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By W. O. Philbrook, K. Natesan

The oxidation kinetics of spherical pellets of zinc sulfide made from Santander concentrates were studied using a thermogravimetric technique. The experiments covered a temperature range-. of 740" to 102O°C, 0-N mixtures varying from 20 to LOO pct O2, and pellet diameters between 0.4 and 1.6 cm. Mathematical models were formulated to Predict the reaction rate on the assumption that a single transport or interface reaction step was rate -controlling. Analysis of the data indicated that the process of oxidation was predominantly controlled by transport through the zinc oxide reaction-Product layer. ROASTING processes, which are reactions between solids and gases, are very important because they are employed in the production of a number of basic metals. These processes are highly complicated, and one needs to consider the transport phenomena of heat and mass between the solids and gases in addition to the kinetics of various chemical reactions involved. Because of such complications there is a lack of knowledge concerning the rate-limiting factors, which may strongly depend on temperature, particle size, gas composition, and solid structure. The oxidation of zinc sulfide, which is of commercial importance in zinc production, falls into this class of reactions. The major goal of this work was to elucidate the roles played by different process variables, such as reaction temperature, gas composition, pellet size, and pellet porosity, on the kinetics of oxidation of single pellets of zinc sulfide. Roasting of zinc sulfide single particles has been a subject of both experimental and theoretical investigations.&apos;-&apos; The reaction is exothermic and may be considered to be irreversible. Such a reaction has been found to proceed in a topochemical manner. In other words, as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,1-9 that the particle retains its original dimensions and the process requires transport of gaseous oxygen across the porous product layer for continued reaction. The reaction may be represented by ZnS(s) + 3/2 O2(g) = ZnO(s) + SO2(g) [1] The solid product considered here is only zinc oxide, since the diffraction patterns of zinc sulfide pellets oxidized partially at &apos;798" and 960°C showed K. NATESAN, Junior Member AIME, formerly St. Joseph Lead Fellow, Department of Metallurgy and Materials Science, Carnegie-Mellon University, Pittsburgh, Pa., is now at Argonne National Laboratory, Argonne, Ill. W. 0. PHILBROOK, Member AIME, is Professor of Metallurgy and Materials Science, Carnegie-Mellon University. This paper is based on a them submitted by K. NATESAN in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science at Carnegie-Mellon University. Manuscript submitted December 2, 1968. EMD lines corresponding to original zinc sulfide and the newly formed zinc oxide. OXIDATION MODEL The generalized model for gaseous oxidation of zinc sulfide is illustrated in Fig. 1. This depicts a partially oxidized sphere of zinc sulfide in a gas stream surrounded by a laminar film of gas. The spherical sample of zinc sulfide of unchanging external radius r0 is suspended in a flowing gas stream of total pressure PT and composition specified by the partial pressures of the individual components. Partial pressures of the gaseous species in the bulk gas phase, at the exterior surface of the pellet, at the ZnS/ZnO interface, and at equilibrium for Reaction [I] are identified by the superscripts b, o, i, and eq, respectively. The overall reaction involves the following ~te~s:&apos;~&apos;~&apos; Step 1. Transfer of reactant gas (oxygen) from the bulk gas stream across the gas boundary layer to the exterior surface of the pellet and the reverse transfer of the product gas (sulfur dioxide). Step 2. Diffusion and bulk flow of oxygen from the pellet surface through the product shell (ZnO) onto the ZnS/ZnO interface and the reverse transfer of sulfur dioxide. Step 3. Chemical reaction at the interface, which results in consumption of oxygen gas and generation of sulfur dioxide gas and heat; at the same time the _________ PARTICLE SURFACE / x^^^^n^X / MOVING INTERFACE core-----/ sJSNxy " /T^T^02 \ V\V$\ ^NWX/ "*/— GAS BOUNDARY x. \\ZnO SHELLV/ / \^ . / &apos; ^ BULK GAS --------N_______ _____,------p£ w \ P« / (f> \ / a \ <i) / <----------------- _(o) ^^--------------(b) °- pso, pso2 ro ri 0 ri ro RADIAL POSITION Fig. 1—Generalized model for oxidation of a sphere of zinc sulfide.

Jan 1, 1970

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..&apos; and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young&apos;s modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen&apos;s5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.&apos; However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.&apos; The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1&apos;5&apos;6&apos;7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,&apos; has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers&apos; measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett&apos;s measurements on lithium indicated an angle of 3". According to the Burgers&apos; mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers&apos; mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

By Nathaniel Arbiter

THE separation of minerals by flotation can be regarded as a rate process, with the extraction of any one mineral determined by its flotation rate, and the grade of concentrate by the relative rates for all the minerals. So regarded, the significant variables for the process are those that control the rates. These variables are of two types, the first describing the ore and its physical and chemical treatment prior to flotation and the second characterizing the separation process in the cells. This paper will examine the variation in rates for a group of separations, will show that a simple rate law appears to govern, and will consider the relation of the control variables to the rates. The use of rate constants for evaluation of performance and efficiency will be discussed. Flotation involves the selective levitation of mineral and its transfer from cell to launder. The flotation rate is the rate of this transfer. It may be defined by the slope of a recovery-time curve for any cell in a bank, or at any time in batch operation. The objective in flotation rate study is an equation expressing the rate in terms of some measurable property of the pulp. This can be either the concentration of floatable mineral in weight per unit volume1,2 or a relative concentration, which will be a function of the recovery." A rate equation for an actual flotation pulp will contain at least two constants, both to be determined from the data. One of these, the initial concentration or proportion of floatable mineral, is not necessarily equal to the feed assay because of nonfloatable oversize or locked particles." The other, a rate constant, is a measure of proportionality between the rate and the pulp property on which the rate depends. The value of the rate constant will be determined by the values of all variables which control the process and will be changed by significant changes in any of them. It is, therefore, a direct measure of performance. Where recovery or grade change continuously with flotation time, the rate constant will be independent of time and will characterize the entire course of the separation. Development of Rate Equations Rate equations can be developed either by analysis of the mechanism of the process or by direct fitting of equations to recovery-time data. Sutherland&apos;s attempt by the first method&apos; suggests that the effect of particle size variation on the rate complicates the derivation of a simple equation applicable to an ore pulp. A further problem with an ore is the concentrate grade requirement, which usually involves a variable rate of froth removal. Thus the final rate for any cell may depend on the froth character and froth height, as well as on the pulp composition. This does not imply that each cell cannot reach a steady state2 in which the rate will depend ultimately on pulp composition. The second method is the fitting of rate equations consistent with the necessary boundary conditions* to experimental recovery-time curves. On the assumption that under constant operating conditions the flotation rate is proportional to the actual or relative concentration of floatable mineral in the pulp, a generalized rate equation may be expressed as follows: Rate = Kcn [I] where K is the rate constant, c is some measure of the quantity of floatable mineral in the pulp at time t, and n is a positive number. In previous rate studies, the value of n has been taken as 1, either by direct assumption," or as a result of the hypothesis that bubble-particle collision is rate determining.&apos; A first order equation results, which after integration in terms of cumulative recovery R, leads to Loge A/A-R = Kt [2] The quantity A is the maximum possible recovery with prolonged time under the conditions used. No conclusive proof for the validity of this equation in flotation has been advanced. The evidence cited in its support consists entirely in the demonstration that it appears to apply to a limited number of recovery-time curves."&apos; It will be shown subsequently that this procedure is not sufficient to establish the order of a flotation rate equation. The possibility that the equation may be of higher order therefore requires examination. If, in particular, the exponent in eq 1 is assumed to be 2, then after integration there results R = A2Kt/1 + AKt [3] with K again a rate constant and A the maximum proportion of recoverable mineral. Eq 3 may be

Jan 1, 1952

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

On the Art of Metallography (Howe Memorial Lecture), by F. F. Lucas; Beneficiation of Iron Ore. Abstract of paper by C. E. Williams followed by Round Table Discussion; A Statistical Analysis of Blast-furnace Data, by R. 8. McCaffery and R. G. Stephenson; Air Discharge of Circular Tuyeres, by R. S. McCaffery and D. E. Krause; Open-hearth Steel Process as a Problem in Chemical Kinetics. by E. R. Jette; Carbon-oxygen Equilibrium in Liquid Iron, by H. C. Vacher and E. H. Hamilton; A Thermodynamic Study of the Phasial Equilibria in the Bystem Iron-carbon (Abstract), by Yap, Chu-Phay; Influence of Dissolved Carbide on the Equilibria of the System Iron-carbon (Abstract), by Yap, Chu-Phay; Inclusions and Their Effect on Impact Strength of Steel, I and 11, by A. B. Kinzel and W. Crafts: Method for Electrolytic Extraction of MnO, MnS, FeS and Si02, Inclusions from Plain Carbon Steels, by G. R. Fitterer; Permanent Growth of Gray Cast Iron, by W. E. Remmers; Some Notes on Blue Brittleness, by L. R. van Wert; Austenite-pearlite Transformation and the Transition Constituents, by A. Sauveur; Age-hardening of Austenite, by F. R. Hensel; Transformational Characteristics of Iron-manganese Alloys, by H. Scott; Composition Limits of the Alpha-gamma Loop in the Iron-tungsten System, by W. P. Sykes; Magnetic Properties Versus AUotropic Transformations of Iron Alloys, by T. D. Yensen and N. A. Ziegler; Dilatometric Study of Chrome-nickel-iron Alloys, by V. N. Krivobok and M. Gensamer; Low-carbon Steel, by H. B. Pulsifer; Bright Annealing of Steels in Hydrogen, by F. C. KeUey; Development of Continuous Gas Carburieing, by R. J. Cowan. Transactions, Institute of Metals Division, 1931. 500 pages. Index. Papers and discussions presented before the Division at Chicago, Sept. 22-26, 1930 and New York, Feb. 16-19, 1931. X-ray MetallograpIhy: X-ray Determination of Alloy Equilibrium Diagrams (Annual Lecture), by A. F. Westgren; Suppressed Constitutional Changes in Alloys. by G. Sachs; Texture of Metals after Cold Deformation; by F. Wever. Theoretical Metallurgy: Studies upon the Widmanatitten Structure. I.—Introduction. The Aluminum-eilver System and the Copper-silicon System; by R. F. Mehl and C. S. Barrett; Studies upon the Widmanstatten Structure, 11.—The Beta Copper-einc Alloys and the Beta Copper-alumnum Alloys, by R. F. Mehl and 0. T. Mareke; Application of X-rays in the Manufacture of Telephone Apparatus, by M. Baeyerts; Thermal Conductivity of Copper Alloys. 11.—Copper-tin Alloys; 111.—Copper-phosphorus Alloys, by Cyril Stanley Smith; Thermodynamic Study of the Equilibria of the Systems Antimony-bismuth and Antimony-lead, by Yap, Chu-Phay. Ganeral: Cemented Tungsten Carbide; a Study of the Action of the Cementing Material, by L. L. Wyman and F. C. Kelley; Influence of Casting Practice on Physical Properties of Die Castings, by C. Pack; Fabrication of the Platinum Metals, by C. S. Sivil; Effect of Certain Alloying Elements on Structure and Hardness of Aluminum Bronze, by 9. F. Hermann and F. T. Sisco. The WorkinG oF Metals: Metal Working in Power Presses, by E. V. Crane; Forming Properties of Thin Sheets of Some Nonferrous Metals, by W. A. Straw, M. D. Helfrick and C. R. Fischrupp; Die Pressing of Braas and Copper Alloys, by J. R. Freeman. Jr.; Plasticity of Copper-sina Alloys at Elevated Temperatures. by A. Morris: Directional Properties in Cold-rolled and Annealed Copper, by A. Phillips and E. 9. Bunn; Effect of Combinations of Strain and Heat Treatment on Properties of Some Age-hardening Copper Alloys by W. C. Ellis and E. E. Schumacher; Constituents of Aluminum-iron-silicon Alloys, by W, L. Fink and K. R. Van Horn; Equilibrium Relations in Aluminum-antimony Alloys of High Purity, by E. H. Dix, Jr., F. KeUer and L. A. Willey; Equilibrium Relations in Aluminum-magnesium Silicide Alloys of High Purity, by E. H. Dix. Jr., F. Keller and R. W. Graham; Constitution of High-purity Aluminum-titanium Alloys, by W. L. Fink, K. R. Van Horn and P. M. Budge; Experiments on Retarding the Age-hardening of Duralumin, by E. H. Dix. Jr. and F. KeUer; Aluminum-silicon-magnesium Casting Alloys, by R. S. Archer and L. W. Kempf; Modulurr of Elasticity of Aluminum Alloys, by R. L. Templin and D. A. Paul; Quenching of Alclad Sheet in Oil, by H. C. Knerr.

Jan 1, 1931

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder&apos;s equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

Jan 1, 1900

By Charles H. Thurman

THE data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. DRAGLINE VS. BUCKET-LINE Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 10¢ gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new, 7-cu. ft. bucket-line dredge, costing upward of $250,000, and with operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These percentages of operating time are important factors in making a comparison of this kind. The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft. (65 ft. below water, 15 ft. above). A 5-cu. yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10¢ gravel 28 ft. deep with bucket line, costing 4¢ per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equipment, fully depreciated. Dismantling, mov-

Jan 1, 1945

By Richard R. Bains

"When l hear - I normally remember 10 percent When I hear and see - I can remember 15 to 25 percent When I hear, see, and do - I usually remember up to 50 percent" While this is not a truism in relation to each and every individual; on the average, this is the case. If we use this as a premise in training operator and maintenance personnel, then it must be obvious that we can&apos;t rely on a mere presentation, even one which includes the needed classroom participation and/or hands on work, to do a thorough job and to make this personnel totally proficient - 100 percent proficient. We have to have some other device some other means to make this a continuing process, a process wherein the people can grow in knowledge while performing their normal duties. We have to feel that the words "normal duties" are the key to the whole program. If you would ask a crusher operator what his duty is, he might say "To run this crusher so that we produce 250 tons per hour of a minus 13mm (minus 1/2 ") product." A maintenance man could say "To fix the unit when there is a problem." Both of these answers are legitimate but, they are only a part of the total picture. In order for each of these individuals to do the best job, he must know not just the specifics about the machine he works with or on - he must know the interrelation of all the machinery in the crushing circuit - how the efficiency of each machine affects the others - why a minor problem on one piece of equipment can generate a major problem for another unit which follows it or precedes it. In short, you cannot separate machine operation and maintenance from the application of the equipment in the crushing circuit - and obtaining this knowledge must be a part of the normal duty of crushing plant personnel. As an example a crusher - any crusher - is designed to crush oversize material. It is not designed to accept feed which is already at or less than the required product size. If sized material goes to the crusher, increase wear results by using the crusher as a chute or the crushing chamber can be clogged up with the fines. This latter point is particularly true with cone crushers, especially in the third (Short Head) stage of crushing. When a Gyradisc is used (fourth stage crushing) it is even more critical that the product be removed before the material goes to the crusher. The crusher cannot control this - the screen ahead of the crusher does. The screen must be of adequate size and be functioning properly to allow the crusher to work at optimum. Screening is both an art and a science. Since there are so many variables which affect the output of the screen, it is always best to have a screen which is larger than the sizing calculations dictate. The screens are the most important elements in the circuit. Without screens, specification materials cannot be made and the size of the screen will ultimately aid or hinder your ability to get the most production possible out of the plant. There is a formula available from all screen manufacturers which is designed to calculate the proper screen size. It takes into consideration the

Jan 1, 1982

NEW MEMBERS The following list comprises the names of those persons who became members during the period Mar. 10, 1916 to Apr. 10, 1916. ALLEN, P. R., Pres., McAlester Coal & Coke Co., Knight Templar Bldg., McAlester, Okla. BERNARD, CLINTON PERCIVAL, Min. Engr., Care Forminiere Mission Kasai, Tschikapa, Congo Belge, W. Africa. CARPENTER, GEORGE 0., Vice-Pres National Lead Co. St. Louis Mo. CLARK, WILLIAM ANDREWS, JR., Min. Engr., Pres., Elm Orlu Mining Co., Butte, Mont. CLAYTON, CHARLES YANCEY, Asst. PrOf. of Metallurgy and Ore Dressing, Missouri School of Mines, Rolla, Mo. COHEN, JULIUS MILTON, Mgr. Croesus Gold Mines, Ltd., Matheson, Ont., Canada. CRAMER, WILLIAM BRONSON, Met. at Concentrator, Old Dominion Copper Min. & Smelt. Co., Globe, Ariz. DAHL, SIMEON H., Mill Supt., Messina Transvaal Dev. Co., Messina, Transvaal S. Africa.

Jan 5, 1916

By Percival Roberts

I DESIRE to present this evening a few notes from the standpoint of a manufacturer upon the subject of tests of iron for structural purposes; not that I have any new facts to which to call your attention, but rather a statement of a few of the objectionable features of the present modes of operation, showing the absolute necessity of important and very radical changes. At the present time, as most of you are well aware, proposals for materials are accompanied by certain specifications as to quality and tests to which the manufactured article must conform. Evolved in many cases from the inner consciousness of some one more expert in theory than in practice, we find a few of the specifications to be good, many bad, and some indifferent. Appended are specimens of specifications of the most prominent engineers and railroad companies, which may be taken as representing the best and most intelligently framed specifications which we now have, arid yet in some pints scarcely satisfactory, owing to misunderstanding of tests as now made. To show the very varied opinions held as to proper quality of iron for bridge-work, I give the tests of two lots of fron made by inspectors with the results, which were referred to the maker with the following commensts : Lot No. 1. Teat of Iron for Eyebars. Reduced area. Elongation. Size. Per cent. Per cent. Breaking load. 4" x 1 3/8 26 25 68,500 Bent 120° around 1 1/2" bar with fracture. Reduced area. Elongation. Size. Percent. Percent. Breaking load. 6" x 1 7/15 24 24 48,820 Bent 110° around 2" bar. This iron should bend 180° without fracture, and is therefore rejected. Lot No. 2. Test of Iron for Brirlye. All measurements taken upon a parallel section of 10". Iron for tension members. Breaking load Elongation. size. per aquare inch. Percent. 1 5/8 49,600 20 14 61,600 27

Jan 1, 1882

By Eugene McAuliffe

The term "mechanical mining" carries an ambiguity which justifies a preliminary word of explanation. . All mining activity conducted in this day is more or less mechanical; that is to say, power expressed in the form of electricity, steam or compressed air is used in some portion of practically every mining activity of consequence. "Mechanical loading" is more nearly correct than "mechanical mining" in reference to present practice. The first substantial effort made in the direction of mechanical mining, subsequent to the application of steam for hoisting and underground pumping purposes, was that of substituting for hand labor undercutting and shearing by power-driven machines. The undercutting of coal by hand represented at one time the most arduous task confronting the miner. Occupying a kneeling position in the thicker beds, or lying on his side in the thinner coal, the task was tedious and exhausting. The first attempt to substitute crude air-driven, and later electrically driven, "punchers," as the percussion type of machine was called, met with much the same opposition on the part of the workers as was expressed by workers in the other industries when any innovation, whether labor-saving or otherwise, was introduced. We should not be too critical of this attitude of mind shown by the mine workers. The peculiarly isolated character of the work carried on in semidarkness by a class of men who to a large extent lived and held themselves aloof from the other branches of society led long ago to the development of a craft consciousness which they have found difficult to surrender. It was not until 1891 that a definite record of the results obtained by the use of undercutting machines of all types was made available, the quantity undercut in that year totaling 6,211,732 tons of bituminous coal from all American mines. The volume of bituminous coal undercut by machines in 1928 totaled 369,687,007 tons, or 73.8 per cent. of the nation&apos;s production. In the light of this experience, we can properly feel that the work of introducing the coal-loading machine as a substitute for hand shoveling is making substantial progress.

Jan 1, 1931

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&apos;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.&apos; 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.&apos;" 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 W. W. Gerberich

SINCE the original formulation of fracture mechanics concepts,&apos;y2 relatively little work has related the fracture mechanics description of metal behavior on a gross, structural component scale to the behavior of its microstructural constituents. The purpose of this note is to suggest the utilization of fracture mechanics to describe material behavior on a microscopic scale. A Fracture Concept for Two-Phase Structures. A critical displacement concept considering the tough unidirectional phase in a relatively brittle matrix is first examined. It is assumed that a flaw exists at position 1 as depicted in Fig. 1. As the crack moves from position 1 to 2 the plastic zone could be of the shape described with the size approximated by the Dugdale3 model: where c is the half-crack length, OO is the applied stress, and oyS is the yield strength. Hahn and Rosen-field4 have presented a simple fracture criterion for homogeneous materials based upon the displacement at the crack tip. They also have shown the equivalence of the critical displacement, v*, to fracture toughness by Kc = (2v*oysE)1/2 [2] The displacement at the crack tip is given by and the displacement at any distance in front of the crack tip may be determined knowing the plastic zone size and utilizing the development of Goodier and Field.5 Recalling Fig. 1, the value of v* for fracture in material M1 may be calculated from Eq. [2] providing the critical stress intensity factor is known. As the material is loaded, when vc > vM1 the crack moves from position 1 to position 2 where it encounters the tough second phase. If vc2 < vm2, then the crack will be arrested providing the width of the M2 phase is sufficiently large. This condition is necessary since the displacement at position 2 has increased due to the longer crack length. Thus, the displacement at the distance X (representing the dimension of the second phase) in front of the crack may be larger than the critical displacement for failure in the brittle material. If v, > vm, then failure will proceed in the brittle material. The value of v, may be calculated as indicated above. This latter consideration is the same as predicting fracture of a brittle second phase at some distance in front of a crack located in a ductile matrix. Experimental Evidence. On a macrostructural scale, tungsten wires in a ductile Be-Cu matrix are seen to fracture well ahead of the main crack front in Fig. 2. Utilizing a Kc value of 14.2 ksi-in.1/2 obtained by Schroder et al.6 for as-received tungsten, the critical displacement 2v*, for fracture is calculated from Eq. [2] to be about 6.5 X 10-5 in. The crack tip displacement, 2vc, is calculated from Eq. [3] to be 0.0028 in. indicating that fracture would occur at a considerable distance in front of the crack tip. From the ratio of v*/vc and the plastic zone estimate of Eq. [I], the distance in front of the crack tip at which a tungsten wire should fracture is calculated to be about 0.195 in. As shown in Fig. 2, a fractured wire occurs at a distance of 0.140 in. (fractured in three places), not at 0.250

Jan 1, 1968

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952