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By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By R. K. Komarek, F. E. Jr. Briber, G. M. Hanson, Fred D. DeVaney, J. H. Blake, C. L. Matson, T. E. Ban, N. E. Shields, R. D. Frans, R. B. Greenwalt

Metallurgically, the term agglomeration is used to describe processes whose goal is to form balls, briquettes, nodules, flakes, or other sized shaped particles from loose, usually fine, incoherent particles. In practice it includes such varying processes as the briquetting of coal dust and other substances, the balling and induration (heating) of such nonmetallics as cement, fluorspar, lightweight aggregates, etc. It includes such widely used processes as the sintering of nonferrous concentrates, such as those copper, lead, zinc, etc. The agglomeration of specific nonferrous metal concentrates is discussed in detail in the section of this handbook devoted to that particular metal. Agglomeration processes are of particular value to the iron and steel industry where the nature of the primary reduction process, the blast furnace, requires for best results a burden essentially free of fines. This is a change that has taken place since about 1960. Prior to that time many fine unsized ores were fed to the furnace. The development of the pelletizing process gave to the industry a chemically controlled closely sized product that increased the produc¬tion rate and reduced the costs so much that unsized fines are seldom used in modem furnaces. Steel plants produce many fine sized waste products such as fine dust (fine ore coke and gangue) and mill scale. These products, which have a valuable iron content, are usually sin¬tered directly at the plant for reuse. Fine sized ore concentrates are usually pelletized at the mine and shipped as pellets to the steel plant. Common practice in some areas producing natural high grade ores is to screen the ore at the mine to about 3/8 in. The oversize is shipped "as is" and constitutes blast furnace feed. The / in. may be shipped to the steel plant where it may be sintered or otherwise agglomerated. At some mines the fines may be pelletizied prior to shipment. With the development of large ocean ore carriers, and with the transportation of slurried concentrates or fines, a trend has developed of constructing large pelletizing plants or other types of agglomeration plants near large consumption centers (i.e., in the Netherlands or Japan) where ores of many types are brought together, ground if necessary, blended, and agglomerated. As an indication of tonnages of agglomerated materials produced, for iron materials alone (the largest share of the total) production in 1970 in the U.S. was Million gross ton Sinter 40.7 Pellets 43.1 Briquettes, nodules, & others 0.1 Total 83.9 During the 1960s, U.S. production of sinter rose from 40.3 million gross tons in 1961 to a high of 48.7 million in 1964, then settled back to almost the 1961 figure in 1970. Pellet production rose steadily from 14.4 million gross tons in 1961 to the 59.9 figure for 1975. Worldwide, sinter production in 1966 was estimated at 340 million mt (mainly in Europe, Russia, Japan, and the U.S.) and pellet produc¬tion the same year at 64 mt (primarily Canada and the U.S.). World pellet production capacity rose to 200 million tons in 1976.

Jan 1, 1985

By J. P. Grieco, F. W. Grieco

"Manufacturing of Jaw CrushersOriginIn 1858 Eli Whitney Blake invented the first successful mechanical rock breaker-the Blake-type jaw crusher. Blake adapted a mechanical principal, the powerful toggle linkage system used to transform rotating motion and energy into oscillating mot ion and tremendous compressive forces. Today these same principals apply and the basic Blake-type jaw crusher is one of the leading machines of its class for heavy duty primary crushing service.In 1881 Philetus W. Gates patented a design for a crusher, the forerunner of the modern gyratory crusher which dominated the field from the late 1800s to the early 1900s. In 1910 the largest gyratory crushers built had 48-inch openings. However, about this time the jaw crusher came to life when the Power and Mining Machinery Co. built an even larger sized opening crusher-a giant 84-inch by 60-inch jaw crusher for a trap rock quarry in Pennsylvania. A 24-inch gyratory crusher became the ideal sized secondary machine for this size jaw. From that time on jaw crushers were looked on favourably as primary breakers and lines were brought up to date to parallel the already developed gyratory lines.FunctionMost heavy duty Blake-type jaw crushers work basically the same way. They are ruggedly designed and capable of crushing material in some cases in excess of 80, 000 p.s.i. compressive strength. They are very simple machines with few moving part s and, with the exception of replacement of renewable parts, are relatively maintenance free. It is quite common to have these machines in product ion for 20 to 30 years. The following will de scribe how these machines work. Large-diameter high-inertia flywheels which are connected to the main eccentric shaft, rotate inside a connecting rod type mechanism called a Pitman. It transforms rotating motion into vertical oscillating motion. This vertical motion is in turn transformed into reciprocating mot ion by means of a system of 2 toggles, each connected to the Pitman. The rear toggle is connected to the fixed rear head, and the front toggle is connected to the swing jaw which is hinged at the top of the crusher. With each rotation of the eccentric shaft the swing jaw opens and closes on rock which is fed into the crusher chamber, crushing the rock in a series of bites. These bites, or strokes as the y are called, usually vary between 1/2 inch to 1 1/2 inch at speeds of 120 to 200 strokes per minute. The reduction ratio of feed input to discharge is usually about 8 to I. Output capacities can vary from 100 tons/hour to 1200 tons/hour depending on the size of machine and its discharge opening. Horsepower requirements can vary from 75 hp to 400 hp.The entire crusher chamber is lined with replaceable 14070 manganese steel liner plates. This material is ideally suited for the job since it hardens as it wears during crusher operation. Manganese is also used in the high wear areas at each end of the toggle plates."

Jan 1, 1985

By J. P. Grieco, F. W. Grieco

"Manufacturing of Jaw CrushersOriginIn 1858 Eli Whitney Blake invented the first successful mechanical rock breaker-the Blake-type jaw crusher. Blake adapted a mechanical principal, the powerful toggle linkage system used to transform rotating motion and energy into oscillating mot ion and tremendous compressive forces. Today these same principals apply and the basic Blake-type jaw crusher is one of the leading machines of its class for heavy duty primary crushing service.In 1881 Philetus W. Gates patented a design for a crusher, the forerunner of the modern gyratory crusher which dominated the field from the late 1800s to the early 1900s. In 1910 the largest gyratory crushers built had 48-inch openings. However, about this time the jaw crusher came to life when the Power and Mining Machinery Co. built an even larger sized opening crusher-a giant 84-inch by 60-inch jaw crusher for a trap rock quarry in Pennsylvania. A 24-inch gyratory crusher became the ideal sized secondary machine for this size jaw. From that time on jaw crushers were looked on favourably as primary breakers and lines were brought up to date to parallel the already developed gyratory lines.FunctionMost heavy duty Blake-type jaw crushers work basically the same way. They are ruggedly designed and capable of crushing material in some cases in excess of 80, 000 p.s.i. compressive strength. They are very simple machines with few moving part s and, with the exception of replacement of renewable parts, are relatively maintenance free. It is quite common to have these machines in product ion for 20 to 30 years. The following will de scribe how these machines work. Large-diameter high-inertia flywheels which are connected to the main eccentric shaft, rotate inside a connecting rod type mechanism called a Pitman. It transforms rotating motion into vertical oscillating motion. This vertical motion is in turn transformed into reciprocating mot ion by means of a system of 2 toggles, each connected to the Pitman. The rear toggle is connected to the fixed rear head, and the front toggle is connected to the swing jaw which is hinged at the top of the crusher. With each rotation of the eccentric shaft the swing jaw opens and closes on rock which is fed into the crusher chamber, crushing the rock in a series of bites. These bites, or strokes as the y are called, usually vary between 1/2 inch to 1 1/2 inch at speeds of 120 to 200 strokes per minute. The reduction ratio of feed input to discharge is usually about 8 to I. Output capacities can vary from 100 tons/hour to 1200 tons/hour depending on the size of machine and its discharge opening. Horsepower requirements can vary from 75 hp to 400 hp.The entire crusher chamber is lined with replaceable 14070 manganese steel liner plates. This material is ideally suited for the job since it hardens as it wears during crusher operation. Manganese is also used in the high wear areas at each end of the toggle plates."

Jan 1, 1985

By Frederick Laist

ABOUT six years ago the Anaconda Copper Mining Co. decided to investigate the possibility of extracting zinc from the ores of certain mines in the Butte district. These ores are of a complex character and contain so much iron and lead that the concentrate contains only 33 to 35 per cent. zinc. Investigations showed that while a high-grade concentrate could not be obtained by ordinary methods, such as tabling and magnetic treatment, a fair grade could be made by the Horwood process. In this method, the concentrate resulting from the flotation of all of the sulfides is given a light roast and this calcine is subjected to flotation in the presence of a large amount of sulfuric acid; the resulting concentrate contains most of the zinc and a residue contains most of the iron. The fact that the lead, copper, and silver are divided approximately equally between the zinc concentrate and the iron residue and the large consumption of acid, which ranged from 50 to 100 lb. (22 to 45 kg.) per ton of concentrates, were serious objections to this plan. The zinc recovery, moreover, was low, as a considerable percentage invariably accompanied the iron. While a profit might be made on the ores by the use of this process, it was thought that other and more promising methods might be devised. After carefully studying the field and doing some laboratory work on various processes that had been suggested, it was decided that the electrolysis of sulfate solutions was the most promising. We soon found, as have other investigators, that the only way to obtain a good zinc deposit is to have the electrolyte free from all metals more electro-negative than zinc, such as copper, cadmium, lead, arsenic, antimony, etc. Arsenic and antimony are particularly injurious, causing very poor current efficiency and small yield per horsepower when present in amounts so small as almost to defy detection-1 mg. or less per liter.

Jan 10, 1920

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By J. E. Hilliard, J. W. Cahn

calculation has been made of the standard deviations to be expected in the measurement of volume fractions by areal analysis, lineal analysis and four point-counting Procedures. The effect of experimetztal errors is not included. Our conclusion is that a point count using a two-dimensional grid will be the most efficient method of volume fraction analvsis providing the grid spacing IS coarse enough. The predicted standard deviation for such an analysis is shown to he in good agreement with that determined experimentally. A metallurgist wishing to estimate a structural property by means of quantitative metallography is often faced with a choice between several different procedures. In such a case, he will naturally wish to know: a) Which procedure is the most efficient in the sense of requiring the least effort for a given precision? b) For a given procedure, what are the conditions for maximum efficiency? c) Under these conditions, how many measurements are required to attain a given precision? It is our aim in this paper to provide at least partial answers to these queries as they relate to the estimation of volume fractions from measurements on a random two-dimensional section of an opaque specimen. The commonly used techniques1,2 for volume-fraction analyses are based on one or more of the following principles: i) For an areal or Delesse3 analysis: That the areal fraction of a three-dimensional feature intercepted by a random plane provides an unbiased estimate of the volume fraction of that feature. ii) For a lineal or Rosiwal4 analysis: That the fractional intercept on a line passing at random through a two-or three-dimensional feature provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. iii) For a point-count analysis: That the fractional number of randomly or regularly dispersed points falling within the boundaries of a two-dimensional feature on a plane, or within the boundaries of a three-dimensional feature in a volume, provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. The absence of bias referred to in these principles does not, of course, imply that the results of an analysis will be free of error, but only that the expected result is equal to the true one. Application of the foregoing principles provide the following six possible experimental procedures: a) An Areal Analysis—This involves the measurement with a planimeter (or other means) of the area of a constitutent intercepted by the plane of polish b) A Two-Dimensional Random Point Count—Apos-sible experimental procedure for this analysis is to superimpose a sheet of transparent graph paper on a micrograph, and then use a table of random numbers to select coordinates for the points. c) A Two-Dimensiotuzl Systematic Point Count-Similar to b) except that the points are distributed in a prescribed manner, usually at the corners of a lattice superimposed on a micrograph or the screen of a projection microscope. d)A Lineal Analysis—A measurement of the fractional line length intercepted. It is usually performed by traversing the specimen under the cross hairs of a microscope and recording the distance travelled in each constituent. e) 4 One-Dimensional Random-Point Count— This could be performed by traversing the specimen with stops at random intervals to identify the constituent then present under the cross hairs. f) A One-Dimensionul Systematic Point Count— Similar to e) except that the traverse is stopped at prescribed (usually equal) intervals. It will be noted that the point-counting procedures b) and c) can be regarded as methods of estimating the areal fraction. Similarly, e) and f) are indirect methods of making a lineal analysis. All of the six procedures described above involve at least one stage of sampling. Thus, quite apart from any experimental errors, there will always be a statistical uncertainty associated with the final results. It is with the calculation of this uncertainty that we will be concerned. To avoid unnecessary repetition, the statistical relationships that will be used in the calculations are collected together in the appendix. For a fuller discussion reference should be made to one of the many textbooks5,6 on statistics. For symbols relating to the specimen structure we will follow as far as possible the terminology used by Smith and Guttman.7

Jan 1, 1962

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By William R. Wayment, Wayne S. Cusitar

INTRODUCTION The process of mining removes valuable and eco¬nomically recoverable minerals from the earth. In the case of hard-rock mining, this process involves breaking and removing ore, while leaving the waste rock or host rock as intact as possible. Prior to mining, ground stresses exist in the ore and the host rock as a result of weight and tectonic forces; for the purposes of this chapter, the ore is considered to support the host rock on both the hanging and footwall sides. Two basic phenomena accompany mining. First, the hanging walls and footwalls tend to move together as the ore is removed. Second, high stress gradients de¬velop in the rock periphery of the opening; the magni¬tudes of the stress gradients vary widely, depending upon the local geometry and conditions. At various times, mining methods have used square¬set timbers, waste-rock backfill, alluvial sand fill, and tailings backfill materials, with or without cement, to replace the loss of support caused by the removal of the ore. Cut-and-fill mining has evolved to use hydraulically placed tailings for the backfill. In the stope, this fill provides massive support to the walls, thereby reducing stresses in the back. It also provides a floor from which men and machines can work to drill and blast, to haul ore, and to scale and bolt the back. In many cases, the addition of cement provides a competent free-standing wall when the fill is exposed during mining of adjacent stopes or during pillar recovery operations. In most cases, the use of fill does not eliminate standard tem¬porary or local roof control measures such as roof bolts and wire mesh. Fill Characteristics It is important that backfill used for ground support be of maximum stiffness in relation to wall closure. The stiffness of the fill is related to its placement bulk density or void ratio. In the case of cemented tailings, this is enhanced by the cement bonds. During stope closure, individual fill particles experience rotation and crushing at point contacts, but they are subject to little relative translation. The stiffness approaches infinity as the void ratio approaches zero, until the ground forces reach equilibrium, and closure stops. The gradation of particle sizes and minimal segregation resulting from good hy¬draulic placement both contribute to a high degree of early stiffness in the closure history of classified tailings backfill. This also implies that the fill should be resistant to creeping under high static loads. All mines experience shock loading situations such as blasting, and many mines experience rock bursts that can apply sudden and very high loads to the fill. Certain conditions of void ratio, particle size, and moisture con¬tent can result in mass fluidization of unconsolidated fill during such shock loading. Two key factors in avoid¬ing fluid behavior are the provision of a well-drained fill through desliming or classification and the achievement of a small degree of consolidation through the addition of cement in ratios as lean as 40 to 1 (2.4% cement). The acceptance of classified mill tailings as backfill material has been enhanced by its relative economy, including its source, preparation, delivery, and stope distribution. Transportation from the backfill prepara¬tion plant on the surface into the stope usually can be accomplished with low power consumption, with low labor costs, with few capital costs, and at high tonnage rates. An additional benefit is a reduction of the storage volume required for surface disposal of the tailings stream, with a resultant improvement in the environ¬ment. The costs of placing cemented tailings backfill generally range from $1.65 to $6.61/t ($1.50 to $6.00 per st) of fill depending upon the cement ratio used. Scope This chapter examines a major backfill program at a mine and mill complex where the backfill facilities are included as a part of the original planning. The backfill preparation plant is intended to make maximum use of remote controls and automation. The logistics asso¬ciated with material storage, handling, and metering in the plant are outlined. Important considerations in specifying equipment for typical service conditions are discussed. The fill delivery system is described, includ¬ing the boreholes, level lines, and stope distribution lines. Stope preparations for fill confinement and drain¬age are described, as are the techniques of placement and distribution. Methods of controlling and directing the flow of drainage water and slimes are presented, along with the facilities and equipment for clarification, pumping, and sludge removal. As shown in Fig. 1, the fill program encompasses most aspects of the mining and refining facilities, so the discussion is brief in each area. The preparation of backfill of a uniform and con¬trollable quality is presented here as a material handling problem. The balance of the presentation concentrates on the logic of the system, the costs where meaningful (in 1977 US $ unless otherwise specified), and some operating "tricks" that have contributed to system per¬formance and reliability. SURFACE PREPARATION PLANT A backfill preparation plant is required on the surface. This plant generates suitable fill material from the stream of mill tailings. Among the functions of the plant are: 1) Slimes are removed to improve the percolation characteristics of the fill; typically, particles finer than 325 mesh are removed from the tailings. 2) Tailings and sand storages are provided so that the steady stream of tailings produced by the mill can be accepted. Provision is made to accommodate the cyclic high-volume demand from the mine. 3) The plant stores the cement and contains meter¬ing and mixing facilities to provide fill of a controllable and uniform quality. 4) The hydraulic backfill delivery system is a part

Jan 1, 1982

By William H. Mount

INTRODUCTION Effective mine ventilation is required to maintain a healthy underground environment for humans. Without effective ventilation, the environment can become unhealthy or hazardous as a result of the depletion of oxygen, contamination with toxic gases, or the buildup of an excessive amount of particulate matter (dust). Each contaminant has an upper limit of concentration that should not be exceeded within an 8-hr period. This is known as the threshold limit value (TLV). The TLV represents an acceptable level of exposure that should produce no ill effects. Unfortunately, more than one contaminant may be present at any one time and the effects of the individual contaminants may be additive, i.e., the effects of each contaminant must be considered simultaneously to determine the potential danger to miners. Possibly the greatest threat to mine-air quality is the uncontrolled underground use of the diesel engine. The diesel engine was invented in 1892 by Rudolf Diesel. His intention was to develop a power source that could burn coal dust as a fuel, but he was unsuccessful in that attempt and had to resort to liquid petroleum fuels (Johnson, 1975). In 1898, the diesel engine was intro¬duced into the United States by Adolphus Busch, who anticipated using it as a prime mover in factories and generating plants. At that time, the diesel engine was a very large and very heavy engine, designed for fixed installations. By 1919, lighter engines were being developed, and by 1931, Caterpillar was marketing a diesel-powered, track-type tractor (Henderson, 1975). Since 1931, the diesel engine has evolved into an extremely popular prime mover in medium and heavy-duty applications. Efficiencies now are on the order of 40% and improvements such as turbocharging and aftercooling have produced engines capable of generating power at a ratio of 0.3 kW/kg (1.0 hp per 5.0 lb) of engine weight. Although the diesel engine is relatively efficient as a mobile power plant, it is far from efficient in terms of the energy produced from the energy potential of the fuel. About 60% of the heat value of the fuel leaves the engine as wasted heat, with about 50% of that heat being emitted through the exhaust pipe and the other 50% being emitted through the radiator or cooling fins. Perfect combustion in an engine would produce only water vapor (H_0), carbon dioxide (CO_), and nitro¬gen (N2) as the byproducts. Since the diesel is not a perfect engine, each pound of fuel burned generates 5.6 m° (200 cu ft) of exhaust gas, containing about 0.009 m3 (0.33 cu ft) of carbon monoxide (CO), 0.009 m' (0.33 cu ft) of nitrogen oxides (NO, NO2, and NOD), and 0.57 m3 (20 cu ft) of carbon dioxide. The balance of the exhaust emission consists of free nitrogen and water vapor (Hurn, 1975). Contrary to popular belief, the diesel is not inherently dirty. Under normal operating conditions, a well-maintained engine neither smokes nor smells. However, the same well-maintained engine can and does produce toxic emissions. A diesel engine is not inherently safe and constitutes a distinct hazard to personnel. This chapter is devoted to a description of the various toxic substances that may be generated by a diesel engine. Although some of these substances may also be produced by blasting or natural causes, the focus of this chapter is on the relationship between the internal- combustion compression-ignition engine (the diesel) and the quality of the mine air. CARBON MONOXIDE Combustion Process During the combustion process (burning) of organic fuels, each atom of carbon combines with two atoms of oxygen, provided that a surplus of oxygen atoms is available. Thus, the carbon is oxidized to carbon dioxide. Most open flames, such as trash fires, camp fires, gas ranges, etc., produce carbon dioxide. However, with insufficient oxygen, incomplete combustion results as the carbon atoms each combine with one atom of oxygen to produce toxic carbon monoxide. Burning charcoal briquettes produce carbon monoxide because the combustion takes place inside the briquettes where sufficient oxygen is not available to the combustion process. Internal-combustion engines, whether burning gasoline or diesel fuel, also produce carbon monoxide. The only oxygen available to the combustion process is that trapped within the cylinder. If the amount of fuel delivered to the cylinder is excessive, there is insufficient oxygen for complete combustion and carbon monoxide production results. In a normally aspirated (nonturbocharged) diesel engine, the amount of air "sucked" into a cylinder is the same on every intake stroke, resulting in complete combustion only at low levels of engine loading, when small amounts of fuel are injected. Higher levels of engine loading cause larger amounts of fuel to be injected into the same volume of air in the cylinder. Unless the volume of air is increased, the combustion process becomes progressively less complete as the amount of fuel increases. Turbocharged engines are able to compensate some¬what for increased loading and increased fuel consumption. The turbocharger acts as a compressor for the intake air, forcing a larger volume of air into the cylinders as the engine speed increases. Hence the turbocharged engine burns cleaner than a naturally aspirated engine and produces slightly less carbon monoxide (Marshall and Fleming, 1971). Much of the underground equipment used today is powered by turbocharged indirect-injection diesel engines. Although these engines emit fewer toxic contaminants than naturally aspirated engines, they do not eliminate the problem. Since the turbocharger is driven by the exhaust gases, rapid accelerations can cause temporary overfueling of the engine until the turbocharger attains a speed sufficient to restore the correct air-to-fuel ratio. During this "turbocharger lag," the combustion cylinders contain insufficient oxygen, causing severe smoking and an increased output of carbon monoxide.

Jan 1, 1982

To provide a means for rapidly evaluating proposed mine layouts in order to avoid potential hazards while minimizing loss of coal. The Approach: Development of a computer program that will compute many possible mine layouts by changing the mine plan until the arrangement giving minimal hazards with optimum extraction is found. How It Works: The Hazard Evasion Program for Mine Planning, developed by the Bureau's Denver (Colo.) Mining Research Center, tests hundreds of possible solutions to a mining layout, and by sorting out the 10 best (based on the criteria of maximum safety for workers with minimum abandoned coal), limits the number of choices that need to be considered and appraised for applicability to a given mine scheme. The program is applicable for room and pillar or longwall mining, for oil and gas well hazards, and for other hazards that can be described mathematically such as channel sands, potential bad roof areas, faulting, voids, or water pockets.

Jan 1, 1974

By H. L. Bourne

Not everyone understands the concept of mineral royalty. Mineral royalty is a fee paid to a landowner by someone who extracts a mineral commodity from the owners property. The royalty contract between the lessor and lessee contains clauses and conditions that are significant to both parties, e.g., annual m1n1mum, escalation factor, duration of the lease, reclamation and assignability. Comparison of royalty rates requires knowledge of many conditions that influence the value of a given deposit. People in several different professions benefit from shared royalty information.

Jan 1, 1989

By Igor E. Mikhaltsev

The goal of investigation of the midwaters and of the bottom of the world - ocean versus technological possibilities. Manned vehicles and maximum depth decision. The methods of solving of the problem. The science and technology alloy. Mutual venture of Academy of Sciences of the USSR and, Rauma-Repola Oy of Finland. MIR-1 and MIR-2 - as twins. No reasons of copy "Sea Cliff" and "Nautilus". Six landmarks of specificity of "MIR"-type submersibles. The manned spheres and three ballast spheres are made of maraging steel; the electric power resource (100 kwh) and maximum underwater speed (5 knots) is two times more than of the analogous vehicles while the batteries are of NiFe type; the MIR submersibles have the seawater ballast (and trim) system which means practically unlimited vertical manoeuvrability ; and the weight in air is equal to "Nautilus" - 18,6 tons (in case of equal energy resource the weight of MIR-1 or MIR-2 would be 17 tons). Some remarks on standard life support (248 man-hours) safety systems and specificity of launch & recovery system.

Jan 1, 1988

To reduce air be respirable dust generated from emptying dry dust collectors on small truck-mounted drills used at surface coal mines.

Jan 1, 1995

Provide longwall operators with an alternative strategy for placement of gob gas ventholes to improve gas production.

Jan 1, 1995