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By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,' namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By C. A. Stetefeldt

IK the dry-crushing of ores, either by stamps, rolls, or other machinery, it is essential that the material should be free from moisture. Hence a contrivance which effects this with economy, and is of durable and compact construction, is a great desideratum. It is claimed for the below-described shelf dry-kiln, that it possesses these qualifications in a high degree. The construction of the shelf dry-kiln is based on the Hasenclever principle. That is to say, a number of inclined shelves are arranged zig-zag above each other in a vertical shaft, having openings or slits where they meet, on which the ore rests in a stratum, the thickness of which is governed by the width of the slits and the inclination of the shelves. If a portion of the charge is removed at the end of the bottom shelf, a sliding motion of the ore takes place on all shelves above, and the top shelf is replenished from a hopper set over it. It will be seen that the shaft is divided by the shelves into a number of triangular prismatic spaces. Through these the hot gases from a fireplace are made to circulate, each space communicating with the next one by a flue arranged in the sidewall of the shaft. These flues being located on alternate sides of the shaft, a continuous passage is formed through the whole structure. After thus stating the principle of the construction, its details will be easily understood by reference to the drawings, Fig. 1 to Fig. 5. The drawings, Fig. 1 to Fig. 4, represent two kilns united into one structure. The cast iron shelves(a) are 2 feet 4 inches wide and 5 feet long, with sides and a back 4 inches high, and are cast a full halfinch thick. How they rest on the brackets(d), and interlock each other, is shown in Fig. 5. Three such shelves, with an inclination of 38') are placed in one row in a brick shaft 7 feet 1/2 inch wide and 4 feet deep. The ore hoppers(g) rest on the iron bems(f). At the end of the bottom shelves are the discharge-doors(b), with shoots projecting beyond the front wall. A swinging apron(e) keeps the ore in place. By dropping it a car below the shoot is filled with dry ore. A number of extra-large pieces of ore may cause a stoppage in the slits ; for such an emergency the openings(e) are provided, through

Jan 1, 1884

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By C. L. Pillar

INTRODUCTION The location, size, character of the ore de- posit and its adjacent formations will deter- mine the mining system best used for its ex- traction. The mining system chosen will have to be engineered to suit the ore deposit and the people that will extract it. What can be done in the Philippines cannot always be accomplished in the upper Northwest Territory of Canada. Mining operations developed under a free enterprise system are planned to achieve a satisfactory return on the capital required to place them into production. Hence, the choices made in planning and developing the mining system must be dictated by sound economics. The mining system planned must favor: 1. Maximum ore extraction of the deposit with minimal grade dilution. 2. The amount of capital expenditure used to develop and equip the mine must be in harmony with the financial policy of the group yet be sufficient to provide a reliable mining system. Excessive frills and extras that are not required for efficient, safe production should not be provided. 3. Mine production costs are determined by the amount of men, material, equipment and energy used in the production process. These must be kept to minimal limits in order to insure dependable, low cost production. Extras that later are needed in the production operation can be added as required by the operator. Basically block caving is a mining system that is normally used to extract deep seated, massive, low grade deposits of copper, molybdenum and iron where stripping ratios for open cast mining are economically prohibited. The caving system is limited in its selectivity. It is a mass production type of underground ore extraction that under favorable conditions is one of the most efficient, low cost mining systems in the world today. Usually block cave mining systems are large. They are capable of producing ore at a rate of 10,000 to 100,000 tons/day from large deposits at costs that are comparable with many open cast mining systems burdened by high waste to ore ratios. Block cave mining systems differ basically in the plan of the area layout, the method of undercutting and the method of draw. The balance of the mining system is the mechanical transportation of the drawn ore to the surface, the mine supply, drainage and ventilation systems. This paper deals mainly with the methods of draw. The method of draw to be used in a block caving system dictates the development plan of the mining area, is highly influential in the method of undercutting to be employed and the supply and ventilation system to be used. There are three basic methods of draw commonly used in today's operations. They are: Gravity draw Slusher draw LHD draw The type of draw planned will have a major affect on: Capital expenditure and time required to bring a deposit into production. Productivity, efficiency and cost of the production operation. Percent recovery of the ore deposit in both tonnage and grade. Degree of production reliability Fundamentally the type-of draw used must be compatible with the physical characteristics of the deposit to be extracted and the financial position of the mining operation. The type of draw chosen must work to advantage with the size, configuration, depth, strength and fracture pattern of the deposit and its adjacent formations. It must favor the financial protection of the planned mining operation. A Gravity Method of Draw requires a finely fragmented, easy flowing product from the caving action of the deposit. To obtain the desired economic advantage the ore deposit must also have sufficient area and height of column to permit minimal development cost on a per ton basis. The gravity system re- quires the maximum amount of development openings and uses the minimum amount of mechanized equipment of all the caving systems. It is unskilled, labor-intensive and is highly sensitive to size of ore fragmen-

Jan 1, 1981

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By H. M. Howe

(Read at. the Lake George Meeting, October, 1878.) MANY direct processes have been proposed for the treatment of oxidized ores of copper by reducing the copper oxide to the metallic state, and by separating it from its impurities by a subsequent fusion. The radical objection common to all the methods which have come to my notice, except those in which sulphur plays the prominent part, is that the very deoxidizing agent which effects the reduction of the copper oxide, inevitably reduces at the same time a very considerable part, if not the whole, of the iron which almost invariably accompanies copper in its ores. The result is that, when the ore is subsequently fused, a very great quantity of the already reduced iron separates from the slag along with the copper, alloying with it, and necessitating costly subsequent operations for its separation. Thus, at Perm, in the Urals,* the product of the fusion of ferruginous copper oxides is a mixture of one hundred and fifty-five parts of highly cupriferous pig iron with two hundred and five parts of very impure and ferruginous black copper, containing some 10 per cent. of carbon and iron, though free from sulphur, and of course very difficult to refine. If, in order to avoid this reduction of iron to the metallic state, the reducing action be made feebler, it inevitably results that a considerable part of the copper as well escapes deoxidation ; and, consequently, the slags are so rich that it becomes necessary to treat them subsequently in order to recover the copper which they contain. Thus, in treating native copper, at Lake Superior, where the reducing action is purposely made feeble in order to prevent the deoxidation of the iron, the slags from the first fusion of the ore carry so much copper as to render it imperative to treat them again, which is done in a cupola. And yet, in spite of so far weakening the reducing action as to cause a notable slagging of the copper, a very considerable reduction of iron actually takes place. These are the two dangers which threaten the smelter of oxidized copper ores. If he wishes to avoid slagging his copper, he must have so strong a deoxidizing action as to reduce a great deal of his * Rivot, Prineipes Généraux du Traitement des Minerais Métalliques, i, p. 79.

Jan 1, 1879

By J. P. Nichols

Modern vibrating screening dates from about 1910 at which time the forerunner of the present day two bearing and four bearing circular motion inclined vibrating screens were first introduced. These simple machines consisted of a screen box holding some kind of a screening surface to which was attached an off-center shaft or a shaft with an off-center weight which was rotated. The rotation of these shafts caused a shivering motion to the screen box and produced the first vibrating screen. In the 1920's and early 30's, the box designs were improved and the mechanisms designs were also improved and by 1940, vibrating screens were an important part of most process plants. In the early days when the screen sizes were dictated by how much could be shoveled onto the screen box and by the force that a particular mechanism could produce, not much thought was given to the proper sizing of the particular units. As mechanism and body design improved the ability to predict vibrating screen capacity at various openings became more important. In the late 1930's, a set of empirical capacities came to be used. with few modifications, these capacities are still in use today, both by those companies that use a formula involving only the amount of fine material in a feed, and by those companies using a formula in which the total feed to a particular screen is used. In either method of calculation, the empirical values are based on these ideal conditions: (1) The material being fed to the screen contains 25% oversize. (2) The feed to the screen contains 40% half size material. (3) The material has a bulk density of 1.6 T/Cu.M. (100 lbs/cu.ft.). (4) The screening surface has an open area of 50%. (5) The material is dry, free flowing and relatively cubical. (6) The maximum screening efficiency required is between 90 and 95%. It is obvious that these conditions do not occur in natural or crushed size distributions. Therefore, modifications must be made to these empirical values to allow for the calculation of a vibrating screen for a particular set of conditions. Before we consider these various modifications, let us look at what happens to material as it is acted on by a vibrating screen so that we can better understand why the modifications are nec-

Jan 1, 1982

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;&apos;-&apos; and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By A. D. Rovig, D. W. McGlashan, Donald M. Podobnik

Crystal-chemical and stntctural properties of sulfide minerals are considered. The information gained is to be used to interpret (I ) freshly broken mineral surfaces, (2) modifications of the mineral surfaces, and (3) reactions at the mineral surfaces. From these basic disciplines, concepts with regard to the changes that surfaces undergo, reactions that might take place, the geometry of the interface, the state of different atoms and ions in the interface, and other physical and chemical properties of an interface must be developed, weighed and applied. The authors first deal with these conceptual considerations from which hypotheses are set forth to describe the environ men tal-interfacial relationships for several sulfide minerals. Qualitative and quantitative explanation of par-ticulate solid separations are unknown entities because of the lack of adequate models and mathematical relationships to explain the activity occurring between the solid and liquid phases. It is a transitional region in which it is difficult to ascertain the mechanisms of adsorption of ions, molecules, etc., on mineral surfaces, as well as other secondary reactions which occur in interfacial regions. Thus, in this paper the authors deal with conceptual considerations from which hypotheses are set forth to describe the environmental-interfacial relationships for sulfide minerals. GENERAL CONSIDERATIONS Interfacial Reactions:Interfacial reactions are the cruxes of flotation schemes as well as other processes such as thickening, filtration and hydrometallurgy. However, as noted by Klassen and Mokrousov: 1 "The problems concerning the surfaces of natural minerals, the laws governing simultaneous adsorption from aqueous solution on these surfaces of a whole series of reagents, the laws of the surface reactions and the properties of water layers separating the minerals, are all known to a first approximation only." An investigator has the privilege of postulating methods of solid-liquid interfacial reactions. REACTIONS WITH WATER - Water consists of hydronium (H3 O 4) and hydroxyl (OH-) ions in the ionized state. That this is so forms the basis for the postulated reaction of the hydrated hydrogen ion with net-negative mineral surfaces as depicted in Fig. 1. In this case water is bonded to mineral surfaces through hydrogen-bridge-type bonds - possibly hydrogen bonds. Although bonding of the van der Waal type may be responsible for this reaction, it is most likely that stronger bonds are involved. Once firmly bonded to the surface, the water layer is known to be quite tenacious. It is further speculated that a shear plane exists at some distance (see Fig. 1) away from the mineral surface. Exact location of this plane is not known, but in all probability it will be positioned across a weak bond of the hydrogen-bond type where the surface-attached water is coordinated to the original hydrated hydrogen ion. REACTION WITH METAL IONS - Klassen and Mokrousov &apos; state: "The presence of an ion in water leads to an immediate formation around that ion of a highly condensed atmosphere of water dipoles and thus to hydration of the ion." The fact is known that multivalent cations are strongly hydrated, usually by six or eight molecules of water, and that anions are not so strongly hydrated. Conceding the fact that thermodynamics, concentration, pH, and physical considerations are of utmost importance in truly explaining a mechanism of metal ions reaction with a hydrated mineral surface, it does seem logical that the mechanism illustrated in Fig. 2 is feasible. In this reaction, the metal ion (M) is coordinated in one dimension - to the mineral-surface hydration layer. Note also that explanation of this reaction requires that the shear plane move to a less stable bond configuration; that is, the shear plane has moved to a position between the metal ion and the other coordinated water molecules which are more free to dissociate. Reactions as depicted in Fig. 2 should cause the formation of an apparent mineral surface which is net-positive. Immediately, it must be noted that measurements of apparent-mineral surfaces serve - within limits - to indicate a degree of ion-surface reaction capability. The major limiting factor he re is one related

Jan 1, 1970

By Nathaniel Herz

(San Francisco Meeting, September, 1915) THE use of zinc dust for precipitating the precious metals from cyanide solutions is well established now in many places, and has many advantages over the shavings method of precipitation. Although much work has been clone on methods of testing zinc dust, as yet no absolutely positive test has been devised to determine the value of the material. Certain facts are known, but often it happens that results on a working scale are not as expected from the laboratory tests. The purpose of this paper is to record some observations made while testing. a large variety of zinc-dust samples in the laboratory. W. J. Sharwood1 has described standard analytical methods, which have been followed, with the changes noted. The regular determinations include zinc oxide, by solution in ammonia and ammonium chloride, lead, and precipitating efficiency. In some cases cadmium was determined by a method similar to that described by J. E. Clennell.2 I will discuss the precipitating-efficiency test in detail. The procedure is as follows: "A solution of potassium silver cyanide is prepared by dissolving 10 grams of silver cyanide (AgCN) and 5 grams of `99 0&apos; potassium cyanide in a little water and diluting up to 1000 cc. It is then adjusted by addition of a little more KCN or AgCN until the solution indicates from 0.12% to 0.15% free KCN by titration with standard silver nitrate. The titration is best made by using a 10-cc. or 20-cc. sample, adding 1 cc. of 2 % potassium iodide, and a slight excess of ammonia, as the end point is then sharper. Or 15 grains of pure crystallized KAg(CN)2 may he dissolved in a liter of water and 1.5 grams KCN added. "Weigh out 0.5 grain zinc dust into a 300-cc. beaker. Add a few cubic centimeters of water and stir until, zinc is well mixed, then pour in 250 cc. of the prepared solution, stirring vigorously. See that all lumps are broken up, and continue stirring for fully five minutes. Stir occasionally (at least every 10 minutes) until the end of two hours from the addition of the solution. Then filter upon an 11-cm. filter, wash precipitate thoroughly, sprinkle with test lead, wrap it carefully in the paper, plaice in a scorifier with about 20 grams test lead, burn paper cautiously in muffle, scorify five minutes, cupel at low temperature and weigh silver. Milligrams silver obtained from 0.5 gram zinc X 0.0606 = percentage precipitating efficiency."&apos;

Jan 8, 1915

By O. W. Ellis

In view of the extensive use of the brasses and bronzes in engineering practice it is indeed surprising that so little scientific work has been done on the oxides in these alloys. Recognition of the ill effects of these compounds is universally accorded, both in foundry procedure and in such specifications as cover the melting of these useful mixtures. In the latter, limits, for example, are placed on the proportions of scrap metal In the charge, and clauses governing the use of fluxes are included, the addition of fluxes to the charge being made with the object of avoiding oxidation during the process of melting and of subducing and separating non-metal-lic matter from the melt.1 In the manufacture of brass it occasionally, though rarely, occurs that the virgin metals, copper and zinc, alone arc used. In the event of virgin metals being employed, that of the higher melting point is always melted first. If it is melted under suitable conditions, little or no oxidation will occur. Whether oxidation has occurred or not, however, can best be determined by microscopic examination of a sample taken from the melt. Avoidance of Oxidation in Furnace Practice When melting virgin copper in crucible practice, the avoidance of oxidation is not difficult, nor is it hard to forestall trouble in the electric furnace. In gas-fired furnaces of the barrel type, however, the avoidance of oxidation is almost impossible, no matter what the condition of the flame, the flux employed, or the amount of charcoal included in the charge. Copper melted in furnaces of this type is almost invariably so highly oxidized as to requirc very considerable additions of such deoxi-dizers as, for example, silicon copper to render it free from cuprous oxide. As a result,, the castings produced are decidedly inferior, on account of the. large amount of silica which is engendered in the metal as a result of the reaction, Cu2O + Si = SiO2 + 2Cu. The deoxidation of such oxidized copper could, of course, be effected by means of zinc with, however, even more disastrous results.

Jan 1, 1930

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1&apos;2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968