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By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By Özgür Bezgin

This paper presents observations on the installation of drilled shafts from two construction projects and an academic study with experimental and analytical parts. The construction projects involved the use of pressurized drilling methods. The experimental part of the academic study involved the use of the auger drilling method. The analytical part of the academic study investigated the effect of drilling methods on the soil-structure interaction and the behavior of drilled shafts under lateral loads. The concept of ?free-length? is introduced for the lateral load design of pressure-drilled shafts that are thought to be fully embedded within a soil media. The academic part of the study presented herein was conducted in Rutgers, the State University of New Jersey.

Jan 1, 2009

The maximum current density at which conventional copper electrowinning plants will result in satisfactory, adherent, and dendrite·free cathodes is determined by the thickness of the diffusion boundary layer. A decrease in the value of that thickness will permit an increase in the current density. This fact is utilized to develop a high current density cell in which the reduction of the boundary layer thickness is accomplished by means of a specially designed electrolyte circulation system. The high current density cell is used to determine the effect of current density on such process parameters as current efficiency, cell voltage, power consumption, and cathode purity. A number of empirical equations are developed for the purpose of estimating the magnitude of these effects.

Jan 1, 1972

By David R. Beadman

This paper discusses how modern techniques of design and construction were used to create the deep stations for the Copenhagen Metro. The deep stations are located in small squares within the city adjacent to many old and sensitive buildings. The architectural design provides a large open atrium to allow natural light to reach the column free platforms to give the citizens of Copenhagen a feeling of safety and security and encourage them to use the Metro. The design and construction contract was undertaken using the relatively new and untried Eurocodes. The resulting stations set new standards of design for underground metros and have pushed forward the frontiers of what is appropriate construction practice to protect the existing and enhance the future environment.

Jan 1, 2000

By P. A. Croce

A total of 17 mine gallery fire tests (23 including sub-tests) were completed during this report period (10/1/76 - 11/30/77), directed at identifying a hazardous timber-set fuel-loading in a mine passageway that is otherwise free of combustibles. Results of these initial tests show that the capability of a particular fuel loading for propagating a fire is dependent upon the imposed ventilation air velocity and the ignition intensity, although this dependency needs to be better defined. It is also apparent that care must be taken when relating gallery test fire behavior to actual mine fire behavior, because of the restrictive length of the gallery. Present data indicate that some modification to the instrumentation scheme may be advantageous before proceeding with future tests.

Jan 1, 1978

By E. Pribonic

Failure of a mine material hoist can cause injuries, fatalities and significant infrastructure damage, along with an associated loss of production. Principal causes of hoist accidents are overwind and underwind. Past and present means of arresting hoisting equipment are marginally effective and utilize destructive systems that are not reusable following an arrest. The use of permanent magnet eddy current arrestor technology is proposed; the history and fundamental science of the technology are presented, followed by real world examples and calculations of performance for failsafe, friction-free, instantly reusable eddy current arrestors as applied to stopping a 30-ton ore skip traveling at 16 metres per second. A comparison of existing arrestor types with the eddy current arrestor is included and limitations of the ECA are also discussed.

Jan 1, 2008

8186. Aquilina, C. Determinazioni relative di gravita eseguite nel 1939 (Relative Determinations of Gravity Made in 1939), Ric. Ingegn, Rome, vol. 10, 1942, pp, 6376. In 1939, the author made a survey of relative gravity in the Mediterranean-basin, 41° 35,5' to 41° 56.3' northern latitude and 0° 10,3' to 0° 28' longitude, referred to Mt. Mario. Ten stations were covered; 25 other stations had been occupied in the vicinity of Rome and in Albanian mountains during previous years. The new measurements revealed gravity anomalies ranging within the following limits: (1) With a free-air reduction, between + 29 and + 120 mgl., average + 60 mgl.; and (2) with a Bouguer reduction, between + 22 and + 87 mgl., average + 41.5 mgl. - V. S.

Jan 1, 1946

By Robert H. Richards

(Pittsburg Meeting, March, 1910.) THIS is in part a review paper, indicating the various steps that have been taken in developing hindered-settling apparatus, some of the standard data that have been obtained, and some of the conclusions one is led to as to the effect of it in improving concentrating-methods and machinery, and in part it brings in some unpublished work. CAUSES OF LOSS IN ORE-CONCENTRATION. In making a study of the separation of valuable minerals from the waste gangue, particularly by water concentrators, it is necessary to define, first of all, what are the causes of-loss that are likely to interfere with the concentration. Having made this definition; we can then study to see in what way the machines make their losses, and plan remedies for them in an intelligent way. Losses may be stated to occur as included grains, as flat or long grains, as fine free mineral, and as absolute slime. We will take, these up one by one, as follows: Included Grains.-Fig. 1 shows by a set of diagrams how included grains may occur: first, where the heavy mineral grains attached to the quartz are of large size; secondly, where they are of small size ; and thirdly, where very fine particles of heavy mineral are included in the quartz. We have to decide in regard to included grains whether they are rich enough to go direct to, the furnace, or poor enough to throw away, or whether they lie between these two points and require recrushing as the only means of severing the values from the waste. This last case is the only one requiring special treatment at our hands. We will therefore consider that next. * By mutual consent, this paper has been presented also before the Colorado Scientific Society, and the Canadian Mining Institute, Montreal.

Feb 1, 1911

By K. K. Kelley

This work is a continuation of a program of study of the measurement and correlation of fundamental thermodynamic data inaugurated several years ago by the United States Bureau of Mines. Previous bulletins in this series were concerned with (1) The Entropies of Inorganic Substances (66),3 (2) High-Temperature Specific-Heat Equations for Inorganic Substances (67), (3) The Free Energies of Vaporization and Vapor Pressures of Inorganic Substances (68), (4) Metal Carbonates-Correlations and Applications of Thermodynamic Properties (71), (5) Heats of Fusion of Inorganic Substances (69), and (6) A Revision of the Entropies of Inorganic Substances-1935 (70). The present bulletin has as its primary purpose the correlation of the thermodynamic properties of elementary sulphur and its inorganic compounds and the presentation, after careful consideration of all available information, of a self-consistent system of thermodynamic relationships for these substances. It is believed that such a set of relationships, concerning substances of such great metallurgical importance as sulphur, sulphur oxides, hydrogen sulphide, metal sulphides, and metal sulphates, is of considerable value in indicating directions of possibly profitable experimental work and in clarifying subjects of technical interest upon which direct experimental information is difficult and expensive to obtain. It cannot be doubted that many problems of technical importance that at the outset appear almost hopelessly complex or obscure either may be solved, if enough information is available, or the specific lacking information clearly indicated by the adoption of the thermodynamic viewpoint. This has been demonstrated many times in the work of the Metallurgical Division, Pacific Experiment Station, Berkeley, Calif. Even when only crude basic information is available, a semiquantitative picture often may be developed by thermodynamic means in which general trends and approximate limits of a proposed process or modification of practice may be clearly portrayed and thus used as guides in further considerations and experimentation.

Jan 1, 1937

By I. Dymov

"The extractive metallurgy of precious metal ores involves gravity concentration, flotation and cyanide leaching. Pre-oxidation, such as roasting, autoclaving, bacterial oxidation and other techniques, is required for processing refractory ores. Selection of the process is mainly driven by the grade, reserve and mineralogy of the target elements. The concentrations of precious metals in the crust are extremely low and highly variable, resulting in ore variability in many gold, silver and PGE deposits. More importantly, precious metals in an ore may occur in two or three forms (i.e. microscopic, submicroscopic and surface-bound), making ore processing of precious metals extremely challenging. The objective of geometallurgy and process mineralogy is to reduce and minimize the technical risk in project evaluation, process selection, mine planning and production forecasting through geometallurgical modelling, representative sampling and subsequent systematic mineralogical characterization and metallurgical testwork. Geometallurgy is a technique to document variability within an orebody and quantify and evaluate the impact of many factors including geology and mineralogy on grinding, flotation, leaching and metal recovery processes, while mineralogy is one of the major predictive and trouble-shooting tools for many new mineral projects and operating mines. This paper presents an overview of fundamentals, methodologies and techniques applied in geometallurgy and process mineralogy and highlights the importance of both disciplines in process selection and plant optimization with applicable case studies. INTRODUCTION Precious metals, including gold, silver and platinum group elements (PGE) occur in various geological settings and ore types. The concentrations of these metals in the crust are extremely low and highly variable, resulting in ore variability in many gold, silver and PGE deposits. More importantly, precious metals in an ore may occur in two or three forms (i.e. microscopic, submicroscopic and surface-bound), making ore processing of precious metals extremely challenging. Process selection is most important in any precious metals project and is mainly driven by the grade, reserve and mineralogy of the target elements. Free-milling ores, such as Kupol in Russia, Hemlo in Canada, Grasburg in Indonesia, UG-2 in South Africa, Lac des Iles in Canada, and Noril’sk in Russia, can be processed using flotation or cyanidation with or without gravity. B2Gold Corp, a Canadian gold company, just started a number of new and under construction free-milling gold operations such as Fekola mill in Mali, Mastbati mine in Philippins and Otjikoto mine in Nambia. However, refractory ores (particularly gold ores), such as the Carlin and Goldstrike mines in the USA, Giant in Canada, Pueblo Viejo in Dominican Republic, Porgera and Lihire in PNG, Kittilla in Finland, Fairview in South Africa and Shuiyindong in China, must be processed using pre-oxidation prior to cyanide leaching. In some mildly refractory gold ores, such as Kumtor mine in Kyrgyzstan and KCGM in Australia, ultrafine grinding is required to liberate fine-grained gold particles. For some gold ores containing both free-milling and refractory components (such as Cripple Creek mine in Colorado, USA), two or more recovery processes may be required. The variability of grade, metal deportment, ore hardness and other parameters is one of the risks that encountered in development and operation of many precious metals projects. To minimize and reduce the technical risk caused by ore variability, geometallurgy and process mineralogy have been used by mining companies in the last two decades to measure and quantify the spatial variability of the deposits that are being developed. This paper presents an overview of fundamentals, methodologies and techniques applied in geometallurgy and process mineralogy, it highlights the importance of both disciplines in process selection and plant optimizat"

Jan 1, 2018

By W. A. Calhoun, M. M. Fine

"One of the most important wartime activities of the Bureau of Mines was the search for new sources of mineral necessary to the prosecution of the war. Part of that effort was in the form of metallurgical service extended to other government agencies engaged in purchasing and stock piling some of the more critical and strategic materials.Fluorite was one of the materials stock piled by the Metals Reserve Company. The fluorite was usually in the form of coarse metallurgical con¬centrate purchased in the United States and abroad. The material was stock¬piled to insure an adequate reserve of fluorite for the metallurgical industries. The domestic production of metallurgical fluorite containing a minimum effective calcium fluoride content of 55 percent,4/ however, gradually increased until production was at least equal to consumption. The stock-piled metallurgical fluorite, therefore, soon became a surplus commodity.On the other hand, the supply of acid-grade fluorite, containing a minimum of 97.5 percent calcium fluoride and n maximum of 1.5 percent silica,5/ was never entirely adequate. Increased consumption of acid-grade material in the aluminum, petroleum, and chemical industries kept that material on the critical list during the war.Under the circumstances, it was felt that a study of the possibility of producing acid-grade fluorite from the metallurgical stock piles would be of some benefit to the war effort. Consequently, samples of fluorite from several of the Metals Reserve Company stock piles were tested by the Bureau of Mines at the request of the War Production Board.Two groups of samples were submitted for testing. One consisted of metallurgical fluorite purchased from Mexico and stock-piled in the El Paso and Laredo, Texas, stock piles of the Metals Reserve Company. The second group of samples was from the stock piles at Gila, N. Mex.The sample submitted from the El Paso stock pile consisted of about 5,000 pounds of minus 4-inch material. Mineralogically, the sample consisted of fluorite contaminated by calcite, chert, quartz, and small amounts of iron and alumina. Although some of the fluorite was reasonably free from gangue at minus 1-inch, much of it remained locked in sizes as fine as 65-mesh.The Laredo sample was about 5,000 pounds of material from five different piles. The samples from each stock pile, A to E, inclusive, were analyzed separately to determine whether the grade of the material in the piles varied markedly. As there was little difference in the analyses, the samples were combined in proportion to the tonnage represented to make a composite sample for testing. The composite sample consisted of fluorite with small amounts of quartz, calcite, and barite. Most of the fluorite was the dark-colored, opaque variety. A small amount of iron-oxide staining was present, and traces of muscovite, clay, pyrite, and tourmaline were noted. The quartz was present as crystals in vugs, and as finely disseminated grains in the fluorite. The druzy quartz and the calcite were free at minus 10-mesh, but the disseminated grains, some of which were 1 to 15 microns in size, were not entirely free at minus 270-mesh. A petrographic estimate indicated that 65 percent of the silica was locked in the 150- to 200-mesh."

Jun 1, 1946

By D. M. Bodily, V. J. Hucka

INTRODUCTION Interest in the recovery of methane from coalbeds has increased rapidly over recent years, because of its potential as an energy resource and to alleviate pollution and safety problems. The resource base of coalbed methane in the United States has been estimated at 11.2 Gm3, roughly equivalent to 20 years consumption (Mroz et al., 1983; Kuuskraa and Brandenburg, 1989). Methane contributes to the adverse environmental impacts of global warming, tropospheric ozone formation (smog), and potentially stratospheric ozone destruction. Association of methane with coal has always presented a safety problem in mines due to the potential for explosions. The rate of release of methane depends on the amount adsorbed by the coal, the adsorption isotherm for the coal, and the size of the coal particles. Mining operations can affect the particle size distribution and the production of fines and therefore the rate of release. The time the mined coal remains in the mine may also be important in determining total emissions. The methane content of some Utah coals was determined in this study. The methane content of the coals is compared with the chemical and physical properties of the coals and the properties of the seam and neighboring strata. Correlations are developed to better understand the formation and retention of methane by these coal seams. METHANE FORMATION IN COALBEDS Three mechanisms for methane formation may be considered: (1) nonbiogenic formation, (2) formation by anaerobic bacteria during plant material deposition and the early stages of diagenesis, and (3) formation from pyrolysis of coal material during coal maturation. Nonbiogenic formation by thermal processes involving carbon- and hydrogen-containing compounds has been proposed as a mechanism for methane formation in the earth. It is not likely to be of importance where other fossil fuel materials are present. Coal would not survive the temperatures required and hence the methane would need to migrate and be trapped by the coal seam. This mechanism is unlikely for coalbed methane. Formation of methane by anaerobic bacteria undoubtedly occurs during coalification, but the methane may not be trapped until the pore system of the coal is developed, and would likely be displaced by methane formed during further coalification. Methane formed by maturation of the coal material as it progresses from peat to coals of various rank is the most probable mechanism for the formation of coalbed methane. Most of the methane is adsorbed onto the walls of microvoids in coal. It has been estimated that the surface area of one kilogram of coal is between 20,000 m2 to 200,000 m2. Surface area measurements depend on the coal and also on the method of measurement. At 20 atmospheres, in some coals, the adsorbed methane is 10 times greater than methane as a free gas. At 100 atmospheres the adsorbed gas can be as densely packed as a liquid. The volume of methane gas held in coal depends on the volume of gas that exists as a free gas and the adsorbed gas capacity. The volume of free gas in the coal can be calculated from the kinetic theory of gases (methane can be assumed to be an ideal gas because errors would not be greater than 1 % for normal mining pressures). Langmuir (1916) derived an equation for the adsorption of gases on uniform surfaces and this is applied to the adsorption of methane on coal:

Jan 1, 1993

By Tevfik Güyagüler

Airborne dust is one of the important environmental problems in mines. Besides conventional dust control methods, recently, extensive studies have been carried out on the elimination of dust before it has actually been formed. Determining to what extend rock characteristics influence the amount of dust produced during different mining activities are considered as a guide for this purpose. The factors analyzed in this study were main mechanical, physical properties and petrographical constituents, namely free and combined silica. In the study regression analysis techniques were applied to investigate the effectiveness of aforementioned factors. INTRODUCTION Nearly every aspect of mining activity contributes to the air pollution caused by dust. Therefore the harmfull effect of airborne dust has been investigated many years and limit dust concentration levels were determined for various types of mine dust. To keep the dust level below limit value different dust control techniques have been applied in mines. So far, the well known techniques regarding dust control focuses on reducing the amount of airborne dust. However, recently various studies have been carried out to avoid the dust before it has actually been formed (Bhaskar and Gong, 1991). In this respect, influence of rock characteristics on dust formation is regarded as a guide for this purpose. The present contribution describes such a study in which the drilling operation is considered as the source of the dust. In this study drilling and dust sampling process were undertaken in a model gallery that simulates an underground working. The mechanical and physical properties of the rock samples were measured in rock mechanics and ore dressing laboratories. Quartz and combined silica contents of the rock samples, on the other hand, were determined in the laboratories of geological engineenring department. Rock samples used in the research were different types of coal measure rocks, namely, sandstone, shale and conglomerate. The rock characteristics studied in this work are brittleness, toughness, rock strength, hardness and hardgrove index as inherent properties; free silica, and total silica contents of rock samples as petrographical constituents. Although there have been various studies to determine the effect of rock characteristics on the dust formation, still the type and extend of effectiveness have not been understood clearly. LITERATURE REVIEW Most of the studies investigating the effect of rock properties on dust formation concluded that they are effective. In such an investigation, it has been found that inherent rock properties influence dust formation (Das, 1973). In the another study, dustiness of the air was considered as a function of the composition, hardness and moisture content (Panov, 1967). It was also accepted that in a drilling operation more fine dust is produced if the rock to be drilled is hard (Skochinsky and Kamarov, 1969). In some other investigations dust production were considered as a function of hardgrove index (Moore and Bise, 1984) or formulated in terms of brittleness, toughness and hardness (Güyagüler, 1991). The effect of the petrographical properties of coal or rock on dust formation characteristics have also been studied (Baafi, 1979) (Panov, 1967). Because of its importance, various researches were conducted the study to find out the effect of free and combined silica content of dust on dust formation. In one of the study, the relationship between quartz in the coal seam and quartz in the airborne coal dust was investigated (Ramani et al, 1988).

Jan 1, 1993

By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O'Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By W. I. Duvall

A brief review of the resonant frequency and ultrasonic pulse methods for obtaining elastic constants of rock samples shows that the equations for an iso-tropic elastic solid commonly used to calculate Young's modulus, modulus of rigidity and Poisson's ratio can result in appreciable error if the rock is even slightly anisotropic. Consideration of the equations that relate bar velocities and free medium velocities to elastic constants for orthotropic, transversely isotropic and isotropic solids shows that a combination of the two methods can be used to determine average elastic constants for a single sample of rock. The determination of elastic constants in different directions requires a large number of tests on oriented samples. The use of both the resonant frequency and ultrasonic pulse methods is recommended so that the determination of both Young's modulus and modulus of rigidity is independent of the determination of Poisson's ratio. The dynamic elastic constants of rock can be determined in the laboratory from measurements on small samples which may be in the form of right circular cylinders (diamond drill core). Either the resonant frequency6 or ultrasonic pulse method1 can be used to determine the longitudinal and shear velocities in the same specimen. The resonant frequency method provides a measure of the longitudinal bar velocity, V,, and the torsional bar velocity Vt; whereas the ultrasonic pulse method provides a measure of the free medium longitudinal velocity, Vp, and the free medium shear velocity, V, . The elastic constants (Young's modulus E, modulus of rigidity G, and Poisson's ratio v) are calculated from the density of the specimen, p, and one of the pairs of velocities by means of equations from isotropic elastic theory. For the resonant frequency method the equations are: It should be noted that Eq. 5 is derived from Eq. 4 and 6 and the relation between the elastic constants for an isotropic solid as given by the first part of Eq. 3. The in situ determination of dynamic elastic constants is accomplished by generating a complex seismic pulse in the rock and measuring the arrival times for the longitudinal and shear phases of the pulse at two distant points.5 From these travel times and the distance of the travel path both Vp and Vs are determined. The density of the rock is determined from samples in the laboratory, and Eq. 4 to 6 are used to calculate the elastic constants. These three methods involve the assumption of isotropy and perfect elasticity, and require the use of the relation v = (E/2G) - 1, which holds only if the elastic constants are the same in at least two directions. The calculation of v by means of Eq. 3 introduces considerable error, as a 1% error in V, and V, results in a 20% error in v. If frequencies for samples with a length-to-diameter ratio greater than four and a length greater than 8 in. are measured carefully, the experimental error can be kept to 1%. However, it is not unreasonable to expect that the variation in Vb and Vt with direction may exceed 1%. Thus, for even a small percentage of anisotropy the use of Eq. 3 can result in considerable error in v. The calculation of v by Eq. 5 also involves some uncertainty as a 1% error in Vs and Vp can result in a 6% error in v. By means of the pulse method both

Jan 1, 1965

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.',' These liquids include surface-active agents," recipitates' and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement

By P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the annealing texture of highly rolled aluminum consists of the four retained components of the rolling texture near (123) [121], rather more sharply developed, and of a cube texture component. Local reorientation corresponds fairly well to 40 rotation around a [111] axis. In copper strip rolled 96 pct, the annealing texture is mainly the cube texture, with the four twin orientations as minor components. The annealing texture of highly rolled brass strip consists of four components of the (225) [734] type. REVIEWS by Wassermann,' Barrett,' Dunn,3 and Richards' give detailed accounts of the numerous publications dealing with annealing textures in rolled polycrystalline metals. Although a considerable amount of information of an empirical nature has been available for many years, even relatively recently the state of recrystallization-texture theory was considered uncertain. The reviews referred to above deal mainly with the description of experimental results, without developing generally applicable principles, suitable for explaining the observed annealing textures. The investigations of Burgers and Louwerse5 and Barrett6 showed that in deformed single crystals of aluminum the orientation of the recrystallized grains deviates drastically from that of the deformed matrix. According to Barrett and to Beck and Hu,7 the relationship between the two orientations can be best described as a rotation of about 40° around a [111] axis. Recent investigations led to similar orientation relationships for various face-centered cubic metals with a simple texture, regardless of whether the annealing process was recrystallization (strain-free grains growing in a highly deformed large crystal of aluminum' or copper: or in deformed cube texture copper") or coarsening (strain-free grains growing at the expense of an essentially strain-free, fine grained, polycrystalline matrix of single orientation texture copper,'" aluminum,' or nickel-iron). Barrett" pointed out the possibility that this orientation relationship may be a result of the orientation dependence of the rate of grain boundary migration. More recently, considerable evidence became available in favor of this view.12,13 In apparent contradiction to the above results, it has been known for a long time that the recrystallization texture of polycrystalline metals is often similar to the deformation texture. This was found, in particular, for the fiber textures obtained by wire drawing, compression, or compression rolling.' Following a suggestion by Barrett,2 Kronberg and Wilson and Beck and Hu7 described a mechanism by which a [Ill] fiber texture, resulting from plastic deformation, may be retained upon recrystallization, even though the orientation of individual recrystallized grains differs from that of the local area of the matrix in which they grow. This mechanism assumes that the reorientation corresponds to a rotation around the [1ll] axis, which is also the fiber axis. The present investigation was undertaken to examine in detail the orientation relationship between deformation texture and recrystallization texture in rolled face-centered cubic metals, using the quantitative methods of texture determination that have recently become available.", '" Quantitative pole figures for the rolling textures of such metals were reported recently." Quantitative pole figures for annealing textures are given in the present paper. It was planned to investigate whether or not the orientation relationship previously found for the recrystallization of deformed single crystals, and for coarsening of single-orientation texture material, is capable of accounting for the observed, often complex, annealing textures in rolled polycrystalline metals. The question whether local reorientation is predominant, even in the early phases of the annealing process, was to be studied with high purity aluminum. by making use of an oxide film and sensitive tint illum-

Jan 1, 1953

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965