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By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By C. Özgen Karacan

The formation of the gas emission zone in longwall mining and the potential amount of gas in this zone are factors of local geology and spatial variability within this geology. Therefore, geostatistical methods can be used for modeling and prediction of gas amounts and for assessing its uncertainty in the gas emission zone of longwall mines. This study used core data obtained from 64 exploration boreholes drilled from the surface to the bottom of the Pittsburgh coal seam in a mining district in the Northern Appalachian basin. After identifying important coal layers for the gas emission zone, semivariogram modeling was conducted for different coal seams to define the distribution and continuity of various attributes. Sequential simulations were performed for stochastic assessment of these attributes to calculate gas-in-place (GIP) in each coal seam. GIP calculations for coals of various gas emissions zones were combined and ranked for their cumulative distribution function to find GIP in the caved zone and in the fractured zone at the 5%, 50%, and 95% quantiles. Fifty percent quantile results were later used to isolate a panel from the whole area and create a mosaic representation corresponding to the daily advance rate of the longwall face. This approach helped to estimate the daily emissions of this panel from the caved zone and from the fractured zone. Results showed that gas-in-place in the Pittsburgh coal seam, in the caved zone, and in the fractured zone showed spatial correlations that could be modeled and estimated using geostatistical methods. This study showed that gas-in- place volumes in the study area may be as high as 12.3 Bscf and as much as 3.5 MMscf per acre of mining.

Jan 1, 2012

T. M. Drown, South Bethlehem, Pa.: Mr. Thackray's paper shows in a striking way the high degree of rapidity and ac curacy exhibited by the chemists of our steel-works in ordinary everyday practice. That determinations made in an hour should present only slight differences in the third place of deci male is certainly matter for surprise and congratulation. This remarkable result has been due, perhaps, in part, to a remark able cause. The managers of works, ignorant of all the diffi culties of the laboratory, have demanded "the impossible " of their chemists—and the chemists have done it! Andrew A. Blair, Philadelphia, Pa.: Mr. Thackray's paper is extremely interesting, especially in its bearing on the question of a standard method for the rapid determination of phosphorus in the laboratories of steel-works. Before discussing the re sults in general, I desire to explain the results obtained by me under method A'. This is the method which I have used in the work of the sub-committee on Methods of the Interna tional Steel Standards Committee. It may be described briefly as follows: Solution in nitric acid; oxidation of carbonaceous matter by permanganate; precipitation of phosphoric acid by molybdate solution; reduction of molybdic acid in the reductor, and titra tion by permanganate. This method was used apparently by only three chemists, Dr. Dudley, Mr. Crowell, and myself. In determining phosphorus by this method, among the most essential points to be considered are the ratio of iron to molyb dic acid, or the reducing action of zinc on molybdic acid as compared to its reducing action on iron, and the ratio of molyb dic acid to phosphorus in the ammonium phospho-molybdate obtained by precipitation from the solution of the steel. In regard to the first point, the usually accepted ratio is 1 to 0.90756, or, as it is roughly stated, 0.9076, which is based on the assumed reduction of the molybdic acid to Mo12019,. This

Jan 1, 1896

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,' is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By Donald A. Bruce

The paper reviews aspects of the construction and performance of prestressed ground anchors installed in soils and weak rocks. Attention is focused on good practice for drilling, tendon fabrication and handling, grouting, stressing and testing. Regional variations - not always logically justified - are described. The performance of anchors in a variety of geological conditions is illustrated with reference to recent full scale test programs. 1. Introduction In the United States there has been steady growth in the use of prestressed anchors in materials other than competent or hard rock, in the years since their introduction in the late 1960's. This expansion has to a large extent been driven by specialty geotechnical contractors who both imported foreign developments and conducted their own basic researches, in locally prevailing conditions. With such data and experience, these engineers have had the confidence to promote "alternative solutions" for difficult earth support problems to receptive designers and owners. In turn, being engaged in the details of design and performance monitoring has given these parties the close exposure necessary for the real transfer and understanding of the technological concepts, and this knowledge has generated positive feedback for the contractors.

Jan 1, 1991

By K. L. Johnson

Networks of monitoring wells were established prior to mining at four longwall mine sites in the Appalachians to monitor the effect of mining on water levels, water quality and well yield. Two of the sites were located in stream valleys and the other two sites were located on hilltops. The depth to the mined seam ranged from 500-850 feet with the deeper cover being associated with the hilltop sites. Maximum declines in groundwater levels during and after mining were an order of magnitude less in the stream valley aquifers than in the hilltop aquifers. However, water levels in hilltop wells located outside the area immediately above the panel were unaffected. Water quality changes in wells as a result of longwall mining were negligible at all four sites. Increases in aquifer transmissivity and well yield were much more pronounced in the stream valley aquifers than in the hilltop aquifers. The significantly larger recharge area for the stream valley aquifers than that for the hilltop aquifers may partially account for the differing responses of these two classes of aquifers to longwall mining. These observations appear to be consistent with the stress-relief fracture model for Appalachian Plateau groundwater hydrology proposed by Wyrick and Borchers in 1981.

Jan 1, 1986

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By S. P. Kinney

Sulfur has been one of the most troublesome elements encountered since the earliest days of iron smelting, and this problem will become of increasing importance as the higher sulfur coke is used, because of the rapidly diminishing supply of low-sulfur coals suitable for the manufacture of metallurgical coke. The deleterious effect of sulfur in iron and steel is well known; therefore, except in special cases, it is desirable to make the iron produced by the blast furnace as low in sulfur as possible. Sulfur enters the furnace in all of the raw materials, but principally in the coke. It comes out of the blast furnace distributed between the iron and the slag; very little passes out of the furnace with the gases. The mechanism of the reactions that cause the sulfur of the coke to pass into the slag and iron has not been studied to any great extent, although the character of the end products, and the conditions controlling the distribution of the sulfur between the iron and slag, are fairly well known. In the iron, the sulfur occurs as ferrous sulfide; or manganese sulfide in case of iron high in manganese. In the slag, the sulfur is present mostly as calcium sulfide. The presence of free sulfur1 and sulfates in blast-furnace slags is to be accounted for on the basis of oxidation of the calcium sulfide after the slag is tapped. The generally accepted reaction for the relation between the ferrous sulfide in the iron and in the coke, and the calcium sulfide in the slag, is that given by Howe? FeS + CaO + CDFe + CaS + CO

Jan 1, 1923

By S. P. Kinney

Sulfur has been one of the most troublesome elements encountered since the earliest days of iron smelting, and this problem will become of increasing importance as the higher sulfur coke is used, because of the rapidly diminishing supply of low-sulfur coals suitable for the manufacture of metallurgical coke. The deleterious effect of sulfur in iron and steel is well known; therefore, except in special cases, it is desirable to make the iron produced by the blast furnace as low in sulfur as possible. Sulfur enters the furnace in all of the raw materials, but principally in the coke. It comes out of the blast furnace distributed between the iron and the slag; very little passes out of the furnace with the gases. The mechanism of the reactions that cause the sulfur of the coke to pass into the slag and iron has not been studied to any great extent, although the character of the end products, and the conditions controlling the distribution of the sulfur between the iron and slag, are fairly well known. In the iron, the sulfur occurs as ferrous sulfide; or manganese sulfide in case of iron high in manganese. In the slag, the sulfur is present mostly as calcium sulfide. The presence of free sulfur1 and sulfates in blast-furnace slags is to be accounted for on the basis of oxidation of the calcium sulfide after the slag is tapped. The generally accepted reaction for the relation between the ferrous sulfide in the iron and in the coke, and the calcium sulfide in the slag, is that given by Howe? FeS + CaO + CDFe + CaS + CO

Jan 1, 1923

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By Harmon D. Nine

DISCONTINUITIES in the strain vs cycles to failure (S-N) fatigue curves have been reported for polycrystalline materials by Porter and Levy for copper,&apos; by Benham and Ford for mild steel,&apos; and by Williams and Stevens for 18/5 stainless steel.3 However, the considerable scatter of the points for polycrystalline materials have made a statistical analysis of the data necessary to confirm the discontinuities. By using oriented single crystals of high-purity material and low grown-in dislocation content, the reproducibility has been improved to a degree which makes statistical analysis unnecessary and clearly shows discontinuities in the S-N curves. A recent publication4 reports an abrupt change of slope in the S-N curve for ( 100) axially oriented copper single crystals fatigued in torsion. The reported discontinuities in the S-N curve, along with a different mode of failure in the two branches of the curve, have been interpreted as being due to two different amplitude-dependent mechanisms. Further work on copper single crystals of (111) axial orientation has now been completed which supports the existence of an amplitude-dependent change in the mechanism of fatigue. In the present study torsional-fatigue experiments were performed at room temperature in air on (111) axially oriented single crystals. The crystals were grown and prepared as reported in Ref. 4. Two different methods of growing the crystals also discussed in Ref. 4 produced crystals of two different perfections: Type I with dislocation density of >l06 per sq cm and Type I1 with dislocation density of <l05 per sq cm. In accordance with the accepted hypothesis that crystal flaws are primarily responsible for the scatter of fatigue lifetimes, particularly at low amplitudes, the values for the three lowest amplitudes for Type I crystal are believed to be uncertain. They are marked in braces in Fig. 1. On the other hand, at amplitudes above a surface shear strain (SSS) of *0.003, the data for both types of crystals are in agreement. Most remarkably the S-N curve for torsional fatigue of (111)-oriented single crystals is composed of three segments separated by rather large discontinuities, Fig. 1. Metallographic and X-ray measurements indicate that the lower branch corresponds to the low-amplitude (F) region of the (100) copper single-crystal results as discussed in Ref. 4, and the two upper branches correspond to the high-amplitude (H) region. The lower discontinuity in the (111) S-N curve and metallographic evidence give further support to the hypothesis that different mechanisms of failure operate for high and low strain amplitudes. Reference to the resolved shear stress diagram, Fig. 2, shows that the highest stressed systems in

Jan 1, 1965

By Yuting Xue, Alper Kirmaci, Taghi Sherizadeh, Dogukan Guner, Khaled Mohamed

Rib brows present a significant safety hazard in underground coal mines in the United States. To address this issue, researchers at the National Institute for Occupational Safety and Health (NIOSH) and Missouri University of Science and Technology (MST) are developing a practical tool to assess both the potential of rib brow formation and the stability of any formed brows. As part of this effort, a monitoring study was conducted to assess the potential for rib brow formation in coal pillar ribs. This study was conducted in a room-and-pillar coal mine where coal pillar ribs are prone to developing rib brows. Although no rib brows formed in the instrumented pillar, data from monitoring and visual observations provided valuable insights into the loading mechanisms impacting the instrumented pillar. These findings helped identify factors that may reduce rib brow formation, including the cavability of the roof in mined areas, the applied rib support, the strength of rock partings, and the overall integrity of the coal seam. The scientific findings published in the case study aid in assessing the potential of brow formation, offering additional evidence for the need to improve rib control methods in underground coal mines.

Feb 1, 2025

By J. Stiksma, J. Dennett, R. Kalanchey, J. Ji, M. Collins, T. Chan, R. Berezowsky

A pilot plant campaign has been conducted by Sherritt Technologies in support of Eldorado Gold Corporation’s evaluation of pressure oxidation technology for the treatment of refractory gold concentrates from the Certej deposit in Romania. Four separate concentrates, containing 3.5 to 5.4 g/t Au, 13.0 to 14.5% S2- and 12.0 to 32.5 g/t Ag, were tested in the eight-day campaign. The major gold-bearing mineral was pyrite. Preliminary batch tests indicated that gold extraction from the oxidized concentrates in subsequent cyanide leaching was adversely affected by the presence of organic carbon in the pressure oxidation feed when chloride in solution was at an elevated level. As such, the process conditions that were tested during the pilot plant operation were selected to either counteract the negative impact of the organic carbon, or to deactivate it during pressure oxidation. Both process routes proved feasible, yielding gold extraction of 95 to 98% in cyanide leaching of the oxidized concentrates. Silver extraction was typically in the range of 80 to 90%, provided that the oxidized concentrates were also processed in a lime boil step prior to cyanide leaching.

Jan 1, 2014

By Mousa Mohammadi

Due to operational advantage of dragline in simultaneous excavation and back-filling, the equipment has gained vast importance in open-pit mining. Besides, absence of auxiliary haulage units and a myriad of other benefits are also credited in favor of excavation of muck piles by the draglines. However, the aspects of production, productivity and economics are of utmost significance in dragline operation and planning. In this light, the present paper is an endeavor to analyze availability and utilization of dragline operations. The paper presents a good amount of data for 4-draglines operating in one of the major opencast projects in India. The study reveals the trends of availability and utilization of these draglines during last 11-years. Furthermore, the study also highlights the salient reasons for loss of available hours and for idling of the draglines. Some startling information and facts have been illustrated in form of graphs and pie charts.

Aug 1, 2013

By G. Merrington, B. J. Alloway

Tailings from three historical mining areas in the UK were leached in columns under a simulated weathering programme which was chosen to represent periods of 1 and 2 years at 3 different ambient temperatures. The total concentrations of Cd, Cu, Pb and Zn in the primary ore minerals present in the tailings showed only a limited correlation with metal concentrations in the leachate. The leachate from columns of tailings that were maintained at a temperature of 25 (+/-3) degrees C contained, on average, 50% more Pb and 75% more Cu than leachate from tailings that were maintained at a temperature of 10 (+/-3) degrees C. The pH values of leachates from all three types of tailings at 25 (+/-3) degrees C were 0.2 units lower than those from columns maintained at 10 (+/-3) degrees C. The concentration of Cd and Zn in the tailings leachates showed no marked difference at the different temperatures. The composition of the leachate was found to be dependent on the type of gangue mineral, the presence of other sulphide minerals and the formation of secondary iron minerals. A comparison of the concentrations of heavy metals in the leachates produced in the laboratory with those in leachates that were collected in the field over a similar period of time from two of the mine sites showed that concentrations were of a similar order.

Jan 8, 1993

By M. M. Foss

Geophysical methods are gaining acceptance in the evaluation of coal mine ground control condition. The use of in-seam seismic investigations has contributed significantly to the body of information concerning ground control feature identification and analysis. Seismic methods have been used successfully in locating voids, faults, fracture zones, roof and floor rock interfaces, and more recently in characterizing in-seam stress distribution. Seismic tomography is an effective tool in data interpretation for several of these applications, but as is the case with other engineering application of geophysical techniques, there are limits as to how much substantive information can be interpreted from a given data set. This paper discusses some of the applications of in-seam seismic geophysical tomography, and the limits to which the transformation from raw data to information should be taken.

Jan 1, 1995

By H. H. Schrenk, W. P. Yant, P. H. Mautz

"In a study of the chemistry and pathology of chronic benzene poisoning, which was conducted cooperatively by the United. States Bureau of Mines, the Barrett Co., and the producers of benzene, it was necessary to make quantitative determinatious of the abzorption, distribution, and: fate of benzene in the organism. Although methods for determining benzene in relatively large amounts were available no satisfactory method was found for removing and determining the small amounts that are present in the tissues or excretions after exposure to conditions which ultimately cause chronic poisoning. This no doubt accounts for the lack of information in the literature on this particular phase of benzene poisoning.The writers have found in work that will be described in a subsequent publication that the amounts of benzene present in the tissues and excretions under conditions of exposure which produce chronic benzene poisoning arc of the order of a fraction to a few milligrams per 100 grams of tissue. This report describes a method developed and found satisfactory for these determina¬tions.RÉSUMÉ OF PERVIOUS METHODSA method for the determination of benzene in tissue was developed by Joachimoglu. 5 In the Joachimoglu procedure the ground organs are mixed with water and acidified with diluted sulphuzic acid, and the benzene is distilled into a receiver containing carbon tetrachloride. The benzene is nitrated in the carbon tetrachloride, the carbon tetrachloride evaporated, the acid mix¬ture neutralized, and the dinitrobenzene extracted with ether. After removal of the ether the dinitrobeuzene is determined gravimetrically. Joachimoglu reports that this method is about 55 to 60 percent quantitative."

Aug 1, 1935