. The more cooperation the metallurgist receives from underground, the higher milling yield will be, which in turn makes for a greater mine profit. There is no pay for metal left in mill tailings. The metallurgist is not in a position to be of help to either the geologist or mining engineer, but can receive valuable assistance from both. Therefore, the metallurgist must win underground cooperation. The mining engineer is usually interested in geology because of its relation to ore control; in milling because that is where the rock goes. However, any overlapping of interest between geologist and metallurgist is quite remote.

Jul 1, 1956

By T. R. Graham, R. S. Dean. J. R. Long

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947