Search Documents

By John W. Bader

Probing a mineralized area with a core drill to find out what's there is fundamentally a simple task, but a costly one. Quite commonly it costs $10, and sometimes more, to extract and assay each foot of drill core obtained. Yet, it is not unusual today to drill hundreds of holes on one mineral property. The initial objective of such probing is almost always simply to determine the potential worth of the ore- body, if any exists, and the question naturally arises: How little sampling is enough for this determination? The mathematics of statistics infer accuracy of estimates largely from the sheer number of samples taken. Mineral exploration usually involves accumulation of large numbers of samples, and thus it is usually not difficult to place narrow confidence limits on either side of the estimated average grade of a sampled orebody. The determination may, or may not, be as accurate as the derivations imply. If it is not, the fault is probably one of misapplication and not with the statistical processes themselves. Un- fortunately, indications are strong that the ordinary statistics of sampling usually cannot be applied to orebody exploration samples with actual attainment of the accuracy of estimate that they express mathematically. For this reason, a more deductive, less mathematical analysis of the sampling may well be worthwhile.

Jan 1, 1970

By R. D. Saltsman

This paper deals with the evolution of a test procedure devised to totalize a coal's ignitibility, its degree of caking, and its coke reactivity and the development of a method for assigning proper combustion indices to stoker coals. The application of this type of work to stoker design is also discussed. It is believed that this work may be the prelude to understanding the effect of various petrographic constituents on the combustion characteristics of a coal or a blend of coals. The inadequacy of our knowledge of the coal combustion process has long been recognized. This was expressed very well by Spicer and Finney.1 "The control of combustion processes in industry and the design of the equipment necessary for efficient burning to take place have always been very much branches of an industrial art rather than of an exact science. This has been especially true of the utilization of coal, a substance so heterogeneous and complex in character that all too little is known about its chemical and physical composition." During the past several years one branch of coal utilization, that of high temperature carbonization, has made significant advances from being an art into being an exact science. This has been accomplished by the development of petrographic techniques for identifying, measuring, and determining the thermal properties of the organic materials which affect the carbonization of coal and the correlation of this information with a pre-existing standard of coke quality, the stability index. The success in using petrographic analysis for predicting the coking properties of coals and their blends suggested that petrographic techniques might be applied to the combustion process for predicting the combustion characteristics of coals. Certainly the different organic entities2 influence the combustion characteristics of a coal as they influence its coking properties. If it were possible to predict combustion characteristics from an analysis of a coal's petrographic composition, it would seem logical that an intelligent investigation could then be made into methods of altering stoker coals to improve their combustion characteristics. The successful application of petrographic analysis in the field of high temperature carbonization was made possible by the pre-existence of the stability index, which is a numerical value of coke quality. The quality of combustion is determined by the sum of the effects of the ignitibility, the caking, and the coke reactivity characteristics of a coal. While the literature is filled with papers reporting the correlation of various analyses to the ignitibility, or to the caking, or to the coke reactivity characteristics of coals, none of these earlier studies could be related to one index. The lack of a single index for combustion quality precluded the application of petrographic techniques for predicting combustion characteristics. SELECTION OF THE COMBUSTION TEST EQUIPMENT The primary prerequisite of any test developed to evaluate the relative performance of stoker coals must reflect the three characteristics of the coal burning process: 1) ignitibility, 2) degree of caking, and 3) coke reactivity. The widespread variations in these combustion characteristics of the available stoker coals are well known. The ignitibility, which has been defined as that characteristic which determines the ease with which the fuel may be brought to a condition of self-supporting active oxidation, varies from where a coal is deemed to be flashy to the opposite extreme of being fireproof. The ignitibility of a coal influences its ability to pick-up from hold fire, greatly affects the degree of bed stability during swing loads, and is a factor in determining the average burning rate obtainable on a given grate. The caking characteristic affects the degree of bed porosity during the devolatilization period, and coals are classified on a scale varying from free burning to highly caking. Caking is not synonymous with bed swelling since a bed may swell two to three times its normal depth during the period of devolatilization yet remain very porous, allowing an efficient and high rate of combustion to take place. Caking is melting

Jan 1, 1964

By C. H. Mathewson

MICROSCOPIC rnetallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent microstructural mosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atomis or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientations and it is always possible to derive one from the other by some form of rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

By C. H. Mathewson

MICROSCOPIC. rnetallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent microstructural mosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of 'particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atoms or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientations and it is always possible to derive one from the other by some form of rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

Jan 1, 1928

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By A.E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By AIME AIME

Council.* PRESIDENT OF THE COUNCIL. ROBERT W. HUNT CHICAGO, ILL. (Term expires February, 1907.) VICE-PRESIDENTS OF THE COUNCIL. WILLIAM P. BLAKE TUCSON, ARIZ. THOMAS F. COLE DULUTH, MINN. IRVING A. STEARNS WILKES-BARRE, PA. (Term expires February, 1907.) HENRY AL HOWE NEW YORK, N. Y. J. B. GRANT DENVER, COLO. JAMES D. HAGUE NEW YORK, N. Y. (Term expires February, 1909.)

Nov 1, 1906

By J. D. Meakin

The self-diffusion coefficients of ß tin have been deterttlltled using a plating and sectioning technique. The principal diffusivities pavallel and perpendicu1ar to the "c" axis are given by the Arrhenius relations Dc = 8.2 exp (-25,600/RT) sq cnl per sec and Da = 1.4 exp (-23,300/RT) sq cm) per sec. The results are discussed in terms of a vacancy mecharism of diffusion. In conjunction with an investigation of diffusion in dilute indium-tin alloys we have reexamined self-diffusion in tin single crystals. The published self-diffusion coefficients of tin, eensham') have always appeared anomalous in comparison to diffusion data for other metals and do not correlate with parameters derived from creep tests.' In addition to the necessity of confirming the self-diffusion values for use in analyzing the alloy work, self-diffusion in an anisotropic lattice is of considerable fundamental interest and confirmation of the published data seemed worthwhile. For a crystal with an axis of symmetry three-fold or higher the diffusivity at an angle 6 to the axis is given by D? = (Da - Do) sin2?+ Do [1] where Da and Do are the principal diffusivities perpendicular and parallel to the axis. For a particular diffusion mechanism, again in a crystal of axial symmetry, these principal diffusivities are [2] Do - ? ?i2 COS?i In these expressions ?i is the displacement undergone by the ith atom and 8, is the angle this displacement makes with the symmetry axis. In this, as

Jan 1, 1961

By John Chipman

RECENT developments in iron alloys containing nitrogen have indi-cated that this element may exert a considerable influence on the proper-ties of the metal. This influence is not always in an undesirable direction and the indications are that nitrogen should be regarded as an alloying element, the amount of which should be subject to control, rather than as an inherently deleterious impurity. In controlling this element in liquid iron to the best advantage, it is necessary to have a reliable background of fundamental data pertaining to solubilities, rates of solution and chemical reactions of nitrogen in liquid iron. Obviously, the first step in such an investigation is the determination of the solubility of nitrogen in pure iron, and this has been the object of the experiments described in this paper. The solubility of nitrogen in solid iron has been measured by Jurich,1 Sieverts,2 Martin,3 and Iwasé4 and the agreement among the first three inspires confidence in their results. No accurate determinations of its solubility in liquid iron have been recorded though several investigators have obtained approximate results. Strauss5 was able to introduce 0.03 to 0.04 per cent nitrogen into steel by the action of either ammonia or nitrogen on the liquid metal. This was accomplished by Eilender and

Jan 1, 1935

Background The annual awards, which have been given by the US National Committee for Rock Mechanics since its inception in 1969, recognize out- standing research in rock mechanics. Such recognition has always been accompanied by a plaque or certificate for the winners and a presentation at the symposium awards banquet. Starting this year, the US National Committee will give the winners even more recognition and allow the rock mechanics community to benefit from the papers by publishing abstracts of the work in the proceedings of the 25th US Symposium on Rock Mechanics and in various society journals and news letters. "We hope this will stimulate the production of more research papers," said William R. Judd, former chairman on the subpanel of awards. "It's beneficial for researchers to have their work published as an award paper." There are four categories of awards: Basic Research, Applied Research, Case History, and Student Masters' Thesis. Approximately ten papers are nominated annually for each category; however, in some years awards are not made in all four categories. For instance, there were not enough case history nominations in 1983 for an award, but there were two equally outstanding recipients of the award for applied research. The winners of the 1983 research awards reflect the wide variety of professions involved with rock mechanics. They are introduced on the following pages by category, and accompanied by an abstract of the paper

Jan 1, 1984

I HAVE told you of two parts of the mould for guns. You lack the third, which is the one for making the breech. This, in addition to being a part that is always ornamented with some piece of sculpture to make the gun beautiful, is that part which forms the bottom and closes the whole mould. It is also the one that sustains the entire burden of the bronze, and it must therefore be made with great consideration and diligence, taking care to make it strong with clay and with iron bands. Various methods are used in making this. Every master does as he knows how, either preferring to do it quickly or delighting to make his work ornate and beautiful. His choice also depends on whether they are to be just artillery or occasions for artistry. There are some who, if the guns are of a round form, make the pattern for the breech on a lathe, either of wood or of clay. If they are fluted, they make the flutes by hand in wood or clay, following the pattern of the board. In a part that perchance might not come out of the mould, they put some tallow underneath or make it entirely of tallow or wax so that it will come out. Likewise, if they wish to make cornices or other projections these can be put on either in wood or in clay. In the same way they also apply leafwork of clay or wax so that it can be taken out by hand or with the fire.

Jan 1, 1942

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By W. E. Showalter

This paper discusses some of the results of combstion-drive tests which were made in a test cell using a sand bed 10 in. in diameter x 10-ft long. The test method is illustrated and described. The relationship between the API gravity of the in situ oil and the amount of air required for combustion drive is discussed in detail. Other things constant, the air requirement for combustion drive increases as the APl gravity of the in situ oil decreases. If the test results apply to actual reservoirs, the lowest-priced oils may cost the most to recover by this method. Information is shown which indicates that the effect of pressure on the amount of hydrocarbon burned is not large. A method of predicting air requirements from the API gravity of the in situ oil is presented. INTRODUCTION Combustion drive is the term used to identify the process of interstitial or in situ burning as an oil recovery method. Part of the in situ oil is burned to generate the energy needed to produce the remainder of the oil. Combustion drive as an oil recovery mechanism remains an economic uncertainty in spite of all the work that has been done by the industry in both laboratory and field?-6 This paper will show some of the results of tests which were made in a test cell for the purpose of studying the nature of the combustion-drive process. It will present data which indicate that the API gravity of the in situ oil is a significant indicator of the amount of air required to drive a burning front through oil sand. Air requirement varies inversely as the API gravity of the in situ oil. EXPERIMENTAL The tests were performed in a cell which utilized a cylindrical sand section 10 in. in diameter x 10-ft long. The thin-walled metal pipe which held the sand was wound with twenty external electrical resistance heaters which, by means of an automatic controller, maintained adjacent sections of the wall of the pipe at temperatures equal to the temperatures of the contained sand. Each heater covered 6 linear in. of the pipe. By this means lateral heat loss from the sand section was minimized, thereby causing the sand section to simulate more closely a horizontal increment of a combustion-drive reservoir. Fig. 1 shows a schematic diagram of the test assembly. Thermocouples to measure the temperature in the sand were located every 6 in. along the length of the sand section. The pipe containing the sand was enclosed in a cell designed for an operating pressure of 500 psig. The inlet air pressure was controlled at the inlet, and the gas flow rate was controlled and measured at the outlet of the cell. The oil sand used for the tests was prepared by mixing first water and then oil with the noncon-solidated sand using a closed mixer similar to a cement mixer. Table 1 shows a screen analysis of the sand. Ninety percent of the sand was 100 mesh or finer. This sand was a mixture of 80 per cent No. 120 Nevada White Sand and 20 per cent Tennessee Hi-Fusion Moulding Sand No. 3. The Nevada sand was a clean silica sand. The Tennessee sand con-

By Thomas MacFarlane

In smelting copper, lead, and silver ores, it is scarcely possible in every case to make analyses of the various parcels of ore, with the view of combining these and the fluxes so accurately as to yield, in the furnace, slags of exactly the most favorable composition. This is even more difficult with ores which require previous calcination, or with mattes which have been roasted in heaps. Even in cases where the greatest pains have been taken and the most elaborate calculations made beforehand, it frequently happens that variations in the working of the furnace interfere with the result so much desired. Generally, the practical metallurgist must be content with ascertaining the average composition of his ores and fluxes, making a calculation once for all as to the most advantageous mixture, and leaving slight changes in its composition to be taken care of as it is passing through the furnace. The various products then afford him the best material whereon to base his judgment as to the manner in which his smelting mixture is working. Of course the character of the slag is one of his chief guides, but it is not always possible from its outward characters alone to form a correct judgment as to its composition. Neither would it be possible or practicable to apply chemical analysis for this purpose, as it would be impossible to wait for its results while working a furnace. Abich was, I believe, the first to point out the relation existing between the composition of volcanic rocks and their densities, and to show that, the latter being ascertained, very correct conclusions

Jan 1, 1880

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By I. N. Knap

Discussion of the paper of HOWARD R. HUGHES, presented at the Now York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 629 to 635. I. N. KNAPP, Ardmore, Pa.-The claims made in the paper for the Sharp & Hughes cone bit are modest. I have used it with satisfactory results. It is a wonder for eating through hard, brittle rock; it will drill through iron pyrites that the fish-tail bit cannot enter. Soft ground is apt to contain concretions that are much harder than the containing ground. ?We have at times in drilling with a fish-tail bit thought the hole was partly in such hard material and partly in soft, thus making a difficult place to drill past in the ordinary way. By changing to a Sharp & Hughes cone bit such obstructions were easily overcome. This cone bit has greatly widened the range of work that may now be profitably accomplished by the hydraulic rotary method of drilling. It is not, however, adapted to drill soft or sticky ground, the old fish-tail bit being better for such purposes. The fish-tail bit usually scrapes its way through the material drilled, but not always. I believe at times it cuts and chips in soft friable rock. That is, the bit seems to bite into the rock, and when sufficient torsion is put on the drill stem it breaks its hold and jumps around and chips the rock from the bottom of the hole, like a stone cutter's chisel, and then takes another hold. This condition occurs only in friable material when the bit is sharp and the feed properly controlled. The Sharp & Hughes cone bit is a most valuable -tool for the rotary driller.

Jan 5, 1915

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