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By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By J. D. Mote, J. E. Dorn

This investigation was undertaken to study the effects of piledup arrays of dislocations on inducing slip, twinning, and fracturing in magnesium bicrystals. A series of variously oriented bicrystals of magnesium having a vertical grain boundary were prepared and tested in tension. It was found that piled-up arrays of dislocations at the grain boundary could, under appropriate conditions, induce slip, twinning- and cracking. The results that were obtained substantiate, at least qualitatively, the general dislocation mechanism for transmission of strain across grain boundaries and the Petch-Stroh concept of fracturing. WHEREAS single crystals of magnesium generally exhibit extensive deformation, coarse-grained poly-crystalline magnesium at subatmospheric temperatures fractures after a few percent elongation.' Although a small amount of ductility is obtained, several features of this fracturing are characteristic of typical brittle behavior. Over a rather broad temperature range the fracture stress is insensitive to the test temperature and the fracture stress increases linearly with the reciprocal of the square root of the mean grain diameter. The course of fracturing is predominantly intergranular, but small fragments of adjacent grains frequently adhere to the fractured surface.2 The brittle behavior of polycrystalline magnesium is attributable to the limited number of facile deformation mechanisms it exhibits at low temperatures. For a general deformation of a randomly oriented polycrystalline aggregate, each grain must exhibit at least five independent mechanisms of deformation to permit accommodation of the imposed deformation from grain to grain.= Although minor amounts of prismatic slip occur in corners of grains where stress concentrations are known to be high, glide in polycrystalline magnesium at low temperatures takes place almost exclusively by basal slip.' The common type of twinning, which takes place on the (1012) pyramidal planes, can under the most favorable orientations, lead to a. strain of only 6.9 pet; the contribution of twinning to the tensile strain would indeed be much less than this in a randomly oriented polycrystalline aggregate of magnesium. Since the three mechanisms of basal slip are coplanar, they are equivalent to only two independent mechanisms, a number insufficient for a general deformation. Consequently, once the permissible twinning has taken place in conjunction with basal slip, no further plastic deformation is possible because of interference to slip at the boundaries of dissimilarly oriented grains. At this stage brittle fracturing takes place due to high stress concentrations at the juncture of slip bands with the grain boundaries; the predominance of intergranular fracturing in magnesium, in preference to transcrystalline fracturing which is prevalent in zinc, has not yet been rationalized. A more atomistic description of the plastic behavior and fracture characteristics of magnesium follows from the analyses made by stroh4 on the stresses induced by piledup arrays of dislocations. Slip first takes place by dislocation motion in the most favorably oriented grains. As the dislocations approach the boundary of a dissimilarly oriented adjacent grain they begin to form an array of dislocations with its attendant stress field. Piledup arrays of screw and edge dislocations introduce high localized shear stresses at the spur of the array; piledup arrays of edge dislocations also induce high tensile stresses localized in the vicinity of the grain boundary. Whereas the shear stresses can induce slip to take place, the tensile stresses, if sufficiently high, can cause fracturing. The localized shear stress will be relieved if sufficient numbers of mechanisms of deformation become operative in the original and the adjacent grain to permit accommodation of the dislocations in the grain boundary. In this event a ductile behavior will be obtained. But if the number of deformation mechanisms is insufficient for complete migration of dislocation arrays into the grain boundary, the tensile stresses due to the edge components of piledup dislocation arrays will continue to increase with increasing applied stress until fracturing takes place. Whereas face-centered-cubic metals have a sufficient number of mechanisms of slip for accommodation of dislocations in their grain boundaries to exhibit ductile behavior, hexagonal-close-packed metals, in general, do not. Consequently, hexagonal-close-packed metals are usually brittle except when conditions such as alloying or temperature permit facile slip by a number of mechanisms. The arguments presented above suggest that the mechanical behavior of magnesium depends on whether or not dislocation arrays in adjacent grains can enter the grain boundary. When such accommodation is possible, ductile behavior is expected; but when such accommodation is impossible, fracturing will ensue. To further test the validity of these arguments it was considered advisable to study the

Jan 1, 1961

By D. L. Albright, R. W. Kraft

High-purity materials have been used in producing as-cast, controlled, colony, and degenerate solidification structures in the Fe-FeS eutectic. Experiments disclosed that this eutectic can be classified as normal and has a natural morphology composed of rodlike iron particles dispersed in a matrix of iron sulfide. The metallography of the various structures was studied, and a preferred crystallography was revealed in the controlled specimens produced by unidirectional solidification. The orientation effects found in these latter specimens are an [001] fiber texture in the -mowth direction of the bcc iron bhase and a texture corresponding to bicrystalline behavior in the hexagonal iron sulfide, with the growth direction near to (2111) poles. The observed texture of the iron phase is considered as indirect evidence that the alloy un-dercooled by at least 75°C before solidification. The unidirectional solidification of binary eutectic alloys has produced materials which exhibit a structure and properties markedly dependent upon the solidification process. In many cases a controlled microstructure with pronounced metallographic and crystallographic anisotropy can be experimentally achieved by proper regulation and balance of the growth rate of the alloy, the chemical purity of the starting materials, and the thermal gradient in the liquid at the liquid-solid interface. The purposes of this investigation were to produce various micro-structures in the Fe-FeS eutectic for subsequent study of their magnetic properties and to correlate the different structures with the solidification conditions in order to obtain a better understanding of the structure of eutectics. The Fe-S equilibrium diagram exhibits a eutectic composed of nearly pure iron and stoichiometric iron sulfide (FeS1.00), with the eutectic reaction occurring at 988°C and 31.0 wt pct S.1 Calculations indicate that this eutectic should solidify with about 9.5 vol pct Fe and 90.5 vol pct FeS, which in turn suggests2 that the micros tructure will consist of a rodlike iron constituent dispersed in a matrix of FeS. This characteristic has in fact been revealed some years ago.3 Thus, controlled solidification of this alloy might yield a material whose micromorphology would consist of very small ferromagnetic iron particles, rod-like in shape and aligned parallel to one another, supported in a matrix of antiferromagnetic FeS. Such specimens, because of the magnetic characteristics of the two phases, would be interesting subjects of study as magnetic materials. Hence the magnetic properties were considered in detail and are reported elsewhere.4 EXPERIMENTAL PROCEDURE The specimens of Fe-FeS eutectic were prepared from ultrapure iron (99.99+ pct) and high-purity sulfur (99.999+ pct). The iron was estimated to contain 60 ppm impurities (99.994 pct Fe) after zone purification.5 The ingots of iron were cut into chips, and the lumps of sulfur were ground into powder. In order to redice any nometallic impurities which might have accumulated during handling, the iron chips were annealed for 5 hr at 750° ± 10°C in a dry hydrogen atmosphere. Immediately after this treatment the chips were blended with the sulfur powder in eutectic proportions; the mixture was tamped into transparent fused quartz tubing and then vacuum-encapsulated under a pressure of 40 to 60µ of Hg. Because FeS expands upon solidification it was necessary to re-encapsulate the initial capsules so that oxidation reactions would be avoided when the inner tube cracked during solidification. For purposes of homogenizing the blended mixtures before solidification, the double capsules were heated to 750° ± 20°C and held for 20 hr; after this treatment the reacted product was weakly agglomerated. Each sample was then loaded into an apparatus for very rapid melting and freezing; this was accomplished by passing a molten zone through the specimen, using induction heating and a traverse mechanism. The resulting specimens solidified in the shape of the quartz tubing. Two sizes of specimens were used in this work, 18 mm diam by 100 mm long and 5 mm diam by 30 mm long. Metallographic examination of several ingots of both sizes after the above consolidation indicated no lack of compositional homogeneity and a random "as-cast" structure, because the travel rate was so rapid that unidirectional solidification was not achieved. Unidirectionally solidified specimens were resolidified in the apparatus shown schematically in Fig. 1, This equipment consisted of a kanthal resistance furnace mounted on the carriage of a zone-melting unit so that the heating element could traverse the length of the sample at a selected rate of speed. Large specimens were solidified with the mechanism tilted at ap-

Jan 1, 1967

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,' in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960

By K. Huessener

This paper attempts a survey of the principles involved in the combustion of blast-furnace gas in boilers and stoves. I do not expect to be able to give much information which is actually new, since the laws and methods of calculation pertaining to this problem are contained in a number of handbooks; but, so far as I am aware, they have nowhere been treated exclusively with reference to this one problem of gas economy. The road which I follow is less that of strictly scientific research than that of the practical engineer, faced by operation problems which require a quick solution by easily accessible means without a prolonged search in scientific handbooks. For this purpose I give a number of tables and diagrams, as well as the results of many years1 practical working experience as combustion engineer, which I trust will prove useful to my readers. HlSTORICAL Considering the tremendous efforts made during the last 15 years to increase the efficiency of all kinds of power plants, it is highly surprising that until a comparatively very recent period, progress in the economical combustion of blast-furnace gas has been so slow, The explanation generally put forth, that fuel has been so cheap that it was hardly worth while to bother about this economy, will not hold good, for the greatest trouble was taken to improve the combustion of coal and to reduce the consumption of steam, The most plausible explanation appears to be the general impression, held as an accepted fact, that gas, especially hot, uncleaned, blast-furnace gas, was not a good boiler fuel. Many managers of high repute had tried unsuccessfully to improve the conditions of its use, and the dictum went forth that efficiencies of over 60 per cent., particularly with high loads, were impossible. This was the situation not only in the United States, with very cheap fuel, but also in Europe, where fuel prices are twice and three times as high.

Jan 1, 1916

By W. O. Philbrook, K. Natesan

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

Jan 1, 1970

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.&apos; It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By David B. Brooks

Identified potential resources of lead and zinc are lower, relative to reserves, than the same ratio for other metals, Either there is little material below present grades or, if it exists, there are no data on it. The author examines both these factors in detail, and also introduces a third possibility. In their 1961 monograph, The Future Supply of the Major Metals, Bruce Netschert and Hans Landsberg noted that identified potential resources (that is, known but submarginal resources) of lead and zinc were much lower relative to reserves (that is, known and supermarginal resources) than was the same ratio for other metals.&apos; Put another way, it seemed that for such metals as iron, manganese, copper, and aluminum, slightly more favorable economic conditions or modest advances in technology would greatly increase reserves by permitting the exploitation of vast quantities of leaner or deeper or otherwise less valuable mineral deposits. But for lead and zinc, Netschert and Landsberg concluded that either: "(1) there is relatively little material below present cutoff grades; [or] (2) such material exists, but for some reason there are no data.&apos;12 This situation, which they called "the lead-zinc anomaly&apos;&apos; has been subsequently discussed by other authors. The purpose of this paper is to carry the discussion further by examining the evidence in favor of (1) and (2) and by advancing a third alternative. There are at least two reasons for devoting time to the lead-zinc anomaly. First, while it is unlikely that we shall have to turn to alternative lead or zinc resources in the near or middle-term future, the longer run resource picture for the two metals is not so certain.3 Both within the United States and for the world as a whole, new discoveries will have to come at a fair pace to keep up with growing rates of consumption. Thus, it is important to see whether there exist lower grade or nonconventional potential sources of two such useful metals that we could turn to at some time in the future. The second reason for studying the lead-zinc anomaly is also related to resource adequacy, but is of more general significance. Depending upon whether the anomaly is technologic, geochemical, spatial, or temporal in origin, we shall be able to draw some conclusions about the resource picture for other metals. Can we expect the apparent pattern of lead-zinc resources to be repeated? If so, will technologic advances in either exploration methods or mineral processing be able to alter the pattern? Or is the pattern unalterably set by geochemical distribution? Most important, are metals characterized by what seems to be an anomaly, different in any way from metals for which low-grade or nonconventional sources already have come to be exploited, as the porphyry deposits have for copper. In sum, investigation of the lead-zinc anomaly represents a case study combining both physical and economic aspects that may open up a neglected area in evaluating mineral resource adequacy. WHAT IS THE LEALLZINC ANOMALY? There are two dimensions to evaluations of the potential of any mineral resource? The first involves the degree of certainty that we ascribe to the estimate: how much do we know about the size of the resource as a result of geological mapping, exploration, and mine development? This dimension is expressed by the terms measured, indicated, and inferred reserves (and, if you wish, &apos;undiscovered reserves&apos;), all of which terms carry with them the implication of exploitability under current cost-price conditions. The other dimension to evaluations of a mineral resource involves the economic limits of the estimate: how will the size of the resource vary with different (usually more favorable) cost-price conditions? (This economic dimension should be understood broadly to include all factors bearing on the cost-price relationship. In this sense it subsumes technology because any resource is exploitable at some cost; the role of technology is to bring cost down.) The latter dimension is expressed in the terms potential or sub-marginal &apos;ore,&apos; and is logically quite independent of the former. For example, we have relatively good measurements of the tonnage of manganese in low-grade deposits in this country, though they are too lean to be considered reserves; on the other hand, we are much less certain of our measurements of new lead and zinc deposits in Missouri, though there is no question but that there is a sizable reserve. Thus, it may be uncommon but is not a contradiction to talk of measured submarginal ore or inferred potential ore.

Jan 1, 1968

By Hugh Marriott

MANGANESE and its ores have been recently dealt with in comprehensive papers to the Iron and Steel Institute by Sir Robert Hadfield, and in a series of papers read before the A. I. M. E. at the Cleveland meeting. I have taken the opportunity of adding this mineral, to my records of the "World&apos;s Mineral Production and Consumption," as recently pub-lished in the Economist ?. The tables bring out the following significant facts: The world&apos;s production has increased by 10 per cent since 1913. India&apos;s production has increased by 3 per cent since 1.913, the supply from this source now being 31.1 per cent of the world&apos;s output. Russia is now producing at about half its pre-war rate and yields 19 per cent of the world&apos;s production. West Africa supplies 12.5 per cent of the world&apos;s total output. Brazil&apos;s present output is 2.5 times that of the pre-war period, being 11.3 per cent of the world&apos;s output.

Jan 9, 1927

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By Hugh S. Spence

THE use of natural feldspathic rocks, as opposed to straight feldspar, for ceramic purposes is not new. "Cornwall stone," a semi-kaolinized granite containing fluorite, has long been used by the English pottery trade instead of feldspar, and "Carolina stone," a similar rock, is now being offered to the American trade. A recent report of the U. S. Bureau of Mines states that trachyte, a glassy volcanic rock, is being used in California instead of feldspar in ceramic bodies. In Germany, phonolite and basalt have been investigated, and possibly also used, as ceramic raw materials, and extensive research has been conducted in Russia in recent years looking to the utilization of the immense bodies of nepheline syenite of the Kola Peninsula, which is the host rock of the apatite deposits now being exploited on a large scale in the Murmansk region; the nepheline is recovered as a by-product of the concentration of the apatite. Long used principally as a raw material for the pottery and allied industries, where, in bodies, glazes, enamels, etc., it serves as a fluxing ingredient and forms, on firing, a glassy bond with the more refractory clay, flint and coloring particles, feldspar has been finding ever increasing employment in glass. In 1936, over half of the nearly quarter of a million tons of feldspar sold in the United States went to the glass trade. Its usefulness for this purpose is due to the resistance to thermal shock which it imparts to glass products, particularly bottles, containers and tableware, because of its alumina content, which averages from 16 to 20 per cent. Active search has been made on the American continent during the past few years for other minerals of feldspathoid type, with comparable or higher alumina content, that may be suitable for glass and other ceramic purposes. One of the most important results of this work has been the delimiting in central Ontario of large bodies of nepheline syenite of excellent ceramic grade.

Jan 1, 1938

By Charles C. Towle, Irving Rapaport

URANIUM mineralization along the north flank of the Zuni Uplift, in the vicinity of Haystack Butte, was discovered by Paddy Martinez, a Navajo Indian, in the spring of 1950. The find was reported to the Santa Fe Railway Co., which initiated a program of exploration upon its holdings in the district in December of 1950. The Anaconda Copper Mining Co. secured numerous leases in January and February, 1951, and began an intensive exploration and development program in March 1951. The district was extended into the Lucero Uplift in August of 1951 by the discovery of uranium mineralization in Todilto limestone by Joy Sinyella, a Supai Indian living on the Laguna Reservation. Initial reconnaissance was performed in the district by the Atomic Energy Commission in November 1950. A field office under the direction of the Denver Exploration Branch of the AEC was established at Prewitt, N. Mex. in January 1951 to study regional and detailed guides to ore, to evaluate the ore deposits, and to promote the development of the district by providing geologic services for the companies and individuals engaged in exploration. With the development of sufficient ore to warrant construction of a mill, the Grants area of New Mexico has come of age as a full fledged uranium mining district. The carnotite-type deposits of Grants, the first of major economic importance found in limestone, have extended the Colorado Plateau carnotite field into the more complex structure of the Basin and Range Province. General Geology The Grants uranium district is in northwestern New Mexico, along the southern flank of the San Juan Basin, between the cities of Gallup and Albuquerque. The region is at a mean altitude of about 6800 ft, vegetation is sparse, and outcrops are excellent. Mt. Taylor volcanic peak, at an elevation of 11,400 ft dominates the surrounding area. The overlying cliff-forming Dakota sandstone is the most resistant formation in the Grants District and characteristically erodes into dissected mesas as much as five miles wide. The principle uranium ore-bearing horizons are found in the underlying Morrison formation, and the Todilto limestone of the San Rafael group. The Morrison weathers into. a series of steep slopes and precipitous cliffs near the lower part of the Dakota-capped rims, while in contrast, the relatively resistant underlying. Todilto [ ] limestone forms broad benches extending out from the base of these Dakota rims as much as five miles wide. The Todilto benches are covered with overburden to an average depth of about 5 ft in the first thousand ft away from the Dakota rim, but increases to about 200 ft at the base of the rim. In many places however, a thick mantle of upper Cretaceous sediments and Tertiary volcanics "obscures the ore-bearing Jurassic, and precludes exploration. . The known uranium deposits of the Grants District are distributed throughout a zone 85 miles long and about 10 miles wide. Stratigraphy Rocks from pre-Cambrian through Tertiary are exposed in the uplifted areas, but uranium appears to be restricted chiefly to two zones in Jurassic sediments. The Jurassic sediments of the Colorado Plateau have been subdivided into three units, in ascending order: (1) Glen Canyon group, (2) San Rafael group, (3) Morrison formation. The Todilto limestone zone within the San Rafael group has produced the bulk of ore to date, but the promise of the Morrison zone is rapidly increasing. The Todilto formation extends about 300 miles east-west and about 100 miles in a north-south direction. It is composed of a lower, extensive, limestone member and a central, more restricted, thick, pure gypsum member. The Todilto is believed to be of lacustrine origin. The Morrison formation in this area is subdivided, rather arbitrarily, into three members: Recapture Creek, Westwater Canyon, and Brushy Basin. Ore

Jan 1, 1952

By J. D. Hunt, D. T. J. Hurle

A uariety of eutectic structures are formed in faceted/nonfaceted eutectics. The various structures are explained in terms of the absence or presence of small facets in the liquid groove. Regular structures are produced when, for purely geometric reasons facels cannot form. The presence of a facet in the liquid groove leads to the formation of an irregular or a cell-like complex regular structure, due to the relative immobility of the groove. A classification of eutectics was proposed by Hunt and jackson, based on the presence or absence of facets on the primary phases (the absence of facets may be predicted from the dimensionless entropy of melting2). Eutectics were divided into three groups: 1) eutectics in which both phases grow in a nonfaceted manner; 2) eutectics in which one phase grows faceted, the other nonfaceted; 3) eutectics in which both phases grow faceted. It was suggested that regular1 rodlike or lamellar structures1 should be formed in the first group, that irregular or complex regular structures1 should be formed in the&apos; second, and that irregular structures1 should be formed in the third. Recently it has been shown that the structural classification is incomplete. Regular rodlike structures (InSb-NiSb eutectic3), or broken lamellar structure (Bi-Zn eutectic, Fig. 8), are formed in alloys of the second group when the faceted phase has a large volume fraction. Hunt and jackson&apos; argued that regular structures could form in faceted/nonfaceted systems, but that such structures would be unstable in the presence of microfacets on the lamella of the faceting phase, because the growth rate at a point on such a facet would depend on the kinetic undercooling at the point of nu-cleation on the facet, and not on the local kinetic undercooling. In these circumstances it would not be possible to consistently balance the compositional and kinetic undercooling over a lamellar structure and thus obtain a stable isothermal interface. In this paper we discuss in detail the origin of the various structures formed in faceted/nonfaceted systems, pointing out that the most important factor promoting the formation of a regular structure is the absence of a facet in the liquid groove. 1) FACET FORMATION IN SINGLE-PHASE MATERIALS Facets form when there is an energy barrier for the addition of a new solid layer on an existing solid. When a barrier is present,2 growth proceeds by the lateral movement of steps across a crystallographic plane. The rate-controlling stage of the process occurs when the step is first formed. Hulme and Mullin6 have shown that faceting in single-phase materials can only occur when both interface curvatures are convex with respect to the solid and when the surface is tangential to the facet plane. When even one of the curvatures is concave a facet does not form because new layers of solid from adjacent regions can always feed the facet plane, Fig. 1. Growth under these conditions is then as easy as elsewhere. Similar considerations will apply to eutectic growth; consequently the shape of the faceted phase is extremely important. 2) LAMELLAR SPACING CHANGES IN EUTECTICS Jackson and Hunt7 have shown that the interface undercooling AT of a growing lamellar interface (neglecting kinetic undercooling) is related to the lamellar spacing, A, and growth velocity, v, by an expression of the form: where m, Ql, and nL are constants of the system given in Ref. 7. Eq. [I] is plotted for fixed v in Fig. 2. Jackson and Hunt postulate that a regular eutectic grows near, but to the right of the minimum in the AT vs A curve. They argue that the spacing cannot be to the left of the minimum because the interface is then unstable to fluctuations in A. It cannot grow too far to the right, because when the spacing becomes too wide an isothermal interface can no longer be maintained over the large-volume-fraction phase.7 It is argued that during any change in growth rate the lamellar spacing remains in the permitted range by the movement of lamellar faults. When the spacing is too wide, the fault, shown in Fig. 3, moves to the left; when the spacing is too narrow it moves to the right. The faults, however, have to be formed. heir formation has been shown to occur when local regions deviate considerably from the spacing defined by the lamellar When the spacing is locally too narrow (it passes to the left of the minimum, Fig. 2), pinching off of the narrow phase occurs. When the spacing is locally too wide, the interface on the large volume-fraction phase can no longer be maintained as an iso-

Jan 1, 1969

By G. L. Wilhelm

Prior to the construction of a 450 tpd concentrator at the Mayflower mine, owned by the New Park Mining Co. and operated by the Hecla Mining Co., the common mining methods were cut and fill, with waste or gob filling and square set timbering with waste fill. Stoping operations were beset with the usual problems related to waste filling methods- storage and handling of fill material from development, costly waste excavations necessary to obtain a portion of the needed waste rock, slow mining cycles due to filling and inefficient ground support. After Hecla Mining Co.&apos;s successful utilization of sandfill in its mines in the Coeur d&apos;Alene district, utilization of hydraulic fill in stoping operations at the Mayflower was a logical development of the modernization plan then in progress. The mine, located in the southeasterly part of the Park City mining district, Utah, is a medium size producer of lead and zinc ores, with gold, silver and copper as secondary minerals. The mine has been producing commercial ore since 1939 from a dual vein system which outcrops at an elevation of 7200 ft in the Wasatch Range. Access to the present mining areas is gained by a 7200-ft haulage tunnel and by an interior, three-compartment main shaft. The present mining horizons are about 2400 ft deep. The average horizontal cut and fill stopes, ranging from 3-15 ft wide and up to 120 ft long, can be classed as small.

Jan 5, 1968

By J. S. Rinehart, W. C. Maurer

The mechanics of impact crater formation in rock, particularly sandstone, has been sutdied, the velocity range being approximately that normally associated with oilwell gun perforators. The bullets were small steel spheres having diameters of 3/16, 9/32 and 7/16 in; impact velocities ranged from 300 to 7,000 ft/sec. The craters have two distinct parts — a cylindrical hole (or burrow) with a diameter the same as that of the impacting sphere, and a wide-angle cup comprising most of the volume of the crater. The burrow is fornred as material in front of the projectile is crushed and pushed aside, forming a cylindrical hole surrounded by a high-density zone. The clip forms as fractures are initiated in front of the projectile and propagate along logarithmic spirals, approximaling maximum shear trajectories, to the free surface of the rock. A most significant observation (made for the first time) was that, below the base of the cup in one type of sandstone, there are a group of similar fractures, not extending to the surface, which are spaced uniformly a few millimeters apart. Each fracture follows roughly the contour of the base of the cup and appears to require a certain threshold impulse to initiate it. These fractures comprise a relatively high fraction of the total, newly exposed surface area. The volume of the material removed by crushing varies as the first power of the impact velocity and the volume removed by fracturing, as the second power of the impact velocity. Penetration varies linearly with the impact velocity and is inversely proportional to the specific acoustic resistance of the target material, the proportionality constant being dependent upon the shape of the projectile. INTRODUCTION Yield of oil from a producing well is frequently enhanced by firing bullets and shaped charges through the well casing into the oil-bearing rock, forming craters and fractures from which oil can flow more readily. The purpose of this investigation has been to develop a better understanding of the mechanics of impact crater formation in rock, particularly sandstone, the velocity range being approximately that normally associated with oilwell gun perforators. FORCES OPERATIVE DURING IMPACT When a projectile moving at considerable velocity strikes a- massive target such as oil-bearing sandstone, intense and complex transient stress situations develop within both the projectile and the rock or sandstone against which it is striking. Usually the struck rock fails, the missile or projectile penetrating into the rock to some depth where it comes to rest or is forcibly ejected from its burrow by expansion of a plug of target material compressed in front of it. When the impact velocity is very high, the projectile itself may fail, breaking apart or becoming distorted; this situation is not considered here, the discussion being limited to nondeforming projectiles. Many experimental studies&apos;.&apos; have been carried out to determine the nature of the mechanics of crater formation and the salient features of the forces coming into play, some of the earliest studies being the French Army experiments performed at Metz between 1835 and 1845.&apos; The stratagem in most instances has been to make a post-mortem examination of the crater, measuring volume and depth of penetration and deducing force relationships from these observations rather than performing the more difficult (usually almost impossible) feat of measuring stresses during penetration. In many materials, the force acting during penetration of the projectile is found to be the sum of two components—(1) a constant force, independent of the velocity, representing some inherent strength of the target material; and (2) a component, proportional to the square of the velocity, representing inertial forces. For such materials, the average force per unit area acting on the projectile at any instant while it is in motion and being decelerated may be written F/A = a + bv2 . . . (1) where v is the velocity of the projectile at that instant, A is the cross-sectional area of the penetrating projectile taken normal to its trajectory, and a and b are constants which are dependent upon the target material and the shape of the projectile. It follows that the total penetration s is given by .........(2) where v, is the velocity of the projectile when it just strikes the target. Values of a and b for spherical projectiles impacting in a loose sand-gravel mixture and compacted earth were obtained in the Metz experiments. For sand-gravel, a and b are 620 psi and 0.0115 (psi) (ft/sec)&apos;, respectively; and for compacted earthworks, a and b are 432 psi and 0.0008 (psi) (ft/sec)&apos;. Figs 1 and 2

By E. A. Beck

For a number of years many attempts have been made to use thermit in order to do away with piping in ingots. Some of these attempts were successful, while others did not give the expected results. Nearly every plant had its own method of using the thermit, and no special care was taken to study the results or to find the causes for lack of success. Formerly the principle of the process was to decrease the piping by introducing a can filled with thermit, attached to an iron rod, into the head of the ingot directly after it had been poured. In this case the thermit reaction took place in the upper part of the ingot, and it was thought that through the heat produced the head would keep liquid longer and piping thus be reduced. In other words, the aim was to keep the head of the ingot open by making use of the heat of the thermit reaction, which would thereby give the gases in the steel sufficient time to escape. This result can be attained by the application of a large enough quantity of thermit, but it would not be economical in general practice, and could only he used for high-grade material. Many steel-makers abroad and in this country have had this experience. The Th. Goldschmidt A. G., Germany, has, therefore, made a special study of this question with the cooperation of a well-known steel company, and has worked out a new method for the application of thermit for this purpose. The results obtained have been most satisfactory and reliable, and this process is now used in Germany on a large scale in many prominent steel-works. The thermit is applied in cans, as in former years, but the principle of the process is entirely different. The object of using the thermit is not to heat the steel and keep it liquid,

Jan 1, 1914

By K. Harms, T. D. Jones

TO unload large tonnages of lead bullion cast in 100-lb. bars is a problem which has confronted the lead refineries for many years. The bars, on arrival, must be restacked for unloading by truck or hand-charged to charging machines. Selected crews of labor, capable of working at sustained speeds for five- or six-hour periods, are required for this exhausting task. Due to the fatigue involved crew personnel changes rapidly. During the war it became increasingly difficult to maintain crews, especially in critical labor areas, so that the development of casting and shipping ten-ton lead blocks from the smelters to the refineries became a must in our operating program. For many years lead refineries, when making interdepartment or intradepartment transfers, have cast lead blocks weighing five or ten tons which are easily handled by crane by merely attaching the crane hook to a steel anchor embedded in the frozen lead blocks. In previous years, the practice was to use regular smelter slag pots which, due to their rounded shape, produced what were called "buttons" by the refinery personnel. The button-type blocks were unsafe as they rolled and tipped easily and were unsatisfactory for stacking since no piling pattern could be followed. To remedy this situation, flat-bottom molds came into general use and later the bottoms were made concave to prevent slipping.

Jan 1, 1946

By Rossiter W. Raymond

As I have attempted briefly to show you, gentlemen, the present position of the mining and metallurgical industries of this country offers in several respects most important indications of radical change. This is an epoch for more than one branch of these industries. We are commencing again to export copper; we have shifted the main production of lead from the Mississippi Valley to the far West, besides developing a new production of that metal in Missouri; we have seen the price of quicksilver go up, and the price of iron go down to such an extent as to affect profoundly, on the one hand, the great business of extracting silver by amalgamation, through the Washoe process in this country and the patio process in Mexico, and, on the other hand, the various manufactures employing iron as a raw material; above all, the manufacture of steel. But the epoch which has occurred in the relative value of gold and silver, in consequence of causes which I shall attempt to explain, and among which the extraordinary increase in the silver product of Nevada is not the least; this epoch is, perhaps, the most striking feature in the review of our situation. Since my official duties in connection with the mining industry of the Pacific slope and the Great Interior Basin have led me to pay particular attention to this subject, I have thought it not inappropriate to lay before you a somewhat extended account of its history. It is a topic of peculiar interest, because of the general use of these two metals as standards of value in the exchange of commodities. Neither of them is suitable to be, for the political economist, a real standard of value. That standard is rather to be sought in some more universal product of labor, such as wheat—the relation