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By S. J. Burns, W. W. Webb

The dislocation arrangements formed during unsteady propagation of cleavage fractures on (010) planes in LiF have been investigated by high-resolution etch-pit techniques and by X-ray diffraction topogvaphy. In impurity-hardened crystals, cracks propagating in any direction on (010) planes at velocities of about 103 cm per sec are usually accompanied by light plastic deformation which is enhanced wherever the crack is allowed to hesitate. Dislocations with [011] type Burger's vectors are often formed looped around the crack tip. They are dragged along with the crack tips leaving edge dislocations lying nearly parallel with the clearage surface about 5µ from it. These dislocations are easily overlooked since they may initially intersect with the cleavage surface infrequently and later may disappear from the crystals due to image forces during aging at room temperature. Although the plastic work associated with these dislocations is only comparable with the reversible (010) surface energy, an instability in crack propagation appears due to a limit of the velocity with which dislocations can be dragged along with the crack. Transition to a fully brittle nonplastic fracture mode occurs when the crack velocity exceeds the velocity with which dislocations can be moved by the stress field of the crack. TRANSITIONS between brittle and ductile modes of fracture appear to be common processes in the behavior of materials in which the flow stress is close to the stress at which brittle cracks can propagate. High-strength engineering alloys fit into this category and the transition from ductile to brittle modes of crack propagation may be associated with catastrophic failures in these important materials. The methods of theoretical mechanics indicate the geometrical conditions in which these processes may occur but the detailed mechanisms controlling the generation of dislocations in the initiation of the plastic mode and the process by which the loss of plasticity occurs on transition to the brittle mode are not yet clear. Since these mechanisms are not amenable to direct observation in engineering alloys we have chosen a semi-ductile alkali halide LiF as a model system in which to observe transition mechanisms between plastic and brittle modes of crack propagation. Cleavage cracks in this system are known to undergo a plastic-elastic transition at velocities between 103 to 104 cm per secl and dislocation configurations in LiF are amenable to study by optical-microscopic observation of dislocation etch pits2 and by X-ray diffraction topography.3 We have been able to identify a dislocation mechanism responsible for the transition from brittle to slightly plastic modes of crack propagation in LiF. A model based on this mechanism permits calculation of the critical crack-propagation velocity for this transition and indicates the importance of the stress dependence of dislocation velocity in determining the critical crack velocity. Of course, this model cannot be carried directly over to more complex materials but it is quite possible that its qualitative features are generally applicable. Dislocations intersecting fresh cleavage surfaces in LiF were reported by Gilman,4 by Forty,5 and by Wash-burn et a1.6 Such dislocations were construed to have been nucleated where the cleavage crack hesitated or stopped, near stress concentrators, such as cleavage steps, on the crystal face. The loci of such dislocations deposited On the cleavage plane in bands were called "stop lines" or "deformation zones". Gilman, Knudsen, and walshl measured the velocity of cleavage cracks in lithium fluoride by evaporating thin resistive strips on the crystal side and recording

Jan 1, 1967

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'-' Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By J. E. Walstrom

While intensive research continues to promote a more complete understanding of the potential and resistivity measurements that comprise the electric log, it is believed that consideration should also be given to translating these numerous and often widely separated findings into a coordinated and readable body of fundamental facts designed specifically for the petroleum engineer and geologist. Although provision is made through publication for a ready exchange of new theoretical concepts. it is also desirable to provide reviews and appraisals of the more established techniques and methods from the operating standpoint so that an economic and practical application may be realized concurrently with the theoretical progress. With these basic premises as a guide the author reviews the presnt state of electric log interpretation. The paper is directed not so much to the logging or research specialist as to the petroleum engineer and geologist to whom the electric log is only one of the many tools which he employs. Frequently, these persons do not have the time to follow in detail the many specialized contributions that appear and, as a consequence. are not in a position to place these contributions in proper relation to each other, or to the art as a whole. The paper reviews the basic steps in making quantitative determinations from the electric log of the amount of oil or gas present in subsurface formations and also discusses the degree of reliability of these determinations under various conditions. The paper also indicates the trend of future developments in electric logging systems and methods of interpretation. INTRODUCTION The electric log has been used about 20 years as a means for studying the formations penetrated by a well bore. The first half of this period is characterized by the development of suitable logging techniques and equipment. Although progress in this direction is continuing at a satisfactory rate, the last ten years are characterized more by an increasing interest in methods of electric log interpretation. During this period, a large number of fundamental papers have been published, expounding various logging techniques and particular phases of the interpretation problem. Many of these papers represent important contributions, and a few are classic. This paper is an effort to outline as concisely as possible and in simple terms the main course of progress in electric log interpretation. More specifically, it is the purpose of the paper to review the necessary elements and basic steps used in making quantitative determinations of water saturation from the electric log; and to point out the degree of reliability of these determinations under different conditions. It is strongly advised that the operating staffs of the drilling and exploration departments of oil companies cooperate wholeheartedly with both the electric logging service companies and research organizations in the testing and development of new logging systems and interpretation methods. One purpose of the paper is. however, to indicate the degree of caution which must be exercised in placing confidence in new techniques and interpretation methods that have not been thoroughly tested in the field. It is entirely possible to be cooperative in trying new methods and yet reluctant to believe in the results until the methods are firmly established. It is important to define the meaning of quantitative electric log interpretation. In the most general sense, an interpretation of the log has been made when the electrical characteristics of the formations, as portrayed on the log, have been translated into terms describing the formation geometry, rock type, or any other physical characteristics of the formations. The determination that the top of a sand is at a certain depth is an interpretation of the log. Structural determinations made by correlating electric logs from a given area are also interpretations of the logs. The term quantitative interpretation, however, will be used in this paper in the restricted sense to indicate the determination of the water saturation of a formation. This determination defines the fluid content of an oil and gas productive formation only if the porosity is known, and it assumes that the remainder of the pore space contains hydrocarbons. This assumption is believed to be true for most oil and gas productive formations. The quantitative electric log interpretation may he said to be a determination of the fluid content only to the extent which the water saturation, under the conditions given above. defines it. THE BASIC STEPS The fundamental steps in calculating water saturation from the electric log are: 1. Determination of the true resistivity of the formations from the apparent resistivities as recorded on the electric log.

Jan 1, 1952

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By H. S. Price, J. C. Cavendish, R. S. Varga

This paper presents a new technique for solving some of the partial differential equations that are commonly used in simulating reservoir performance. The results of applying this technique to a simple problem show that one obtains accurate pressure values near wells, as well as accurate pressure pdients, which can be explicitly calculated. The method is completely rigorous in that convergence of the discrete numerical solution to the continuous solution for both pressure and pressure gradient is established. High-order, piecewise-polynomial approximations are used near the wells where pressure gradients are steep, while low-order, piecewise-polynomial approximations are used elsewhere to reduce greatly the calculation time. This combination is shown to give a uniformly good approximation to the solution. These approximations, obtained by using a Galerkin process with suitable Hermite subspaces, are shown to be theoretically and numerically superior to the usual approximations obtained from standard finite-difference techniques. Not only are much greater accuracies obtained, but computer times are also greatly reduced. The application of this technique to multiphase flow problems (e.g., single well coning problems) would have considerable practical interest, but such extensions of this technique with full mathematical rigor have not been made as yet. However, the numerical methods presented here are general, and in principle extend to multidimensional, multiphase flow. Moreover, the preliminary results given in this paper are sufficiently encouraging that we feel the effort in attempting these extensions is justified. INTRODUCTION The problem of obtaining accurate pressure distributions and pressure gradients around wells is of considerable importance in the numerical simulation of reservoir performance. The most common approach to solving this problem is to use finite difference techniques (see McCarty and Barfield9 or Peaceman and Rachfordl0). This approach, however, has many disadvantages, the major one being that many grid points are generally necessary for accurately describing the pressure distribution and the pressure gradient around wells. This need for a fine grid results in large computer times and often in prohibitively high costs. Besides investigating the method of finite differences, some authors, such as Welge and weber17 and Roper, Merchant and Duvall,13 have considered a combination of analytical and numerical techniques with some success. These approaches, however, are all nonrigorous and quite often cannot even be applied. In this paper, we present a numerical formulation of high-order accuracy, based on the Galerkin method, for solving this problem. We treat here only the partial differential equation that describes steady-state, single-phase flow. However, the methods presented are general and in principle extend to multidimensional, multiphase flow. Specifically we treat special cases of the problem in two dimensions described by: where G is a rectangle (with sides parallel to the coordinate axis) with boundary ?G, ?/?n denotes the outward normal, and y and B are non-negative constants such that y + B > 0.

Jan 1, 1970

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By Kirtland Marsh

THE manufacture of gas masks by the Chemical Warfare Service, U. S. A., required preparation of the carbon used in the canisters. The largest plant for the production of this carbon was situated at the works of the Astoria Light, Heat and Power Co., at Astoria, N. Y.; this paper will deal1 with the pyrometry equipment at that plant. Commercial charcoal was found unsuitable for use in gas masks because of its low power of absorption and its poor resistance to abrasion. The best raw material for the production of carbon was found to be coconut shells, but any kind of nut shells or fruit pits were used when sufficient quantities of coconut shells could not be obtained. The shells were first carbonized in retorts, the carbon was then crushed and screened between 8 and 16 mesh, and finally submitted to a special heat-treatment in air; steam treatment was later substituted for treatment in air. The production of gas-mask carbon on a commercial scale was begun at Astoria about Aug. 1, 1917. Temperature control was essential during the initial carbonization of the shells, as well as during the air or steam treatment, and pyrometers were installed for this purpose. The installation and maintenance of all pyrometry equipment was done by the pyrometry department, consisting of an officer in charge, an assistant, and two men. A special pyrometry laboratory was maintained in which all repairs were made.

Jan 9, 1919

By R. T. DeHoff, L. J. Buteau, J. Kronsbein

Network topology is introduced and used to describe sinter bodies at various stages of the sintering process. The matrices of incidence, loop-branch. tree-branch, and cut-branch are constructed and their relationship to the three-dimensional void space and the common two-dimensional bounding surface is established. The sintering body is assunzed to remain connected but this is not so with the void space. The topological invariants known as Betti numbers are related to this observed fact and provide parameters which measure the progress of the sintering process. They are extracted from the matrices by means of known algebraic operations. Experimental procedures are given which permit actual construction of the various matrices and determination of the Betti numbers by serial sectioning of the sinter bodies. A sinter body is produced by exposing a large number of metallic particles (0.00001 to 0.3 in. diam) to a temperature that is near but below their melting point. When these particles are maintained at such a temperature for a sufficient length of time, it is found that the interparticle contacts become welded. As time increases, these welds, often referred to as necks, grow. All of the space between the particles constitutes a single connected void; an ultimate consequence of sintering is the breaking up of the void into separated parts. A mathematical apparatus for describing the geometric characteristics of a sinter body at each stage of the process was first proposed by F. N. Rhinesl when he introduced the application of topology to this problem. He described the sinter body in terms of one of its topological invariants, the genus. The most important advantage of a topological description is invariance with respect to continuous deformations. This means that particle sizes and shapes need not be considered, resulting in considerable simplification and generalization of the geometric description. In the case of a sinter body, wherein the internal geometry is particularly complex, the simplification provided by topological concepts is absolutely essential. The important parameters in the Rhines model are the number of particles and the interparticle contacts. The invariant considered called genus is given by Euler's formula for the connectivity of two-dimensional surface of the sinter body. This surface includes the pore-solid interface. The Euler formula is G = C - P + 1 [1] where C = number of interparticle contacts, P = number of particles, and G = genus of the surface bounding the sinter body. In topology the term genus may be used to mean the number of self re-entrant cuts that can be made on a closed surface without dissecting it into more than one connected surface. Its use is restricted to the surface and does not apply to the three-dimensional volume enclosed or excluded by it. In the case of sintering, the volume enclosed by the surface is defined as the sinter body; the volume excluded will be referred to as the void space. There is an intrinsic reason for using genus as a characteristic number associated with a sinter body. The genus is related to the Gaussian curvature by the integral of the product of the principal curvatures taken over the entire surface of the sinter body, as given by

Jan 1, 1965

By A. Kelly, S. Sato

Tensile tests have been performed on aluminum single crystals of 99.99 pct purity at 196°K. The resolved shear stress when the stress-strain curve becomes concave to the strain axis depends on orientation, being always higher for crystals with an initial orientation close to the sides of the unit triangle. Observations have been made, with the optical microscope, of the appearance of slip lines on polished surfaces of the crystals. Particular attention has been paid to the first appearance of cross-slip. It is confirmed that marked cross-slip is first seen when the stress-strain curve becomes concave to the strain axis. Measurements are reported of the lengths of the slip lines observed on top and side faces of the crystals at various stages of the deformation. The lengths of the slip lines vary inversely as the flow stress for all crystals, independent of crystal orientation. From measurements of the lengths and separations of the slip traces it is possible to estimate the number of dislocations which are annihilated at each cross-slip site. It is concluded that the annihilation of screw dislocations of opposite sign is the most important cross-slip process occurring. FRIEDEL1 recently pointed out that the stress-strain curve of many pure metals of face-centered-cubic structure can be considered as composed of three stages. Plastic flow commences with a region showing a small rate of hardening which is approximately linear. This has been called "easy glide*. It is followed by a region of more rapid hardening in which the slope of the curve is again approximately constant and this, in turn, is superseded by a final part of the curve which is concave to the strain axis. Following Diehl2 we may designate these regions as stages I, II, and III respectively. The onset of stage 111 occurs at lower stresses at higher temperatures. The appearance of the slip lines formed during these various stages has been described by a number of workers?-5* The object of the present work was to make detailed observations of the lengths and separations of slip lines for a number of crystals of different orientations deformed at the same temperature and strain rate. Although much previous work has been published on the deformation of aluminum single crystals the importance of measurements of these quantities has only recently been realized—they are essential for experimental tests of recent theories of work hardening.' 9 In aluminum, deformed at room temperature, stage 11 of the stress-strain curve is very weakly marked, as the stress for the onset of stage 111 is attained soon after the end of easy glide. In the present experiments it was decided to use a temperature lower than room temperature so that stage II of the curve was better developed. However, at temperatures as low as 90°K slip lines are not measured easily with the optical microscope.5 For this reason 1960k was chosen as a suitable temperature. Even at 1960k however, stage III of the curve commences at glide strains of 6 to 10 pct and hence

Jan 1, 1960

By Hsun Hu, R. S. Cline

The annealing behavior and the mechanism of re-orientation during recrystallization of iodide titanium cold-rolled 94 pct have been studied in detail. Results indicate that recrystallization occurs by the nucleation and growth of new grains, as in other common metals. Recrystallization nuclei form by the coalescence of subgraim, and the change in texture as a result of recrystallization is largely due to selective growth among the nuclei formed. The annealing of titanium is characterized by a wide range of overlap of the various stages of the annealing process, which may be responsible for a range of activation energies observed, and for the apparently gradual change in the annealing texture as a function of time or temperature. The deformation and recrystallization characteristics of titanium and zirconium are very similar. In cold-rolled strip, the deformation texture consists of two symmetrically oriented components, each having the basal plane laterally tilted at about 30 deg from the rolling plane and the [1010] direction parallel to the rolling direction. Upon annealing for recrystallization, the change in texture can be described, for simplicity,* as rotations around [0001].2'6'8 According to McGeary and Lustman,' recrystallization occurs in zirconium through normal growth of the subgrains, which they called "domains", without the nucleation of new grains; and the magnitude of rotation around the [0001] axis increases gradually during the progress of recrystallization. If these conclusions were true, the mechanism of recrystallization in zirconium would be basically different from that in most metals, since it is commonly known that recrystallization with reori-entation always involves the migration of high-angle boundaries. In an attempt to clarify the situation, the mechanism of reorientation during recrystallization in iodide titanium cold-rolled 94 pct was studied in detail. The structural and textural changes upon annealing at various temperatures were examined by optical and transmission-electron microscopy, X-ray pole figures, pole density distribution measurements, and micro-beam techniques. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. An iodide titanium crystal bar was are-melted and solidified in a cold-hearth crucible under a purified argon atmosphere. The solidified ingot had dimensions of approximately 3 by 1/2 by 3 in. One face of the ingot was somewhat uneven, but was as clean and shiny as the remaining parts of the ingot. Large grains with a Widmanstatten internal structure were clearly shown on the shiny surfaces, indicating the occurrence of P — a transformation upon rapid cooling from the melt. Analysis of the are-melted ingot indicated C 0.033, N 0.010, H 0.013, 0 0.002 in weight percent, and traces of iron, copper, and silicon as detectable impurities. The ingot was cold-rolled -40 pct to 0.300 in. thick with a reduction of 0.005 in. per pass. The defects on the uneven side of the ingot were then removed by machining. This reduced the thickness to 0.285 in. The piece was then recrystallized by annealing at 800°C for 1 hr in a fused silica boat charged into a fused silica tube furnace under a vacuum of 10~5 mm Hg. To refine the grain size, the recrystallized metal was again cold-rolled 40 pct to 0.170 in., then annealed at 700°C for 1 hr. These treatments yielded a strip with a uniform equiaxed grain structure, having a penultimate average grain diameter of 0.04 mm and a hardness of approximately 90 Dph. Final rolling reduced the thickness from 0.170 to 0.010 in., corresponding to a reduction of 94 pct. The strip was rolled in both directions by reversing end for end between passes. Surface lubrication was provided by oil-soaked pads attached to both rolls. Specimens of 1 in. length (for X-ray examinations) and +in. length (for hardness and microstructure examinations) were cut from the rolled strip, and a width of & in. was cut from the edges of each specimen by a jeweler's saw. These specimens were then etched in a solution of 10 cu cm HN03, 5 cu cm HF, and 50 cu cm H,O to 0.008 in. thick to remove the surface metal, as well as the distorted metal at the saw cuts, prior to annealing or measurements. To minimize any surface reaction with the atmosphere, all specimens were kept in an evacuated desiccator. Isothermal Anneals. All annealing treatments were conducted in vacuum in a fused silica tube furnace as described earlier. The temperature of the furnace was controlled to within *2"C. The specimen was placed in a fused silica boat, then pushed into the hot zone of the furnace. It took about 5 to 6 min for the specimen to reach the furnace temperature. After the specimen was held at temperature for a desired length of time the boat was pulled to the cold zone of the furnace; the heating-up period was excluded from the isothermal annealing time. Thus, the uncertainty in annealing time is higher for very short anneals, but negligible for long anneals.

Jan 1, 1969

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By R. K. McGeary, B. Lustman

The textures produced in zirconium by cold and hot rolling, and by recrystallization above and below the transformation temperature were determined. Thermal expansivities were measured in the thickness, transverse, and rolling directions of preferentially oriented zirconium and were correlated with the texture scatter in these directions. REVIOUS investigations have indicated that minor differences between hexagonal close-packed metals of similar axial ratio may appear with respect to the textures produced both on cold rolling and on subsequent recrystallization. In the case of magnesium, beryllium, and titanium, metals of axial ratio similar to that of zirconium, the ideal orientations produced by rolling are fundamentally the same, although marked variance is reported in the degree and type of scatter about the mean orientation; in those instances where recrystallization textures were observed, they were reported to be similar to the rolling textures. Measurement of the anisot-ropy of thermal expansion of both rolled and re-crystallized zirconium could not be correlated satisfactorily with the textures reported for the above metals, and therefore a study was made of the preferred orientations produced in zirconium. Reported below are the textures produced in zirconium by cold and hot rolling, and recrystallization above and below the transformation temperature, together with the results of thermal expansion measurements. Determination of Preferred Orientation Two types of zirconium were investigated: 1— "crystal bar" zirconium obtained from the Foote Mineral Co., produced by the thermal decomposition of zirconium tetraiodide, and 2—zirconium ingot obtained from the Bureau of Mines prepared by melting sponge zirconium in a graphite resistor vacuum furnace in a graphite crucible. The major impurities present in the two materials used are listed in Table I. Several of the pole figures were later checked with 0.03 pct hafnium crystal bar material and the results were identical with those to be shown for the 1.5 pct hafnium material. The materials were cold rolled to 0.014 in. in thickness as shown in Table 11. Specimens were cut from the 0.014 in. thick rolled sheets and etched to thicknesses of 0.002 to 0.010 in. Such specimens were used for exposures up to a 50' to 60" angle between the beam and plane of the specimen; for higher angles a wire shape, similar to that described by Bakarian,' was formed on an end of the original 0.014 in. sheet. A fine-bladed abrasive cut-off wheel was used to slot the sheet and to form the cylindrical cross-section. The wire shaped ends were then etched to 0.006 to 0.010 in. in diam. Although absorption of X-rays in the wire-shaped specimens does not vary with angle of rotation, the line width around the diffraction rings was not uniform, because the wire was narrower than the X-ray beam, and this condition caused some uncertainty in the estimation of azimuthal intensities. Furthermore, scanning was not practicable with this type of specimen so that spottiness of the rings due to large grain size was excessive for specimens which had been heated above about 650°C. Nevertheless, satisfactory information could be obtained for high angle exposures from the negatives by the use of both types of specimens. Transmission Laue photograms were taken using unfiltered molybdenum radiation (47.5 kv, 18 ma) and a 0.025 in. pinhole. With the film 8 cm from a 0.005 in. thick specimen exposures of about 30 min were adequate. For specimens with a coarse grain size, a device that scanned about 0.15 sq in. of sheet surface was used. An attempt was made to plot the pole figures by use of an X-ray spectrometer as described by Norton.' However, for the particular technique used, the intensity variations obtained were not considered definite enough to give reliable results, especially for the large grained recrystallized and transformed specimens. This method was therefore abandoned in favor of the standard photographic method. Nine exposures were taken of each specimen: seven exposures with the beam perpendicular to the rolling direction and at 0°, 10°, 20°, 35", 50°, 65", and 80" to the transverse direction, and two exposures with the beam perpendicular to the transverse direction and at 60" and 80" to the rolling direction. Additional exposures were then made where necessary. The intensity variations of the diffraction rings were estimated by eye. It was usually possible to estimate 3 degrees of intensity from the photograms but in some cases 2, 4, or 5 degrees were estimated. Experimental Results The preferred orientation was determined for the following treatments: 1—cold-rolled, 2—low temperature rolled, 3—cold-rolled surface layer, 4— cross-rolled, 5—hot-rolled, 6—recrystallized below the transformation temperature, and 7-—recrystallized above the transformation temperature. I—Cold-Rolled Textures: The slip plane in hexag-

Jan 1, 1952

By Stanley D. Michaelson, Norman Weisis

The purpose of beneficiation is to increase the economic value of an ore by elimination of waste rock or by separation of minerals that require separate reduction, without destroying the physical and chemical identity of the minerals. Flotation has replaced older methods of beneficiation to a very great ex- tent, nearly entirely in the case of the copper, lead, and zinc minerals and less completely in the case of such other minerals as iron, coal, and titanium. Flotation is also used to recover barite, fluorspar, feldspar, cement rock, spodumene, vermiculite, silica, beryl, and potash in the nonmetallic field, and cobalt, vanadium, germanium, antimony, mercury, molybdenum, manganese, nickel, gold and silver, cadmium, and bismuth for metals. The rapid growth of flotation to pre-eminence cannot be attributed to its low cost, because gravity, magnetic, and electrical methods may in some cases cost only half as much. But for ores containing finely disseminated minerals, these other methods are successful only in exceptional cases, for example the magnetic taconites or titanium-bearing sands. For low grade ores with coarse texture or spotty mineralization the advantages of low-cost gravity methods and highly efficient flotation are often combined, as in the beneficiation of coal and some ores of lead and zinc, phosphate, tungsten, and manganese. When an ore is responsive to either flotation or non-flotation concentration, or to combinations of the two, the choice depends upon cost of the process only when dealing with ores of low value; in other cases it is dictated by either the process efficiency or the product specification. Generally speaking, flotatio.1 is so efficient as compared with other methods of concentration that process cost is rarely an important factor in its selection. It is said, "The metal in the mill tailing has already been mined." Once the mining cost has been paid it doesn't increase total costs very much to do a thorough job of milling. With the exception of the few types of ores that are not amenable to flotation, the chief reason for preferring electrical and gravity methods to flotation may lie in the specification of the product. Flotation demands fine grinding, and specifications may not permit this with many nonmetallic ores or coal. Another reason is the size of investment-where capital is hard to obtain or the life of the property is short, the justification for a flotation plant may not exist, and one must be content to skim off the cream. y not exist, and one must be content to skim off the cream. Gravity processes often cost less than flotation because a large part of the waste rockcan be rejected without costly grinding, no chemicals are required,

Jan 1, 1962

By G. S. Tint, M. Herman, V. V. Damiano

Dislocation arrays and substructures were studied in cadmium doped zinc crystals using a newly devised etching technique. Cadmium precipitates delineating the dislocations were revealed by etching a surface closely parallel to the (0001) slip plane. Cinephotomicrography of the continuous etching process revealed the three-dimensional aspects of dislocations in the bulk crystal. Dislocation etch patterns were studied in both deformed and annealed crystals after suitable aging at room temperature. The effect of annealing was evidenced by a rearrangement of the dislocations into low-angle boundaries and hexagonal networks. ETCH pit techniques have been used extensively to study dislocations in both deformed and annealed bulk metal crystals. Ideally one hopes to obtain a one-to-one correspondence between the etch pits and the points of emergence of the dislocations at the surface. One then attempts to deduce the way in which dislocations are arranged in the bulk crystal from the arrangement of etch pits on the surface. It is clear that one can obtain only limited information of the dislocation configurations inside the crystal from etch pit studies of single surfaces. Considerably more information is obtained if one is able to follow the course of the dislocations through the crystal using progressive etching technique. Techniques of this sort were used by Gilmanl to study dislocations on the slip planes of NaCl crystals and by Damiano and Tint2 to study dislocation arrangement in zinc crystals grown from the melt. The present paper makes use of a technique first described by Tint and Damiano3 to observe and continuously record the dislocation structures which appear while a crystal surface was being progressively etched. Studies were made on cleaved (0001) surfaces to reveal the dislocations along their length on the surface closely parallel to the slip plane. The technique for revealing segments of dislocations along their length by etching is well known. Wilsdorf and Kuhlmann-wilsdorf4 revealed disloca- tions along their length in aluminum containing a few percent copper, when precipitates segregated along the dislocations. The technique was used by Low and Guard5 to study dislocation configurations on the slip plane in Fe-Si alloys containing carbon. In the present work the technique was applied to zinc containing cadmium since it was shown by Gil-man6 that a cadmium-rich phase could be made to precipitate from supersaturated solutions along dislocations in zinc. Segments of dislocations delineated by the precipitates were revealed by etching a surface prepared by cleaving the crystal. The three-dimensional nature of dislocations and substructures was thus studied from the cinephotomicro-graphic record of the continuous etching process. EXPERIMENTAL Single crystals of zinc containing the order of 0.1 pct Cd were prepared by slowly lowering a graphite crucible containing the melt through a temperature gradient of 15°C per cm at a rate of 1.5 X 10-3 cm per sec. "As grown" crystals were aged for periods of 1 month at room temperature, then cleaved in liquid nitrogen, and etched according to the procedure used by Gilman.' The etchant containing 32 g of CrO3, 6 g of hydrated Na2SO3 in 100 ml of water behaved as a chemical polish for zinc and etch pits were produced at the site of precipitates or inclusions. After the precipitates or inclusions were removed from the surface, the etch pits left behind were eventually polished smooth. This behavior enabled one to continuously observe the surface while the specimen was immersed in the etchant. Best results were obtained when the specimen surface was vertical and the reaction products of polishing were continuously removed by gravitational convection. Some crystals were heavily deformed in excess of 25 pct strain, others were lightly deformed the order of a few pct by compression such that the deformation occurred essentially by basal glide. Some crystals were etched immediately after deformation, others were allowed to age at room temperature for several weeks prior to etching. Heavily deformed crystals were annealed at various temperatures and etched on the cleavage plane immediately after annealing, others were allowed to age at room temperature for several weeks prior to etching. The etched structures of deformed and annealed structures were studied. Similar experiments were conducted on 99.9999 pct pure zone refined Tadanac zinc crystals which

Jan 1, 1963

By M. G. Benz, J. F. Elliott

The austenite solidus of the iron-carbon system has been determined using a series of diffusion couples, each of which consisted of a specimen of austenite held in contact with a melt saturated with austenite. After the equilibrium distribution of carbon had been established by diffusion at a specified temperature, i.e. the austenite specimen had become austenite of the solidus conzposition, the diffusion couple was cooled, sectioned and anazlyzed for carbon. The solidus was found to be a straight line: A revised iron-carbon temperature-composition diagram is presented, COMPOSITION has a marked effect on the temperature at which austenite begins to melt and the austenite solidus of the iron-carbon system describing this effect has been the subject of many investigations.1-10 The significant results of these investigations are presented in Fig. 1. The experimental methods and purity of the materials used in them are summarized in Table I. In plotting the data in Fig. 1 no attempt has been made to convert these results to the International Temperature Scale of 1948," except for the data of Adcock,5 as this conversion would do little to reduce the uncertainty that exists as to the position and shape of the solidus. A point of major concern in evaluating these data is that the alloys studied, except those used by Adcock, were not binary alloys of iron and carbon, Table I. Also, it would appear that several of the methods did not permit equilibrium to be established through the system being studied. All that can be said for the results of these investigations is that they indicate only approximately the location of the solidus with the uncertainty as to its location at 1 pct C being approximately 100°C. The current investigation was undertaken to provide reliable data by which the austenite solidus could be established. It was hoped that information on the liquidus also could be developed at the same time, but experimental limitations prevented this as austenite segregated from the liquid on cooling. After a careful study of possible experimental methods and extensive laboratory tests, it was decided that the use of a series of austenite-liquid diffusion couples would provide the most reliable results. This paper describes the method and its results and also includes a complete iron-carbon temperature-composition diagram based on what are considered to be the best available data. EXPERTMENTAL METHOD The diffusion couple used for this investigation consisted of a small cylindrical pellet of austenite held in contact, at a specified temperature, with a melt saturated with austenite. The composition of the cylindrical austenite pellet was chosen to be approximately 0.1 wt pct C less than the estimated

Jan 1, 1962

By W. S. Sanner

Experiments were conducted to determine the quantity and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. A low, a medium, and a high-volatile anthracite were studied. Specific gravity separation followed by grinding, screening, and refloating at lighter specific gravities yielded small quantities of material purified to 1.0% ash, as follows: from low-volatile anthracite, 0.7%; from medium-volatile coal, 1.0%; and from high-volatile coal, 2.3%. The reduction in ash had no appreciable effect on the volatile matter or sulfur content of the coal. The limited quantities of material containing 1.0% or less ash obtainable indicate that if ultraclean coal is desired, a practical approach should include the processing units as an integral part of a convc.ntiona1 dense-media washing plant. Anthracite preparation practices during much of the industry's history were geared to maximum recovery of the larger sizes, pea through egg, which were used in hand-fired, domestic furnaces. Those sizes were cleaned to meet trade requirements, and the smaller sizes were usually higher in ash content. The impression, thus, was that ash content of anthracite always increased as the sizes got smaller. It was presumed that it was impossible to wash the finer sizes to extremely low ash contents. Following World War 11, the classical domestic market began to decline and the finer sizes assumed an increasingly large share of the market. For example, in 1949l 61% of the production was still pea and larger. Fig. l2 shows that -by 1955 these sizes accounted for only 50%, and in 1965, they were only 39% of the total anthracite produced. With the reduction in the market, increased quality was demanded, especially in export markets, and an increasing number of dense-media magnetite washers were installed in new and existing cleaning plants. In 1965, the coarse coal prepared at 59 breakers in the anthracite fields was sampled by the U.S. Bureau of Mines (USBM); approximately 50% of these plants were equipped with dense-media magnetite washers.3 Since 1950, more attention has been focused on the use of finer sizes for numerous industrial uses, including iron-ore sintering, pelletizing, foundry coke-making, cement manufacture, production of calcium carbide, and of carbon electrodes, etc. Most industrial uses require relatively clean anthracite, such as 10 to 11% ash for sintering and foundry coke, 7% for aluminum melting-pot cathode carbon, and 5% for carbide production. Hence, cleaning methods have been improved to the extent that dense-media washers, hydraulic cyclones, and flotation cells have been introduced as fine-coal-cleaning devices. It is now possible to wash the buckwheat, rice, and barley sizes (9116 X 3132-in.) to ash contents as low as 8 to 10% in dense-media devices, but washing the -3132-in. sizes to those limits presents more difficult problems, due mainly to the fineness of the material. This USBM investigation was conducted to determine the amount and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. The goal was to reduce the ash content to a level acceptable for industrial carbon uses, including electrode manufacture, which generally requires an ash content of 1% or less. While low-ash content is of primary importance in selecting industrial carbons, the amounts of other constituents are also important, including iron, silicon, titanium, nickel, vanadium, and sulfur. They were not considered in this work, since their occurrence in deashed anthracite has been studied elsewhere.4 The results of the present investigation were used to design a flowsheet, suggesting a method for producing ultraclean anthracite as part of conventional preparation practice, using dense-media vessels, crushers, pulverizers,

Jan 1, 1970

By A. Paul Bond

Two series of 17pct Cr iron-base alloys with small, controlled amounts of carbon and nitrogen were vacuum-melted in an effort to detertmine the meclz-uniswls of inter granulur corrosion in ferritic stain-less steels. An alloy containing 0.0095 pct N aid 0.002 pct C was very resistant to intergranular corrosion, even after sensitizing heat treatments at 1700" to 2100o F. However, alloys containing more than 0.022 pct Ni and more than 0.012 pct C were quite susceptible to intergranular corrosion after sensitizing heat treatments at temperatures higher than 1700°F. This corrosion was observed after the usual exposure tests and after potentiostatic polarization tests. Electronmicroscopic examination of the alloys susceptible to intergranular corvosion revealed a small grain boundary precipitate; this precipitate was absent in the alloys not susceptible to such corrosion. Thc electronmicrographs indicate that intergranu1ar corrosion of ferritic stainless steels is caused by the depletion of chromium in areas adjacent to precipi-tates of chromium carbide or chromium nitride. It also seems likely that the precipitates themselves are attacked at highly oxidizing potentials. Confirma-tion of the proposed mechanisms was obtained in tests on air-melted ferritic stainless steels containing titanium. The titanium additions greatly reduced susceptibility to intergranular corrosion at moderately oxidizing potentials but had no beneficial effect at highly oxidizing potentials. A major obstacle to the use of ferritic stainless steel has been their susceptibility to intergranular corrosion after welding or improper heat treatment. It appears that sensitization of ferritic stainless steel occurs under a wider range of conditions than for austenitic steels. In addition, a greater number of environments lead to damaging intergranular corrosion of sensitized ferritic stainless steels than to sensitized austenitic steels. The chromium depletion theory of intergranular corrosion is widely accepted for austenitic stainless steels'" although there: are some objections.3 On the other hand, several alternative mechanisms proposed for ferritic stainless steels include precipitation of easily corroded iron carbides at grain boundaries,' grain boundary precipitates that strain the metal lat-tice,5 and the formation of austenite at the grain bound-arie.6 The application of the chromium depletion theory to ferritic stainless steels has been discussed extensively by Baumel.7 The present investigation was undertaken to determine which of the proposed mechanisms can be sub- A PAUL BOND IS Research Group Leader, Climax Molybdenum Co of Michigan, Ann Arbor, Mich. stantiated with experimental data obtained on ferritic stainless steels. High-purity 17 pct Cr alloys containing small controlled additions of carbon or nitrogen were therefore prepared, and then examined electro-chemically and metallographically. EXPERIMENTAL PROCEDURES Materials. Two series of experimental alloys were prepared from electrolytic iron and low-carbon ferro-chromium using the split-heat technique. In this technique, the base composition is melted, and part of the melt is poured off to produce an ingot. To the balance of the melt, the required addition is made and the next ingot cast. This process is repeated until a series of the desired compositions is cast. By this procedure the impurity levels are essentially constant within each series. All the alloys in the carbon-containing series were melted and cast in vacuum. The base composition in the nitrogen series was melted and cast in vacuum; subsequent ingots in the series were melted with additions of high-nitrogen ferrochromium, and cast under argon at a pressure of 0.5 atmosphere. Two additional alloys were produced starting with normal purity materials. They were induction-melted while protected by an argon blanket and cast in air. Table I gives the composition of the alloys. The 2-in.-diam ingots produced were hot-forged and hot-rolled to a thickness of 0.3 in. and then cold-rolled to 0.15 in. All specimens were annealed at 1450°F for 1 hr. The indicated sensitizing heat treat-s s ments were performed on annealed material. All heat treatments were followed by a water quench. Specimen Preparation. For the 65 pct nitric acid test, 1 by 2 by 0.14-in. specimens were wet-surface ground to remove surface irregularities and polished through 3/0 dry metallographic paper. For the modified Strauss test, $ by 3 by 0.14-in. specinlens were similarly prepared. Immediately prior to testing, the Table I. Compositions of the Alloys Composition, pct Alloy Cr hio C N 270A 16.76 0.0021 0.0095 270B 16.74 0.0025 0.022 270C 16.87 0.0031 0.032 270D 16.71 0.0044 0.057 271A 16.81 0.012 0.0089 27 IB 16.76 0.018 0.0089 271C 16.69 0.027 0.0085 271D 16.81 0.061 0.0O71 4073' 18.45 1.97 0.034 0.045 4075† 18.5 2.0 0.03 0.03

Jan 1, 1970