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By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,' detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By R. E. Boehler, N. C. Ludwig

At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory&apos;s thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers&apos; experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman&apos;s observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph&apos; and also in a textbook.&apos; Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very

Jan 1, 1961

By R. C. Craze

During the past 20 years. research and development in the study of reservoir behavior have dealt principally with flow of oil through sandstones. Many reservoir studies of sand fields have proved valuable in promoting recovery efficiency. This paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone reservoir studies to the study of limestone reservoir performance. The characteristics of limestone porous systems, porosity-permeability relationships, distribution and occurrence of oil, and characteristics of flow through such systems are discussed. Recognition is made of the similarities or differences which these factors exhibit in limestone and sandstone systems. Comparisons between operating data for typical limestone and sand reservoirs are presented. It is indicated that the distribution and movement of fluids in and through porous limestones follow the same fundamental principles underlying such processes in sandstones. This fundamental similarity may readily be discernible in the performance of many limestone reservoirs. The volumetric balance and unsteady state radial flow equation, the fluid displacement equation, use of electrical analogue devices, and other analytical techniques to study the behavior of limestone fields appear fundamentally applicable, but do require thorough understanding of the properties of the formation, of the fluids, their behavior during flow, and adequate production operating data. Need for more complete coring and comprehensive examination of core properties is stressed. The results of "active oil" studies, and of flow and interference tests are presented. Well spacing, well completion, and efficient rates of production in limestone reservoirs are briefly discussed. INTRODUCTION Limestone and dolomite reservoirs constitute the largest source of supply of crude oil in the world. an estimated 60 per cent of present production coming from carbonate reservoirs. In many large geologic provinces such as Mexico. the Middle East, and more recently Canada, almost all the oil is found in this type of rock. In the United States, all of the major oil-producing areas except California and Pennsylvania contain oil-bearing carbonate formations. The discovery in recent years of large oil reserves in the Silurian, Devonian, and Ordo-vician formations in West Texas, in addition to the large reserves in the Permian, has accentuated the interest of operators, geologists, and engineers in limestone formations and in the many problems associated with understanding the performance of these reservoirs. The rapid increase in discovery of oil in limestone formations and the present-day position of prominence held by these fields in the production and reserve picture in all parts of the world emphasize the horizons opened to the reservoir technologist in the field of geological and production research. Pertinent to an interpretation of the behavior of limestone reservoirs are the methods of analysis which may be utilized and a possession of full knowledge of the many factors which influence the analytical procedures. During the past 20 years a well-developed science of reservoir engineering has been built upon the research of many workers who studied the fundamental nature of oil reservoirs, characteristics of the porous media, properties and behavior of the contained fluids, and the mechanics of flow. Application of these studies to production practice has resulted in greater recoveries and more efficient field operation. The major portion of this evolutionary process has been founded upon studies of sand fields. The applicability of these more thoroughly developed techniques for studying sand fields to the study of the behavior of limestone fields becomes a factor of technical and practical significance. In the light of the technological background available to the reservoir analyst, this paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone studies to the study of limestone reservoir performance. LIMESTONE RESERVOIR CHARACTERISTICS The characteristics of limestone and sandstone reservoirs are similar in many respects and they both may occur under similar structural conditions. Fundamentally, the distribution and movement of fluids in and through the porous limestone media follow the same basic principles which dictate such processes in sandstones. Herein lies a fundamental similarity, which may readily be discernible in the performance of many limestone reservoirs. In some limestone fields, as in many sand fields, widely varying formation properties and distribution may reveal themselves in deviations in the performance of the reservoir, in the behavior of wells, and in fluid flow through the rock, and make difficult the delineation of reservoir behavior. Only by reservoir studies, core analyses, and coordinated laboratory and field experimentation can the effects of the many influencing factors upon the nature of limestone production be determined. FORMATION CHARACTERISTICS The chief difference between limestone and sandstone, aside from their chemical compositions, is the difference in the geometry and origin of the porous systems in the two kinds of rock. In sandstone the porous system results entirely from the openings among individual sand grains which occur during deposition. The geometry of the openings between the sand

Jan 1, 1950

By R. H. Lee

WITHOUT doubt, one of the most frequent and serious annoyances connected with the practical running of a blast-furnace, especially in single-furnace plants, is caused by low steam, in spite of the fact that all boilers at blast-furnaces have grates for burning coal, and that coal is more or less continuously burned upon them, from three to a dozen men being pretty constantly engaged around the boilers as firemen or coal- and ash-handlers. At times, when the furnace is ? tight," all available men are put on to assist the regular firemen; yet sufficient steam cannot be got to keep the engines up to their regular number of revolutions, while the stoves, deprived of the gas which has been sent to the boilers, run cold, so that, when the furnace loosens-up and resumes the regular rate of driving, the blast is very considerably below normal temperature, and a.&apos; cold," or at best a " high-sulphur," east is the result. Again, it often happens that a furnace, running at its best, becomes temporarily a little too hot; the pressure rises; the amount of gas made&apos; is diminished; the steam soon commences to go down; and a small scaffold is likely to form before the furnace has been brought back to the proper rate of driving, and thus enabled to take its regular amount of blast. The usual remedy is either to "jerk" the furnace by a sudden, brief intermission in blowing, or to cool the furnace by lowering the heat of the blast; but if the lower blast-temperature be maintained too long, the hearth and descending stock may be cooled below the " critical temperature " mentioned by Mr. .Johnson, and the furnace may go to the other extreme, and become cold. This is especially the case when coal or coke, high in sulphur, is used:

Jul 1, 1906

By James T. Kemp

AN historical society of particular interest to mining engineers all over the world was born in Cornwall in 1935. A hundred-year-old winding engine then finished its long labors at the Levant mine on the cliffs near Lands End, England. The engine was to be dismantled and scrapped. A few men living near-by, appreciating that this event was one of the final acts in closing a long century of extraordinary mining and engineering evolution. armed a committee to prevent the destruction of the old mine hoist and succeeded in purchasing the engine. They restored the engine house and in time arranged with the Manor of Trewellard, owners of the land, for a 99-year ground lease on a peppercorn rental.

Jan 1, 1947

Jan 1, 1944

Jan 1, 1944

Jan 1, 1908

Jan 1, 1909

By J. W. Miller

One of the major problems confronting coal producers in this highly competitive era is whether or not the potential profit to be made from the products of coal flotation would warrant the capital investment required for the necessary equipment. The author supplies two theoretical cases to illustrate methods for computing such costs.

Jan 3, 1961

Jan 1, 1947

Jan 1, 1947

By Emmanuel Detournay, Charles Fairhurst

A method is proposed for computing (a possible solution of) the ground reaction curve, for use in tunnel support analysis, in cases where the initial stress field is not hydrostatic. Rock around a circular tunnel is assumed to behave as an elasto-plastic material with a Mohr-Coulomb yield envelope.

Jan 1, 1982

By H. Rush Spedden, Arvid Thunaes

Pilot plant test work in 1942 and 1943 showed that by a combination of desliming, fine-size classification, and Sullivan deck concentration it is possible to recover heavy minerals such as cassiterite at least as fine as 10 microns in size. This appreciable improvement in gravity concentration practice has been substantiated by several full-sized plants.

Jan 8, 1950

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Jan 1, 1938

By C. Richard Tinsley

Non-ferrous econometric metal models available from consultants are reviewed for structure and computer access, using copper as an example The evolution of a computerized metals price forecasting system for a consumer of non-ferrous metals is outlined including front ends, bridge equations, and supporting databases. An empirical sensitivity analysis technique is described. A postscript discusses the subscription costs of these models.

Jan 1, 1977

Jan 1, 1965

By B. Ball, C. H. Cox, S. N. Yap

Electrokinetic measurements on cassiterite were made in the presence of sodium di-hydrogen phosphate, mono-hydrogen arsenate, bisulfite, and sulfate. Flotation studies were also conducted using sodium dodecyl sulfonate in the presence of these salts. It was found that the anions specifically adsorb on cassiterite in the order H2AsO-4 H2PO4 HSO3 SO4 and consequently cause flotation depression. The adsorption mechanisms of the various inorganic anions are discussed in detail.

Jan 1, 1980