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By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962

By W. H. Gauvin, N. J. Themelis

I N ADDITION to its practical importance in the beneficiation of iron ores and in direct-iron processes, the study of the reduction of iron oxides involves many aspects of challenging theoretical interest. The complexity of the reduction process combined with the fact that under different experimental conditions the controlling stage for the reaction may not necessarily be the same, has led experimenters in this field to a wide diversity of opinion regarding the reaction mecl1anism. As a rule, each investigation has been restricted to the study of one or two variables over a comparative]~• narrow range of experimental conditions, and consequently, it be-comes necessary to examine the significance of each published work in the light of the results of other experimenters in the field.

Jan 1, 1962

By Louis P. Domingues

As part of a study on high-temperature ceramic materials, the ammonium sulfate, carbonate, nitrate, oxalate, and sulfate salts of yttrium, lanthanum, and cerium were analyzed thermogravimetrically. The temperature ranged from room temperature to 1,500° C. Each salt was decomposed by heating at a rate of 2.5° C. per minute, and some of the salts were subjected to additional rates of 5° C. per minute or 10° C. per minute. The decomposition sequences have been identified, and the temperatures of formation of intermediate compounds and of the oxides have been determined. The minimum oxide formation temperature of a given lanthanum salt exceeds that for the similar salt of yttrium, and both exceed that for the same salt of cerium except for one cerium carbonate. Variation of the heating rate indicates a thermal lag in the materials and produces the shift of formation temperatures to higher values and loss of resolution in the weight-loss distribution as the heating rate increases.

Jan 1, 1962

By Arnulf Muan

PHASE relations in three isothermal sections (l000°, 1100°, 1200°C) of the system Ag-Fe-Pd have been determined as part of a program to develop improved crucible materials for containing low-melting iron silicates at low oxygen potentials. The following experimental method was used: Two- to 3- g samples of each of forty different alloys within the system Ag-Fe-Pd were made up from metals of 99.9 pct purity. The mixed metal powders were contained in a 1-cc crucible of dense recrystal-lized alumina and heated in a protective atmosphere (90 vol pct A, 10 vol pct H2), first to complete melting for approximately 30 min and subsequently at the desired equilibration temperature (1000°, 1100°, or 1200°C) for approximately 24 hr. The samples were then quenched rapidly to room temperature and examined metallographically as well as by X-ray techniques. Unit cell dimensions were compared with standards obtained by study of one-phase alloys of known compositions. The results are summarized in diagrams (a), (b), and (c) shown in Fig. 1. Heavy solid curves outline areas comprising compositions of mixtures consisting of the phases labeled for each area. Mixtures in which liquid is the only condensed phase present are confined to very narrow areas adjacent to the Ag-Pd join at high silver contents. An enlarged, distorted picture of the phase relations prevailing in these areas is shown in the upper-left circular insert. Particular attention is directed toward the misci-bility gap which occupies major parts of the composi-

Jan 1, 1962

By Rodney P. Smith

THE solubility of columbium nitride in ? iron has been determined for the temperature range 1191o to 1336°C from the nitrogen content and metallogra-phic examination of a series of Fe-Nb alloys.* (0.0 to 0.92 pct Nb) equilibrated with a purified gas mixture of 1 pct hydrogen in nitrogen. The method is the same as that used by Darken, Smith, and Filer' to determine the solubility of aluminum nitride in y iron. The variation in the furnace temperature during an equilibration period was about ± 2.0°C. Each sample was approximately 1/2 in. wide, 2 in. long, and 1/16 in. thick. A time series at 1200°C using samples of highest columbium content indicated that one day was sufficient for equilibrium; however, to be on the safe side all samples were left in the furnace for either two or three days. Afterequilibration, the samples were brought to room temperature by quenching in water. The experimental results are shown in Fig. 1. To be in accord with the values reported by Wriedt and Gonzalez2 and the temperature coefficient of our results at higher temperatures, the nitrogen content of iron at 1191oC is assumed to be slightly lower than our experimental value. Our data for the single-phase regions are not sufficiently accurate to establish an interaction coefficient for nitrogen in these alloys. However, the change in nitrogen content with change in alloy content for a number of systems (Fe-N-A1;3,1 Fe-N-Ni;372 Fe-N-Si.3949 Fe-N-V;3,5 Fe-N-Cr;3,6 Fe-N-Mo3,7) has practically the same value for the liquid alloy at a temperature near 1600°C as for the solid alloy at temperatures near 1200oC when the alloy content is below a few percent. On this basis the lines through the single-phase regions have been drawn with a slope corresponding to an increase in nitrogen of 0.0013 pct per 0.1 pct Nb.3 The straight lines through the two-phase regions were drawn with a slope corresponding to a one-to-one atom ratio of nitrogen to columbium in the nitride. The X-ray

Jan 1, 1962

By A. M. Gaudin

The flotation process has been applied extensively in the mineral and chemical fields. This paper reveals results obtained by an exploration of an application to the biological field. In many ways this study was indeed an exploration since so many factors are different. In the mineral field, the particles, both those floated and those not floated, cover a wide range of sizes and shapes; in the biological field, the particles of one population are primarily of one or two sizes and one or two shapes. This identity in size and in shape gives biological systems the advantage of homogeneity. In the mineral field the particles may be as coarse as a millimeter; in the biological field the size may be a micron, or less. In the mineral field the particles may have a gravity several times that of water so that their apparent gravity is quite substantial. Microorganisms, on the other hand, may have a gravity so near that of the liquor that their settling velocity in the liquor is vanishingly small. These two facts conspire to make bubble-particle encounter in the pulp-body less likely. Finally, microorganisms are living, reproducing, and dying-all of which does not help the experimenter get a balance of materials. The analytical problems, too, are extraordinarily difficult, for the organisms can contain only elements that occur in their environment, although at a different level of concentration. The chemical composition of the surface of microorganisms is readily altered. In spite of these areas of difficulty, microorganisms can be floated to leave practically water-clear tailing, they can be floated from each other and, in fact, the same organism can be fractionated into a float that differs from the sink. SIZES AND SHAPES OF ORGANISMS Most ore pulps are described with reference to the percentage of the pulp that is fine enough to pass a 200-mesh sieve. Thus a copper-ore pulp may be 80% -200 mesh. Since 200 mesh equals 74 µ, a 2000-mesh particle would be 7.4 µ in diameter, and a 20,000-mesh particle would be 0.74 µ. The microorganisms with which this work is concerned are of the order of magnitude of 20,000 mesh. We have worked with Escherichia coli, the colon bacillus, Bacillus cereus, Bacillus subtilis, Bacillus megaterium, and Serratia marcescens. In some pioneer work, Dognonl,2 reported the use

Jan 1, 1962

By A. S. Appleton, M. B. Bever, G. E. Dieter

A gold-silver alloy was deformed by explosive loading at shock pressures up to 510 kbars. The stored energy and hardness increased over the whole range of pressures; the largest rates of increase were observed between 120 and 150 kbars. In this range, markings rkavacteristic of defornation twins first appeared; higher pressures produced markings in all grains. These effects are compared with those of conventional deformation processes and are discussed in relation to probable structural changes. In recent years, increasing efforts have been devoted to the investigation of the effects produced in metals by the passage of high-intensity shock waves of explosive origin. By properly utilizing the energy released by the detonation of a high explosive, it is possible to generate pressure pulses of the order of 500 kbars and higher. (One kbar equals l0 9 dynes per sq cm or approximately 1000 atm.) The passage of a shock wave through a metal occurs at pressures which are very much greater than the yield strength. As the shock front passes a point in the metal, the pressure rises almost instantaneously, and continues to act at the point for a few microseconds. Thus, metals subjected to explosive shock loading experience a nearly instantaneous increase in pressure, and a subsequent release of pressure, which is almost as rapid. Under these conditions mechanical twinning and shear transformations occur readily. smith1 has investigated the metallurgical changes in copper and iron resulting from exposure to explosive shock waves. He found an appreciable increase in hardness in both metals. In copper, a hardness greater than that resulting from 95 pct reduction in thickness by rolling was obtained, yet in the explosive deformation, the thickness of the specimen decreased only a few percent. After explosive loading, the micro-structure of copper showed markings characteristic of mechanical twins. The amount of stored energy resulting from explosive loading is of interest. Measurements of the stored energy of cold work as a function of strain, temperature, strain rate, and composition have been made with gold-silyer alloys deforyed by rolling, orthogonal cutting,3 drilling,4 filing, wire drawing, and torsion. The investigation reported here was also carried out with a gold-silver alloy and its results can be compared with those for the deformation of this alloy by more conventional methods. EXPERIMENTAL PROCEDURES An alloy containing 82.6 wt pct Au and 17.4 pct Ag was purchased in several batches from Handy and Harman Co., New York, as annealed rod 1/4 in. dim. The rod was cold-rolled to a sheet approximately

Jan 1, 1962

Redetermination of the Chromium and Nickel Solvuses in the Chromium-Nickel System by C. J. Bechtold and H. C. Vacher, p. 14 The text of pages 16 and 17 is in improper sequence. The correct version will appear in the bound volume.

Jan 1, 1962

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

Spectrochemical methods were developed to determine beryllium in the concentration range 0.0015 to 4.0 percent in siliceous mineral beneficiation products. Two methods are described. They are (1) a fusion-pellet-spark procedure (spark method) and (2) a sustaining alternating-current arc procedure (arc method). In the spark method the sample is fused with lithium tetra-borate and vanadium pentoxide. The resulting bead is crushed, mixed with powdered graphite, and briquetted. This is analyzed spectrographically using controlled high-voltage spark excitation. In the arc method the sample is diluted with germanium metal, graphite, and vanadium pentoxide. Weighed charges are packed into cupped graphite electrodes and subjected to excitation with a sustaining alternating-current arc. Vanadium serves as internal standard for both methods. Effects due to matrix variations in samples and standards are eliminated either by fusion with lithium tetraborate in the spark method or by dilution with germanium and graphite in the arc method. Beryllium determinations show deviations from accepted chemical values of approximately 5 and 8 percent for the spark and arc methods, respectively. Analyses can be made more rapidly by the arc procedure with a sacrifice in precision and accuracy. Either method can be applied to the determination of beryllium in silicate rocks.

Jan 1, 1962

By C. A. Godden, T. N. Atkinson

Metallographic techniques developed from studies of corrosion films and electroplated coatings on aluminum alloys, are discussed. These methods, the result of work at the Naval Research Establishment, give extremely flat fields at the interface despite the large difference in hardness, in cases where electrolytic polishing could not be used. Techniques to overcome the similarity in refractive index of immersion oil, aluminum ox1d~, and mounting plastic are also considered, as are methods for improving visual and photographic contrast in areas of interest. A device for marking specimens is also de-scribed. ELE•CTROLYTIC polishing is inapplicable in the study of surface films on aluminum, whether corrosion films or electrodeposits. Mechanical procedures must there-fore be followed. Sample flatness and edge retention are of paramount importance. Special measures are required in the study of oxide films, because of the close proximity of the refractive indices of aluminum oxide, mounting plastic, and immersion oil.

Jan 1, 1962

By W. M. Tuddenham

It would be most difficult to place a date on the beginning of the revolution in analytical techniques that we have witnessed in recent years; but there is no question that the period since the end of World War II has seen a major change in thinking with respect to control and accounting analyses. For reasons relating to competition, much of this change was brought about in the chemical industries and only more recently has begun to affect directly the mineral industries. In considering the subject outlined in the title of this paper, one might well be tempted to discuss solely the more exotic methods of control and automation which have come into being in the past short while. In this paper, however, an attempt will be made to take a broader view and consider not only the application of newer purely physical methods of control but also those phases of chemical plus physical analyses that have bearing on our industry.

Jan 1, 1962

By Arnulf Muan, Hobart M. Kraner

Ferromanganese alloys react with aluminu-silica brick in blast furnace hearths and cause the formation of new phases with low refractoriness and consequent failure of the refractory lining. The nature of these reactions is explained on the basis of petrographic observations, thermodynamic data, and Phase equilibrium considerations. Animproued hearth design resulted from these findings. The production of ferromanganese in blast furnaces presents many problems which are not encountered in the production of iron in the same furnaces. One of the most serious of these problems is the rapid failure of refractories caused by their reaction with the ferromanganese metal. The present paper describes such a "hearth attack", its symptoms, causes, and cure. Following an introductory discussion of operating practice in ferromanganese blast furnaces, results are presented of a petrographic examination of samples from a furnace which had to be shut down because of refractory failure. The causes of this failure are then analyzed on the basis of petrographic observations combined with thermodynamic and phase equilibrium data available in the literature. The latter type of data were subsequently used as a guide in recommending improvements in hearth designs which have since proven themselves successful in practical operations. I) FERROMANGANESE BLAST FURNACE PRACTICE It is considered good practice to blow in a furnace on iron and operate it in this way for a period of time preliminary to producing ferrornanganese. During this time, iron generally penetrates the bottom refractories six or more feet below the original working surface of the hearth. Not only does this metal pervade the joints to these depths, but the pores of the refractories are usually also filled by molten iron. The high throughput of the iron furnace provides ample heat to maintain a high temperature in the hearth refractories. This, together with a high ferrostatic pressure, causes porous clay brick of the hearth to shrink. During subsequent use of such a furnace in ferromanganese production, the iron in the pores of hearth brick if; replaced to some extent by ferromanganese. The replacement is usually not complete. This is probably due to the lower metal throughput and lower prevailing temperatures resulting from this in the brick of the hearth bottom. When the ferrornanganese furnace is banked—or when the temperature in the furnace falls due to a furnace delay—-manganese oxidizes even though the atmosphere is largely CO. Considerable expansion accompanies this oxidation of manganese from metal to oxide. The hearth refractories are then subjected to the disintegrating forces of the volume expansion. These forces may in extreme cases be large enough to lift the furnace off its mantle supports as was described in a previous paper.' When cooling takes place slowly, however, and the temperature remains at a fairly high level, the refractories undergo fluxing action by the MnO. This latter reaction and the reduction of SiO2 of the clay brick is the general subject of the present paper. The observations to be described herein were made on a ferromanganese furnace located at the Johnstown plant of Bethlehem Steel Co. The furnace was lined entirely with clay refractories and had operated on iron for 266 days and on ferromanganese for 96 days prior to being taken off because of a hearth wall failure. II) PETROGRAPHIC EXAMINATION AND CHEMICAL ANALYSIS The photograph reproduced in Fig. 1 shws a cross section of the upper part of an 18 by 9 by 4-1/2 in. bottom block removed from the blast furnace. This brick came from a depth of approximately 6 ft below the original working face of the bottom. It will be noted that the 4-1/2 in. dimension is almost the same as when the brick entered the furnace. Three characteristically different zones marked I, II, and III on the print of Fig. 1 are apparent. Results of chemical analyses of the original brick and samples from each of these zones are listed in Table I. Petrographically the various zones were characterized as follows: The central zone marked I was essentially un-reacted brick. The microstructure consisted of fine needles of mullite, and the pores in this entire area were filled with iron. This is characteristic of

Jan 1, 1962

By A. Michalkow

DELN ITE Mines Limited is located in Deloro township, on the west end of the south break of the Porcupine Camp. Mining operations are currently being carried out on the downward extension of a system of quartz veins in an andesite zone. This zone has been followed from surface to the present bottom level of 5,250 feet. The changing mineralogy of the vein system has involved an increase in tourmaline content from the surface downwards, so that the veins at the lower levels are composed of dark brown quartz-tourmaline. The drilling problem presented by these extremely hard veins was partially alleviated by the development and adoption of a one-inch drill bit. All blast-hole drilling is now done with the one-inch bit, without any difference in hole spacing.

Jan 1, 1962

By Harry Perry

Although the markets for coal in the United States have changed rapidly over the last three decades, the uses of coal, namely, to produce heat and power or coke have been left almost unchanged. The coke is used either as a chemical reducing agent alone or as a reducing agent and source of heat. Most of the heat and power markets for coal require no coal processing, although for more than 50 years, many proposals to skim the more valuable substances in coal before burning have been advanced. Thus, the only large tonnage market requiring processing of coal is high-temperature carbonization to make coke. At present, coal requires processing for some small markets, but for future potential large markets, such as gasification, conversion to liquid and gaseous fuels, and conversion to chemicals, coals will require more processing than is now being done.

Jan 1, 1962

By Joseph Grumer

Theory pertaining to the exchangeability of fuel gases on appliances has been extended to exchanges of propane or butane with mixtures of these. In particular, new considerations were developed bearing on the hazard of an occasional emission of carbon monoxide and flashback and blowoff possibilities. The new considerations involve using current requirements for approval of liquefied petroleum gas appliances. These requirements were used to predict allowable tolerances in chemical composition of liquefied petroleum gases for existing appliances. In addition, changes in gasline pressure were computed which may be substituted in place of fuel exchanges during testing of appliances,

Jan 1, 1962

By R. P. Marshall, L. P. Costas

The solid solubility of lithium in aluminum was determined by two independent techniques, electrical resistivity and microhardness, and the results are in close agreement. The solubility limits X-ray diffraction studies of the intermetallic compound LiAl indicate that its composition is nearly independent of temperature when in equilibrium with the terminal solid solution of aluminum. THE investigation of the aluminum-rich portion of the aluminum-lithium system at the Savannah River Laboratory was prompted by the observation that over-aged alloys consistently differed from the equilibrium states predicted by the latest published diagrams. Chemical analyses of these alloys showed their impurity contents to be quite low; therefore, the results obtained should have very nearly coincided with true equilibrium. A survey of the literature disclosed that previous studies had been made with metallographicig or electrical resistivity methods,4'5 but that agreement between results and technique was poor as evidenced in Fig. 1, which also includes the present results for comparison. The discrepancies have been attributed to impurities,3 and this is undoubtedly true in the early work.1'4'5 The latest Studies,''~ conducted with starting materials of higher purity, employed metallographic analysis, a technique that is quite sensitive to local homogeneity and depends strongly on subjective interpretation. In the present work the problem of defining solubility limits was approached in two ways. The first measured a physical property, electrical resistivity, at the equilibrium temperature. The second, a micro-hardness characterization of a diffusion zone, is a room temperature evaluation of a mechanical property under conditions removed from equilibrium. A close correlation between two such basically different approaches would strongly justify confidence in the results. I) MEASUREMENT OF SOLUBILITY OF LITHIUM IN ALUMINUM BY ELECTRICAL RESISTIVITY Experimental Procedure. Alloys for electrical resistivity measurements were made by melting and

Jan 1, 1962

By Hargraves A. J

With increasing depth, stresses and stress phenomena are becoming more important considerations in Australian coal mining.A large number of compressive and tensile strength tests was made on coal and rock cubes cut from samples taken in various Australian collieries. In addition, an empirical impact strength test was carriedout on fragments of the same samples, to obtain a correlation with compressive strength.In one colliery, flat-jack measurements were taken to assess stresses in coal ribs and in the roof.INTRODUCTIONBy world standards, some of the New South Wales collieries are approaching depths of cover considered a maximum for bord and pillar the normal Australian coal mining method. Several South Coast collieries are winning coal at depths of about 1500 ft., and future operations are being planned at deeper cover. Some areas of these deep workings produce considerable quantities of seam gas.Phenomena associated with high stress and copious gas under pressure in the seam violent phenoma presenting a danger and a nuisance in mine working - have occasionally occurred, and the phenomena are being investigated as a whole (Hargraves, 1958), and separately as a gas problem (Bolt and Innes, 1959; Hargraves, 1962) and as a stress problem. This paper relates to the latter - to investigations into the strengths of coals and coal measure rocks, and into the stresses in and about coal seams...

Jan 1, 1962