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By Elma van der Lingen

Gold is considered the most inert of all metallic elements, but the metal can show catalytic activity when prepared by specific techniques. Preparation techniques being used to prepare gold catalysts systems mainly involve precipitation methods incorporating gold compounds or complexes. This paper introduces a totally different method for the preparation of gold-based heterogeneous catalysts that can be used for oxidation and reduction reactions, as well as electrocatalysts. The method involves alloying of gold with a less noble metal, such as aluminium, to form a gold-containing intermetallic precursor. AuAl2 was produced by melting gold and aluminium together in a vacuum arc furnace under a protective atmosphere. The aluminium is then dissolved from the AuAl2 precursor by means of NaOH to produce a highly porous gold structure. The paper also reports on a method of incorporating transition metal oxide(s) with the porous gold to form an active heterogeneous catalyst. Promoter elements can also be melted with AuAl2 to improve catalytic activity. Alloying has the advantage that the promoter element can be in contact on atomic level with the gold. In-situ xray photoelectron spectroscopy (XPS) studies have also been done on the porous gold catalysts to further clarify the CO oxidation mechanism on gold-based catalysts.

Oct 1, 2003

By T. K. McCranie, A. H. Tousley, A. H. Kackman, L. R. Gregory, A. Jr. McElrath, R. J. Krekel

In Roman and earlier civilizations the term cement was applied only to mixtures of lime, pozzolana, sand, water, etc., used as a mortar to bind larger stones. Today, portland cement, the subject of this section, can be briefly defined as follows: The product obtained by finely grinding clinker produced by calcining to incipient fusion (i.e., sintering) an intimate and properly proportioned mixture of argillaceous and calcareous materials. History The Egyptians were probably the first to join building stones with a mixture of sand and a cementitious material (i.e., having the property of or acting like cement). It is generally accepted that the cement used by the Egyptians on such structures as the Great Pyramid was calcined gypsum, Later the Greeks began to calcine limestone for use as a mortar with sand and water. Still later, broken brick and tile were added to the mortar to make the first concrete. The Greeks and Romans found that some sands produced mortars that were especially resistant to the action of water. Hydraulic (i.e., underwater-hardening) cements formed by combining slaked lime, water, and finely divided siliceous materials (e.g., pozzolana) possess superior strength and are capable of resisting the destructive action of water. They were used on the Pantheon, Colosseum, and other structures, some of which are still standing. In 1756 an English engineer, John Smeaton, found that an argillaceous limestone (i.e., containing an appreciable amount of clay as an impurity) produced a cement with greater resistance to the action of water. Despite Smeaton's findings, the use of the old mixture of lime and pozzolana long retained its popularity. Significant contributions in cement technology from England, Swe¬den, France, and Holland were made in the next 68 years. However, the invention of portland cement is generally credited to Joseph Aspdin, an Englishman, who in 1824 patented "portland cement." The name was selected because, on hardening, it resembled the natural building stone from the Isle of Portland, England. The patent features mixing ground limestone and argillaceous materials in appropriate proportions and calcining (i.e., expelling CO2 by roasting) the mixture. This superseded the existing practice of calcining naturally occurring argillaceous limestone. In about 1845 Isaac Johnson, also English, conducted experiments on proportioning the components and calcining them at higher tem¬peratures. His accomplishments are accepted as the beginning of the present-day portland cement industry. The U.S. cement industry originated with the demand for good hydraulic cement for building structures such as the Erie Canal, which was started in 1817. The first discovery of cement rock (i.e., naturally occurring argillaceous limestone with near-optimum ratios of calcium carbonate, alumina, and silica) near Fayetteville, N.Y., was made by C. White. In 1818, White secured a patent for the manufacture of natural cement from that deposit. Subsequently, several natural cement plants were built in 1830-1840 at Rosendale, N.Y., and in the Lehigh Valley of Pennsylvania. David Saylor, who participated in establishing a natural cement plant at Coplay, Pa., in 1850 discovered that a superior cement could be produced by calcining the rock at higher temperatures than hith¬erto. In 1871, Saylor obtained a patent and commenced the manufac¬ture of portland cement. By 1890, there were 17 portland cement plants in the United States with a combined annual output of 62,300 tons. At the end of 1970, the number of plants producing portland cement in the United States (including Puerto Rico) was 169, down from a maximum of 185 in 1967, with total annual shipments of 73.4 million tons valued at $1,298 million. (Fig. 1). In 1970, annual world production of hydraulic cement (which includes pozzolanic materials, hydraulic limes, natural cement, alumina cement, and portland cement, all of which are in current use in various parts of the world) reached 630 million tons (Table 1). Flowsheets of typical U.S. cement plants are shown in Chapter 13. Chemical Composition and Physical Properties It is generally accepted that portland cement clinker consists of a mixture of compounds or synthetic minerals. The four principal compounds are:

Jan 1, 1985

By Gary Hawthorn

"Laboratory testing, by Lakefield Research determined that, in spite of the relatively high pyrite content of the Golden Rose (GR) orebody, it would respond well to gravity concentration followed by either direct cyanidation or cyanidation of a flotation concentrate.Economics favoured the former choice which became the adopted process flowsheet.During the latter stage of the feasibility study, the Dekalb 500 tpd copper flotation mill became available in the Highland Valley of British Columbia. This plant was purchased by Emerald Lake Resources, and was moved to the Golden Rose minesite.The crushing and grinding circuit were retained and the original flotation circuit was replaced with a 400 mtd gravity plus cyanidation circuit. The plant commissioning commenced in August 1987, and by early September was processing 300 tpd.HistoryThe Golden Rose Mine was operated by Cominco during the period 1935 to 1941 processing 146000 tons grading DAD oz/t Au at a rate of 110 tpd .The process flowsheet consisted of gravity plus amalgamation followed by cyanidation.Metallurgical TestingThe underground mining areas were below the level of Emerald Lake, and had flooded on abandonment in 1942.Samples for metallurgical testing were collected from exposed faces underground once the mine had been dewateredin 1984.In spite of the anticipated high pyrite content of the ore samples, it was apparent from the success of the previous operation that the pyrite did not interfere with the gold recovery.Laboratory testing, at Lakefield, determined that, from a technical perspective, two metallurgical options existed, as shown in Tables I and 2.Note that the very high pyrite content of the ore precluded the possible direct marketing of concentrate. The process flowsheet, therefore, had to contain a cyanidation circuit for the operation to succeed financially.Although the anticipated metallurgy was excellent with either option, the 2.1 % increase in gold recovery with the gravity plus cyanidation option made this the clear choice."

Jan 1, 1989

By D. Turnbull, R. E. Cech

FISHER, Hollomon, and Turnbull have developed a theory for the nucleation of martensite. They first tested the theory on Fe-C alloys and low alloy steels. The major factor influencing nucleation of martensite was considered to be statistical composition fluctuations occurring in small regions at high temperature and frozen-in on quenching. These local regions of varying size and composition serve as nucleation centers. They become supercritical, one by one, as temperature is progressively lowered, resulting in temperature-dependent or athermal transformation. Fisher next applied nucleation theory to substi-tutional solid solution alloys. Detailed predictions were made for Fe-Ni alloys because of the availability of free energy data on this system. It was shown that composition fluctuations that were significant energy-wise did not occur, and nucleation frequencies could be calculated from average properties of the system. Nucleation was predicted to occur as time-dependent and having the functional relationship to give a C curve of nucleation frequency vs temperature. The analysis further predicted that the nucleation frequency was extremely sensitive to composition. Experimentally, it would be found that the transformation in some compositions is so slow that measurable amounts will not form in a reasonable length of time. With other compositions, only slightly different, the nucleation frequency becomes so great that the material becomes transformed while still distant in temperature from the maximum nucleation frequency. On quenching an alloy of such composition, the observed transformation kinetics would be similar to those found in Fe-C alloys. Cech and Hollomon repeated experiments of Kurdjumov n which the kinetics of transformation were similar to those predicted by Fisher for Fe-Ni alloys. The alloy studied in this investigation contained 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn. Fisher,' using an idealized model for the extent of transformation as a function of the number of martensite crystals per grain of parent phase, derived nucleation frequencies from the transformation curves of Cech and Hollomon. Complicating influences such as coupling effects between grains in the polycrystalline specimens were neglected. Nevertheless, excellent agreement was found between the theoretically and experimentally derived nucleation frequencies. These experiments, however, could not provide a critical test of the theory. Experimental nucleation frequencies could vary widely from those calculated, depending upon the extent of deviation from ideal partitioning and the extent of coupling effects. Further, since the compositions of material theoretically analyzed and experimentally determined were different, the free energy changes involved in the experimental work could only be estimated. Also, the effect of heterogeneities on the transformation kinetics was not considered. For these reasons, it was decided that experiments designed to test the validity of the Fisher analysis must be conducted on binary Fe-Ni alloys, which were the ones considered theoretically by Fisher. The martensite transformation in Fe-Ni alloys has been the subject of considerable study. Machlin and Cohen have shown that transformation proceeds in a manner quite unlike that in any other ferrous alloy system. They found that single crystals would transform to a large extent in a single burst. In large grain polycrystalline specimens, frequently more than one grain and sometimes the whole specimen would transform at the same instant in this manner. Results on filings indicated that different particles would undergo the burst transformation at widely different temperatures. These results support the conclusion that the transformation behavior could not be described by a single nucleation frequency as would be the case if the nucleation were homogeneous. It appeared that further work was necessary to define the factors responsible for burst-type transformation, so that the conditions could be altered to favor homogeneous nucleation of martensite if such could be accomplished. This report summarizes the results of some experiments conducted with powdered Fe-Ni alloys for this purpose and the re-

Jan 1, 1957

By S. Dallaire

With the attainment of high temperatures it becomes possible to process any kind of material (particularly ceramics) in their liquid state. In the plasma spraying process, the material to be sprayed is rapidly heated until it is molten and is propelled by high velocity gases onto a surface where it adheres, to give protective coatings for a wide range of applications. The method could be considered as one of the most versatile and rapid to build up thick deposits (of plastics, metals, ceramics, cermets) and also free-standing artifacts for particular requirements without resorting to lengthy forming and sintering studies. Although plasma spraying is at the production stage in industry, advanced processes have also been developed for economically producing a wide range of new materials. This paper illustrates the benefits of the process and evaluates the challenges it represents.

Jan 1, 1987

THE object of all classification is to group together things which are alike, and separate those which are unlike. This object is essentially a practical one, enabling us to apply past experience to new conditions: Many costly large-scale experiments lose half their importance for want of proper description of the coal used, and the consequent impossibility of predicting other coals will behave in the same way. I do not, therefore, make a fundamental distinction between "scientific" and "use" classifications, except in so far as use depends on conditions, such as size or impurities which are not related to the nature of the coal substance itself. The characters chosen to define the classes of coal must be such as are accompanied by as many other properties as possible. It is not to be expected that any system of classification will enable us to predict every property of coal, since all specimens have an individuality of their own. But specimens can be grouped by a number of resemblances into species. Further, species which resemble each other can be grouped into genera.

Jan 1, 1928

By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By P. K. Chatterjee

"The operations of a large-scale open-cut mine are simulated to produce a user-oriented interactive digital model. SIMULA is chosen as the programming language and a sophisticated data base system is designed to consider the complex information network of large mines. The main features of the program are the mine planning and mine evaluation modules. These modules are responsible for the computation of truck-shovel performance and other equipment details in a mine. Stochastic methods are employed to generate event times. The use of a Data Base Management System and the data base provide an efficient method of information storage and retrieval. Truck allocation techniques have been examined in detail and comparisons between random dispatching and conventional methods are made. The model is intended for mine operators and engineers and the program is well structured and very readable. It is hoped that these features will make the model readily acceptable.IntroductionThe Department of Mining and Metallurgical Engineering at the University of Queensland has been conducting research into computer simulation methods in mining since 1972. The research has been mainly applied to actual operations, with both open-cut and underground mining being equally emphasized. The results of the research to date have not only strengthened the methodology of the approach to complex mining problems, but have also increased confidence in the use of modelling and computer simulation technique s in mining.The model described in this paper translates a complex LHD situation into a user-oriented interactive digital model using SIMULA. The present methods of evaluating truck dispatching and trolley assist are tedious and laborious. This model provide s the engineer with readily acceptable means of rapidly assessing the relative merits of these techniques in a large-scale open-pit operation. Poor utilization figures in many current operations (for example, 40% for trucks, 70% for shovels) are of serious concern to mine officials and computer-controlled dynamic truck dispatching systems have been considered by some of these mines to improve equipment utilization ."

Jan 1, 1981

By W. B. Evans, D. P. Taylor

"ANFO has two major disadvantages as an explosive low density and no water resistance. ANFO can be blended with more dense, water-resistant explosives to form ""Heavy ANFO"". The use of emulsion or slurry explosives as a matrix is an attempt to correct deficiencies on the basic ANFO while maintaining cost effectiveness.This paper will deal with four main topics.1. Product description, general properties, strengths and weaknesses.2. Technology of ""Heavy ANFO"" , the emulsion matrix concept and the range of products.3. Relative performance and economics in various rock types.4: Current status in Canada and worldwide, and the expectations for future use.IntroductionANFO has been in use for roughly three decades and remains the explosive of choice where conditions are suitable. ANFO has not become the universal explosive - despite its undoubted superiority in cost effectiveness - because it has serious flaws as an explosive. The most serious of these flaws are the low density and absence of water resistance in ANFO. Low density implies a low concentration of explosive energy in a borehole. The amount of energy available can be increased by. adding an energetic material, generally aluminum, or by drilling more holes. Both solutions add considerably to the over-all costs. The absence of water resistance in ANFO is inherent and can only be overcome by changing the fundamental nature of the product. The history of research in the explosives industry since the advent of ANFO is mainly the story of the various attempts to overcome one or both of ANFO's shortcomings.Many technologies and products have been developed to compete against ANFO, among them slurries, emulsion s and the so-called Dense ANFOs (ANFO with an extra nitroalkane liquid sensitizer). None of them was cost-competitive with ANFO so their market penetration has been limited to wet holes or specialized applications. The exception to this result is Heavy ANFO. The aim here was to have the best of both worlds, the high density and water resistance of emulsions or slurries plus the low cost of ANFO. The concept is very simple. ANFO is about 50 % air, roughly 30% in the prills and 700,10 between the prills . The air in the prills provides the necessary sensitivity but the air between them is waste volume. If one fills this volume with a high density, waterproof product, the resultant mix will be denser and more water resistant than ANFO and with very little added cost. This basic concept was invented by B. Clay in the 1970s and is covered by Canadian Patent No. 1 115 959. The water resistance and/or density of the mix can be tailored by changing the emulsion level. Because Heavy ANFO is relatively inexpensive while providing good in-hole densities and water resistance, it can compete successfully against all other bulk products. It competes against ANFO and Al / ANFO by allowing pattern expansion and reducing over-all costs while it competes against emulsions and slurries on price."

Jan 1, 1987

By Eckley B. Coxe

Having been appointed, on February 19th, 1890, a member of the Commission created by the Legislature of Pennsylvania for the purpose of investigating the " Waste of Coal Mining, with the View to the Utilizing of the Waste" (waste in this case referring specially to the small sizes of anthracite heretofore thrown away), my attention was naturally directed to the mash economical method of burning these small sizes.* Although I had been Familiar with the burning of anthracite for • many years, I found when I came to study the matter carefully that I was far from thoroughly understanding it, particularly with reference to the hurning of the smaller sizes, and that the literature of the subject, which was not very extensive, had more of a tendency to confuse than to enlighten me. I began therefore to investigate the subject so as to arrive if possible at some definite principles applicable to the question. With the aid of my assistant, Mr. John R. Wagner, I began at Drifton a series of experiments upon the burning of small anthracites. We first erected a small furnace with a grate 3 feet long and 2 feet wide, with which we experimented about two months. From the information thus acquired, we designed and built another furnace of about the same size, which gave us facilities for extending our investigations still further. After experimenting several months with the second furnace, we built a third one, which was much larger, having a grate area of about 68 square feet, which was exactly the size of the grate used in the boiler-plants of' Coxe Bros. &

Jan 1, 1894

By Frank W. Harris

THE strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chemical and physical considerations, the high conductivity required for copper wire in the electrical industry generally precludes the possibility of obtaining tensile strength through the use of alloys. Consequently, this strength is largely a matter of the physical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., are matters of prime importance. The experiments described here have been carried out during the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigation of some of the questions mentioned above, with the object of studying the physical structure of hard drawn copper wire and the influence of certain factors on that structure. The work has been of an exploratory nature, rather than comprehensive, but it was thought that the results might prove of sufficient general interest to warrant their publication. The bulk of the hard drawn copper wire used in places where strength is an important factor is manufactured to strict specification, based usually in the United States on that of the American Society for Testing Materials (B-1-23). This specification calls for almost as high a value of tensile strength, consistent with elongation, as it is possible practically to obtain, and only physically perfect material can be relied on to meet such a specification. Obvious defects, such as laminations produced through fins in the original rods or brittleness due to overdrawing, are usually recognized and need only passing reference. Laminations can be detected by twisting and untwisting the wire several times; they will show up on the surface in the form of fins. Fig. 1 shows a very bad example of this defect. The wire may be perfectly smooth before twisting but when such laminations are present they will readily show up under this treatment. This trouble is caused by similar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which the wire in Fig. 1 was drawn.

Jan 1, 1928

By Daniel Hodouin, Robert Lanthier, Yve Dube

"A procedure f or constructing a grinding mill dynamic model is proposed. This model is used in a dynamic simulator of are grinding circuits. The simulator is designed for flexible flow sheets involving different grinding mills and particle classifiers and is able to accept several single variable PID control loops. The dynamic model is validated on a laboratory ball mill, and calibrated to an industrial installation. The simulator is used for characterization of grinding circuit dynamic behaviour and tuning of control strategiesIntroductionThe ore grinding operation is a critical step of the ore preparation process because it is the last comminution stage before the separation of minerals. The properties of the ground minerals to be concentrated, control the quality and efficiency of the separation process. This is why it is important to control properly the operation of the last grinding stage, commonly constituted of a closed circuit ball mill with classifier . To provide an adequate fine product, the grinding operation should compensate for the perturbations of the feed characteristics (size analysis, grindability, etc.). The main objective is to maintain a constant size distribution for providing stable operating conditions to the separation units. Simultaneously another usual objective is to operate the grinding circuit at a maximum capacity.Automatic control applied to grinding circuit s is the appropriate approach to improve its operation. Most frequently average optimal operating conditions are determined from steady -state performances of the circuit , and the automatic control is used for stabilizing the operation at selected values of the process variables . In the traditional approach, one or several single input! single output (SISO) control loops are implemented and empirically tuned. Advanced control practices'!' are based on a quantitative analysis of the circuit dynamics, which could also give a basis for the tuning of conventional SISO 100ps(2)."

Jan 1, 1987

By R. L. Schmidt, J. D. Verhoeven

The diffusion coefficients and electrotralzsport mobilities of aluminum, gallium, and arsenic have been determined in molten germanium with the capillary reservoir technique. The diffusion coefficients are slightly higher than those determined by the solidification technique of Brirton et a1.1 It was found that aluminium and gallium migrate to the cathode in molten germanium) whereas arsenic migrates to the anode under an electric field. A possible technique for producing p-n junctions by means of electric field freezing is discussed in view of the experimental data. In the past decade or so the literature has abounded with articles concerning the solid-state properties of the semiconducting elements germanium and silicon. It is surprising by comparison how little has been published concerning the liquid-state properties of these materials. In the production of doped germanium or silicon the diffusion coefficient of the dopant in liquid germanium or silicon is an important quantity. Yet, to the best of our knowledge, no one has ever made a direct measurement of the diffusion coefficient of solutes in either molten germanium or silicon. A number of authors'-4 have determined some diffusion coefficients by the indirect technique developed by Burton et al.1 This technique appears to give numbers of the correct order of magnitude but it does depend upon a number of assumptions in the analysis and also requires prior knowledge of the viscosity of the melt. In the present work a more direct measure of the diffusion coefficients of arsenic, gallium: and aluminum in molten germanium has been made. It has been shown independently by two groups of authors5, 6 that, when an electric current is passed through the interface of a solidifying metal containing an impurity, the resulting electrotransport in the liquid boundary layer at the interface offers a mechanism for control over the redistribution of the impurity accompanying the solidification. These authors show that the degree of control is proportional to the mobility, U of the impurity atoms in the liquid boundary layer, where the mobility is defined as the drift velocity relative to the solvent per unit electric field. In principle the results apply to the solidification of a doped semiconductor and offer an interesting technique for control of the doping of a semiconductor. In the present work the mobilities of aluminum, gallium, and arsenic were determined in molten germanium in order to evaluate the potential usefulness of electro-transport as a technique for solute control when applied to the solidification of doped germanium. EXPERIMENTAL PROCEDURE Both the diffusion coefficients and the mobilities were measured using high-purity alumina capillaries and a resistivity technique for analysis. A schematic diagram of the electrotransport apparatus is shown in Fig. 1 and the details of the cell design are shown in Fig. 2. For the mobility experiments electrical contact with the bottom of the capillary was made with graphite, as shown in Fig. 2. In order to prevent electrical contact with the melt the graphite was coated with a thin layer of alumina using a plasma spray torch. The cell assembly, a graphite electrode, and another assembly containing two blank capillaries were fastened to the lavite disk shown in Fig. 1. To make a run the system was evacuated and the doped germanium was outgassed at the operating temperature of 1030°C. The cell and blank capillaries were then submerged beneath the melt and a slightly positive pressure of helium was introduced to fill them. After passing current through the cell for a given time the cell and blank capillaries were raised from the melt and the furnace was shut off. The temperature of the cells dropped below the freezing point of germanium within 1 to 2 min after the furnace was shut off.

Jan 1, 1968

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By G. Willard Quick

FAILURES in railroad rails have been of vital concern to engineers; railroad executives, rail manufacturers and the general public for years. Failures from transverse fissures originating from internal nuclei have received particular attention in the past 20 years. Dr. J. E. Howard first reported this type of failure in 1911, as being responsible for a wreck-on the Lehigh Valley R. R. in which several lives were lost. Since then many transverse fissures have been found. In 1919, Waring and Hofammann1 etched longitudinal sections of rails in hot acid and found cracks extending both longitudinally and transversely in certain used rails as well as in some new rails.. Since then it has been thought by many that these "shatter" cracks are the nuclei from which transverse fissures subsequently develop in service. Methods for reducing the rate of cooling rails on the hot. bed have been devised to decrease the temperature gradient and consequently the stress gradient in the rails. A study of the tensile properties of rails at elevated temperatures was made by Freeman and Quick,2 who investigated the properties at temperatures through which rails pass on the cooling bed after leaving the hot saw. In their investigation a special study was made of the ductility of the steels in the temperature range 400° to 700° C. In this temperature range it was found that certain rail and other steels showed a marked decrease in elongation and reduction of area. The phenomenon was called "secondary brittleness" and the temperature range the "secondary brittle range." A tentative explanation was presented that internal failure such as "shatter cracks" and "hair cracks" in rails are the result of thermal stresses developed in the steel structure while cooling through the secondary brittle range. The investigation showed that the magnitude of the phenomenon varies for different heats, but that it did not differ for specimens from different ingots or for different rails in a particular ingot. It was also shown that annealing rail steel at a temperature either above or below the critical

Jan 1, 1932

Jan 1, 1965

By H. J. Rose

Sixty-five million net tons of coal were carbonized in the by-product and beehive coke ovens1 of the United States during 1924. This tonnage represented 13.4 per cent. of the bituminous coal which was mined in that year. Table 1 shows production and disposition.2 Table 1.—Production and Disposition of Ocen Coke in 1924 By-product Beehive Total Coal charged into ovens, tons................ 49,061,339 15,914,310 64,975,649 Coke produced (exclusive of screenings and breeze), tons............................. 33,983,568 10,286,037 44,269,605 Average yield of coke, per cent ............. 69.3 6.46 68.9 Disposition of coke, per cent.: Blast furnace.......................... . . 82.6 Foundry............................... . 13.3 6.6 Domestic.............................. . 1.4 6.7 Water gas manufacture and all other uses.. 4.6 . 4.1 Cokes having somewhat different combinations of chemical and physical properties are desired for the various uses listed above, and these properties depend primarily upon the types of coal used. American coals have a wide range of purity and coking quality, and the chief subject of this paper will be the selection of coals for the manufacture of blast furnace, foundry, domestic, and water-gas coke, in by-product coke ovens. It will obviously be necessary to include a discussion of those physical and chemical characteristics that are generally considered essential or desirable for each type of coke. Suitable Coals The examination and development of new sources of coking coal are important because of the irregular and limited distribution of high-grade

Jan 1, 1927

By Henry R. Linden

The demand for natural gas continues to increase at higher than anticipated rates, partly because of its widening price advantage over most other fossil fuels when the cost of air-pollution control is included. However, there are clear indications that the natural gas supply from the conliguous 48 states and continental shelves will not keep up with this rapid growth in demand indefinitely. Projections are presented which define the extent of potential deficiencies from the 1970's to the year 2000. Among the sources of supplemental gas - imported pipeline natural gas from Canada and Mexico, tanker import of liquefied natural gas, and synthetic pipeline gas from coal and oil shale -by far the most abundant at potentially competitive costs is pipeline gas from coal. The state of development and relative economics of the various coal gasification processes are reviewed. It is shown that synthetic pipeline gas could become a very substantial market for bituminous coal and lignite at current mine-mouth prices - 60-70 million tons of coal for each trillion cubic feet of synthetic pipeline gas produced. This corresponds to only slightly more than the current annual increase in gas demand. Although annual discoveries (gross additions to proved reserves) of natural gas in the United States are still on a general upward trend from the current level of 22 trillion cu ft annually, most forecasters do not expect this to increase substantially in the foreseeable future. For example, the updated (to include 1966 and 1967 data) mathematical model of natural gas discovery and production in the U.S. developed by the Institute of Gas Technology (IGT)' projects that discoveries will level out at about 25 trillion cu ft annually in the late 1970's and during the 1980's and then decline to about 21 trillion cu ft by the year 2000 (Fig. 1). This adds up to a new supply for the period 1968-2000 of about 790 trillion cu ft. Experts who usually reflect the producers' viewpoint, such as Radford L. Schantz of Foster Associates,* are relatively more pessimistic. In contrast, a forecast just made by the U.S. Dept. of the Interior is much more optimistic.3 It assumes an increase in gas discoveries of 2.2% per year over the period 1965-80, reaching about 30 trillion cu ft in 1980. If this rate of increase were extended to the year 2000, annual discoveries would reach 46 trillion cu ft at that time, for a total over the period 1968-2000 of about 1100 trillion cu ft. To these forecasts of new gas discoveries must be added proved reserves of roughly 290 trillion cu ft,4 bringing total U.S. supplies for the rest of the century to nearly 1100 trillion cu ft (IGT) and possibly as high as 1400 trillion cu ft (U.S. Dept. of the Interior). This is approximately the same range as that of two estimates of total remaining recoverable natural gas supply: Potential Gas Committee, 980 trillion cu ft5 and IGT, 1450 trillion cu ft.6 Only the 1965 estimate by the U.S. Geological Survey7 suggests that economically recoverable natural gas supplies will not be exhausted around the end of the century. These forecasts are, naturally, based on the assumption that changes in technological, economic, and regulatory environment as they affect the gas industry will be of an evolutionary, not revolutionary, nature. The various forecasts of potential natural gas supply must now be compared to forecasts of natural gas demand (Table I). The general consensus is that the recent Future Requirements Committee projection to 1990' (extended to the year 2000 by the most recent U.S. Bureau of Mines (USBM) projection9) represents the minimum gas requirements (Table 11). They add up to a total of 1030 trillion cu ft for the period 1968-2000. Even this minimum anticipated gas demand exceeds the total remaining supply estimate by the Potential Gas Committee and would nearly exhaust the proved reserves plus new discoveries projected by IGT. The supply situation would appear much tighter if the demand projections of the Texas Eastern Transmission Gorp.10 and the American Gas Assn.(A.GA.)'' were used (Table I). Yet, these higher forecasts probably do not include the effects of such new markets as gas fuel cells, use of liquefied natural gas as a transport fuel, etc. They also may not fully reflect the impact of air quality control on the fuel market. Obviously, the probable discrepancy between projected supply and demand can only be accommodated in four ways. 1) Rapid increase in exploration and drilling activity to provide new supplies in the amount projected by the optimistic U.S. Dept. of the Interior forecast, coupled with an increase in net pipeline imports from Canada and Mexico from the present 0.5 trillion cu ft per year

Jan 1, 1970

By G. E. Agar, J. J. Barrett

"Traditionally, batch bench-scale flotation tests have been used for evaluating flotation reagents by comparing the results of tests done with various additions of the reagent in question. Usually, comparisons are made of the concentrate grade and recovery or some figure of merit involving an empirical combination of both. In some cases, statistical methods have been used to make the comparison and even to identify optimal combinations of reagents.None of the preceding technology utilizes the fact that flotation separations can be described by relatively simple kinetic equations that will serve not only to quantitatively describe the influence of a reagent, but will also aid in designing an optimal separation procedure. Examples of the use of a first-order rate equation for evaluating the impact of a reagent addition and for optimizing the reagent addition are given.IntroductionThe classical method of evaluating flotation reagents is to conduct batch bench-scale tests while varying one factor at a time. Some of the shortcomings of this technique have been pointed out and statistical design and evaluation of experiments has been advocated. Although the statistical approach is superior to the one-at-a-time method, it still is dependent on the results of a batch test conducted for a specific duration.That flotation is primarily a rate process than can be described by a first-order rate equation has been recognized for a long time, but the application of this knowledge to the evaluation of reagents has received little attention. In this work, it is demonstrated how the parameters of the first-order rate equation can be utilized to evaluate the influence of reagents on flotation."

Jan 1, 1983

By Augustus Locke

In 1900, when. the public first heard of "secondary enrichment," the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chal-cocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales' advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this argument. Especially pertinent was the proof that (1) the deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accomplished more easily than that of pyrite, enargite, or chalcopyrite. The microscopic evidence has been accumulating for ten years and it demands

Jan 1, 1924