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By Maria D. Mastalerz, Wei Wang, Maria E. Holuszko, Amit Kumar

In this study, the micro-FTIR analysis was used to investigate in-situ surface properties of coal and its components (macerals) and these were directly correlated to the coal hydrophobicity as measured by the contact angle before and after reagent addition to understand the suitability of the reagent for flotation. The micro-FTIR technique can provide a semi-quantitative analysis of the chemical functional groups on coal surface, exactly where the contact angle is being measured. Selected functional groups and their ratios that provide information about aromaticity, the contribution of oxygenated groups, and aliphaticity are used to evaluate the reactivity between reagents and various coal components. The observations made in relation to the susceptibility of some reagents towards certain coal components should lead the way to a smarter way of using process design in terms of reagents selection for coal flotation.

Jan 1, 2017

By Gordon T. Austin

Garnet is the general name for a family of complex silicate minerals having similar physical properties and crystallizing in the isometric (cubic) system. All garnets have the same general chemical formula but vary greatly in chemical composition. The name garnet is derived from the Latin word granatus, meaning like a grain, which refers to the mode of occurrence wherein crystals resemble grains or seeds embedded in the matrix. GEOLOGY Mineralogy Chemical Properties: The general formula for garnet is A3B2(SiO4)3, whereas A can be calcium, magnesium, ferrous iron, or manganese, and B can be aluminum. ferric iron, or chromium, or rarely titanium. The formulas and names of common garnet species are: [ ] Almandite and almandite-pyrope solid solution garnets are the best abrasive types, but andradite, grossularite, and pyrope also are used. All species of garnet have been used as gemstones. The structure of garnet consists essentially of isolated SiO, tetrahedra connected by oxygen-cation-oxygen bonds through the distinct A and B group cation sites. Within this structure magnesium, ferrous iron, and manganese easily interchange and substitute for each other in the A cation position, and calcium does so less readily. Additionally, aluminum, femc iron, and chromium substitute for each other to a limited extent in the B cation position. This ability to substitute or exchange ions without changing the crystal structure is called isomorphism, and garnet is one of the finest examples of a isomorphous series. Because of this isomorphism there is complete solid solution between certain garnet species but not between others. Fig. 1 illustrates these solid solution relationships. Some rare species of garnet are known that illustrate the wide range of cation substitution that the garnet crystal structure can accommodate. They include: [ ] These rare species are not of interest for industrial applications, but can be of interest to mineralogists and the gem industry. Physical Properties: Garnet displays the greatest variety of color of any industrial mineral. Garnets have been found in all colors except blue. For example, grossularite can be colorless, white, gray, yellow, yellowish green, various shades of green, brown, pink, reddish, or black. Andradite garnet can be yellow- green, green, greenish brown, orangy yellow, brown, grayish black or black. Pyrope is commonly purplish red, pinkish red, orangy red, crimson, or dark red; and almandite is deep red, brownish red, brownish black or violet-red. Spessartite garnet can be red, reddish orange, orange, yellow-brown, reddish brown, or blackish brown. A few garnets exhibit a color-change phenomenon. They are one color when viewed in natural light and another color when viewed in incandescent light. Because of the great variation in color of garnet within each species and similarities in color between garnets of different species it is recommended that garnet identification not be based on color alone. The Mohs hardness of garnet varies from 6.5 to 9.0. Grossularite and uvarovite have a hardness of 6.5 to 7.5; andradite is 6.5 to 7.0; and pyrope, almandite, and spessartite are 7.0 to 7.5 in hardness. There are reports of almandite having a hardness of between 8.0 and 9.0. As with hardness, the specific gravity of garnet varies considerably. The specific gravity may be as low as 3.2 or as high as 4.3 depending on chemical composition. Garnet crystallizes in the isometric system with rhombic dodecahedra and trapezohedra the most common forms. Crystals also form in combinations of dodecahedra and trapezohedra or either of these in combination with hexoctahedra. Crystals can have cubic or octahedral faces, but these are rare. Under favorable conditions of formation garnet will crystalize in nearly perfect forms that rival study models. Garnet also forms as irregular blebs, grains, knots, or masses, with or without distinguishable crystal faces, and as coarse- or fine-grained granular masses that appear to be totally lacking in crystal form. The fracture of garnet also shows great variation. In some garnets, particularly those that are well crystallized and glassy in appearance, the fracture is subconchoidal to conchoidal. Other, more poorly crystallized garnets exhibit a fracture that can only be described as uneven. Garnet occasionally has an indistinct dodecahedral cleavage. Certain species of garnet from specific locations have a pronounced laminated structure consisting of planes of weakness along which parting takes place. This parting may resemble cleavage, but since it is mechanical and not related to crystal structure it is not true cleavage. The optical properties of garnet are sensitive to even small changes in chemical composition or strain in the crystal structure. For this reason each species does not have a single index of re- fraction (IR) but has a range of 1Rs. Uvarovite in its pure form should have an IR of 1.870, but in nature samples vary from 1.74

Jan 1, 1994

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By Dave Southworth

After Abe Lee discovered gold (in April 1860) near the site of present-day Leadville, Colorado, he and is group staked nearly all of California Gulch with "speculative claims." They did so in an effort to grab any property that might be potentially profitable. But the plan did not work. New prospectors demanded a miners' meeting, from which arose the official "Bylaws of California Mining District, California Gulch, Arkansas River." These bylaws, adopted on May 12, 1860, established provisions as to the number, size and type of claims that could be filed. Fair laws invited more newcomers. By mid-summer, 5,000 people with tents and wagons were scattered from one end of the gulch to the other.Among the earliest arrivals to the region that spring were Horace Austin Warner Tabor and his wife, Augusta. H.A.W. Tabor, who was to become a pillar in the development of Leadville, arrived at California Gulch during a food shortage. He sacrificed his oxen so that hungry miners could eat. By doing so, he immediately became the friend of many. Augusta established a little store where she sold her baked goods and provided meals. Like most of the men, Horace prospected the surrounding hills. He only did so, however, for a short time. California Gulch yielded more than $5 million in gold during the next five years. By 1866, however, the placer gold was gone and most of the miners had packed up and left. Charles J. Mullen and Cooper Smith, who were grubstaked by a Philadelphian named J. Marshall Paul, found a new, rich lode at the Printer Boy Mine in 1868. It was the first underground gold mine in the Leadville area and marked the transition from surface mining to underground hard rock mining. Its discovery created a new but modest flurry of activity. Heavy black sand covered the region and made gold mining difficult. In 1875 William Stevens and Alvinus Wood decided to have the sand assayed. They discovered that it contained 15 ounces per ton of silver and was rich in carbonate. Stevens and Wood kept their find a secret for nearly two years. When the word spread in late 1877, the silver boom was on. In 1878 prospectors, merchants and others trickled into town from all directions. Dr. David H. Dougan closed his office. in Alma, crossed Mosquito Pass and set up shop in Leadville. Nobody seemed to need a doctor, however, and Dougan sat in his office for 28 days without a customer. On the 29th day he received word that there had been a mining accident and he was needed immediately. -That was the begin¬ning of his illustrious career in Leadville. Dougan was a successful physician, became mayor in 1881 and was later president of the Carbonate National Bank. Leadville was a simple community of log structures in 1878. By June of the following year, however, it had blossomed considerably. According to Cass Carpenter, as of May 1,1879, Leadville had "...19 hotels, 41 lodging houses, 82 drinking saloons, 38 restaurants, 13 wholesale liquor houses, 10 lumber yards, 7 smelting and reduction works, 2 sampling works for testing ores, 12 blacksmith shops, 6 livery stables, 6 jewelry stores, 3 undertakers and 21 gambling houses where all sorts of games are played as openly as the Sunday School sermon is conducted." Additionally, there were 36 brothels. When George E. King and other architects arrived, Leadville took on an air of elegance and sophistication. In sharp contrast to some of the Victorian-style, gingerbread-laced homes in Leadville, its suburbs were comprised of many tenement shacks and plain cabins mixed with a few commercial buildings, many mines and smelters. Mines sprinkled the area east of Leadville like pepper from a pepper shaker. Wherever there was a cluster of mines, a camp usually sprang up. Most were very close together. South of Leadville the giant Arkansas Valley lead smelter sprawled out between Stringtown and Bucktown in an area known as Smelter Valley. Founded in 1879 as the Billing and Eilers Smelter, the Arkansas Valley plant was operated by the American Smelting and Refining Company. Several other smelters operated in the vicin¬ity. In April 1878, Horace Tabor grubstaked prospectors August Rische and George Hook. For $64 worth of supplies and tools, he was guaranteed a one-third interest in their findings. Rische and Hook discovered the Little Pittsburg (often spelled Pittsburgh) Mine and made Tabor an instant millionaire. Tabor once purchased a "salted" mine, the Chrysolite; but instead of considering it a bad deal, he further developed the property and struck rich silver ore. Later, Tabor purchased the Matchless Mine for $117,000, possibly the only investment he made without partners. During its peak years, the Matchless yielded $1 million worth

Jan 1, 1998

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By Matthew Janes

The RC Harris Filtration Plant, which treats the majority of the fresh water for over 2.5 million Torontonians, is a Canadian Architectural Heritage site demonstrating a classic example of Art Deco Architecture. The facility is undergoing an expansion to install an underground sludge treatment capability. Perched atop a bluff on the North shore of Lake Ontario the structure enjoys a commanding presence on the Lake Ontario shoreline. A series of underground tanks were proposed for the hillside below the structure, which when covered would preserve the building?s architectural presence. However, the plan required two, stepped excavations 12 m and 10m deep into compact, wet sands over stiff clays and clayey silts. Concerns regarding the original structure influenced designers to set the lateral deflection limit for the front footing of the existing structure at 4 mm, (0.03% excavation depth). The design-build team indicated at the time of tender that the movement criteria was unattainable using the tender design. Analysis indicated installation effects and overall elastic movement of the soil mass beneath the building would result in movements of 7 to 9 mm at the structure. Through extensive FLAC analysis and a novel construction geometry the design-build team crafted an alternative that produced significant savings over the original concept. Based upon the analysis the design-build team negotiated a new deflection criteria dictating a maximum of 2.0 mm of movement across the critical expansion joint between the Filter Building front footing and the tank slab beyond. The contractor invested in additional pre tender soils investigation to support the refined design process. The FLAC analyses indicated the Filter Building movements would be elastic and distributed up to 50 m back beneath the front footing of the structure. An extensive precision monitoring program proved construction related movements of 6 to 10 mm horizontal at the front footing. Extensometers placed at two locations over the critical interior tank expansion joint showed no measurable movements. The overall monitoring program, including inclinometers, tilt meters, tie back extensometers (smart cables) and tie back load cells indicated a good match between recorded movements and loads and those predicted by FLAC Analysis.

Jan 1, 2006

By Denise Y. Dizon

The objectives of this study were to document the hydrologic impacts of longwall mining on streams, identify the factors affecting the extent of stream dewatering, and develop empirical trends to predict the extent of dewatering and recovery of streams in advance of mining. This study on stream impacts is a companion to a stud; conducted on ground water impacts from longwall mining, which was done as part of the same research project at the' same locations and times. The study areas are three mine sites in north- central West Virginia. Mine A, located in Upshur County, has relatively thin mine overburden under the valley streams (105-115 feet). Stream monitoring there continued the earlier work of Cifelli and Rauch (1). Stream dewatering was severe with streams often going dry over the longwall panels during baseflow conditions. The lost water was probably flowing to the mine. Dewatering began in streams over the mine entry areas adjacent to the panels and as much as 380 feet from the nearest panel edge. The angles of dewatering influence ranged 22 to 72 degrees with respect to the nearest mined panel edge. Discharge then typically increased as the streams- flowed across the panel edge, but then decreased again over the panels. These streams were often ponded by local reversals in hydraulic gradient caused by land subsidence, and often dried up after flowing a few hundred feet across the panels. This occurred over panels that were previously mined up to eight months before. Mine B, located in Monongalia County, has relatively thick mine overburden (475-485 - feet) under the major stream. Stream dewatering was severe there during warm season baseflows, with complete dewatering occurring then over the longwall panels. This dewatering occurred over mined panels up to five years old, probably in response to a major anticlinal axis lineament and fracture zone in the stream valley. Mine C. located on the West Virginia -Pennsylvania border, has relatively thick mine overburden (about 585-630 feet) under the monitored streams there. stream dewatering was only partial, and these streams typically recovered their lost discharge downstream of the mine, indicating that lost water was not recharging to the mine. Only longwall panels less than one year old were associated with stream dewatering.

Jan 1, 1990

By P. E. Hildebrand, S. W. Mao, C. N. Crain

Hydrologic and economic criteria figure in many obvious ways in water resources development, but they are rarely linked quantitatively, and most of the applications are pertinent only to the case in point. In the preparation of a regional plan for the massive program of groundwater development in the Punjab, situations have arisen where the choice among two or more alternatives was made by analyzing the economic implications of critical hydrologic parameters. Two of these situations which are of more or less general interest are described herein. The first involves basic development policy, i.e., the question of whether groundwater development should be based on the demand of the economy, or the conservation concept of safe yield. The analysis demonstrated that mining of groundwater is clearly indicated for areas where alternative supplies are unavailable. The second problem involves integrating hydrologic data into an economic model to determine optimum well design. From an analysis of all pertinent factors, a simple nomograph was derived for determining well specifications on site during construction. The nomograph can be modified for use in any alluvial terrain. In the Northern Zone of the Indus Plains —the region known as the Punjab- Pakistan is proceeding with integrated development of water and land resources on a scale never before contemplated. The heart of the development plan is a massive program of groundwater development to supplement canal irrigation supplies and to provide drainage relief to the irrigated lands. By the close of 1966 about 2500 high-capacity wells were in operation and furnishing the water supply and drainage requirements for nearly two million irrigated acres. The development plan calls for the construction of a total of nearly 30,000 wells with an aggregate capacity of 120,000 cfs by 1980. This is part of an integrated program eventually affecting over 20 million acres of irrigated lands. [This development program is administered by the West Pakistan Water and Power Development Authority (WAPDA) for which the firm of Tipton and Kalm-bach, Inc. serves as regional planning consultant for the Northern Zone. The material presented herein is derived from planning studies which have been made in connection with the preparation of a regional development plan for the Northern zone.] Pakistan is proceeding with this large-scale development of land and water resources at a time when she is at the threshold of an almost calamitous population growth. Furthermore, she is attempting this development at a time when most of her usable land is already occupied and her food demands exceed current production. Here in the Northern Zone is one of the largest continuous areas of irrigated land in the world, easily irrigated, with a warm, dry climate and ample potential supplies of surface water and groundwater. Except for an abundance of land and labor, other primary resources are lacking or in very limited supply. The agriculture sector so dominates the economy that only by means of an effective development of the agricultural resources can other sectors grow and contribute to a viable economy. Because of inadequate irrigation, farming here has not effectively participated in the twentieth century revolution in agriculture, and only by means of massive development of potential supplies can Pakistan catch up. Capital for any kind of mass development must come from the outside. But the overriding restraint to development of the land and labor resources is the availability of water. ECONOMICS OF DEVELOPMENT The decision-making process in planning regional development becomes increasingly complex as the various sectors of the economy become more highly developed. Where, as in this case, one sector dominates the economy and its development can be considered the key to development of other sectors, the decision-making process is simplified and it is easier to identify alternatives and to trace the prob-

Jan 1, 1970

By C. Laird, C. E. Feltner

An investigation into the effect of a material's slip character on its high strain fatigue properties has been carried out using copper and Cu-7.5 wt pct A1 as representative wavy and planar slip mode materials, respectively. In copper, the constant term and exponent in the Coffin-Manson equation, ?EpNf1/2 = const, are unaffected by the temperature of testing or the history of the metal. On the other hand, in Cu-7.5 wl pcl Al, while the exponent is invariant, the constant is increased with respect to copper and increased further with decrease in temperature. The life in Cu-7.5 wt pct A1 is double that of copper at room temperature and about four times at 78°K. Fractoflaphic studies indicate that these diffevences in life are associated with the early stages of cracking. In copper, severe surface rumpling provides crack nuclei at pain boundaries independent of' testing temperature or the history of the metal. In Cu-7.5 wt pct Al, the planar slip mode of deformation prevents grain boundary folding; crack nucleation is therefore mainly transgranular and the increase in life with respect to copper is associated with a prolonged linking-up stage of such transgranulay cracks. At the lower temperature the increased difficulty of cross slip inhibits multiplication of trans-granular cracks and retards the linking-up process, giving a further enhaancement in life. It is expected that such behavior will be found general in materials of wavy and planar slip mode, respectively. STAGE II crack propagation in high strain fatigue takes place by a repetitive process of crack tip blunting in the tension part of a fatigue cycle followed by resharpening of the crack in the compression part.1-3 This mechanism has come to be called the "plastic relaxation process".3 At very high strains (lives to failure less than 103 cycles), most of the life of a specimen is spent in crack propagation by the plastic relaxation process.4,5 Since the differences in the cyclic strain hardening behavior of metals and alloys are comparatively small in this strain range,6,7 the amount of blunting at a crack tip depends primarily on the applied strain amplitude. The rate of crack propagation in this life range is therefore nearly constant with respect to material and temperature of testing. In the longer life portion of the high strain fatigue range (l03 to 103 cycles to failure), a considerable fraction of the lives is spent in crack initiation and Stage I growth. Grain boundaries have frequently4,5,8 been found to be the sites for this growth which is also associated with a surface folding process.4'5 Such folding behavior may also be general in any material having a grain structure and capable of plastic deformation. It has therefore been suggested475 that the universality of the Coff in-Manson law,9'10 constant,* where ?Ep is the plastic strain range and Nf the number of cycles to failure, is reflected in the approximate invariance of both the crack initiation and propagation behavior. It happens that, in most investigations of the phenomena associated with failure,4,5,8 materials with a wavy slip mode have been used as vehicles for the studies, or else "normally" planar slip mode materials have been tested under conditions giving rise to wavy glide deformation, e.g., stainless steels cycled at high temperature.'' The purpose of the present investigation was to determine whether or not different cracking phenomena would occur when the slip mode of a material is planar and if the associated life to failure would be different than that of a wavy slip

Jan 1, 1968

By W. P. Clement, M. C. Bell

"PT International Nickel Indonesia, a subsidiary of Inco Limited, mines and processes nickel laterite ores for the supply of nickel matte, primarily to the Japanese market. It has large ore reserves and a substantial portion of its energy requirement is supplied from its own hydro-electric plant. Since the early 1980s, the company has increased its production level and has dramatically reduced its unit costs. Projects are in progress to further decrease costs and recently a major expansion - 31% increase in nominal capacity - has been undertaken, consistent with marketing opportunity in Japan. The expansion project, which has a low capital cost per unit of production, is outlined in this paper.IntroductionPT Inco is a fully integrated mining and smelting facility located in Indonesia on the island of Sulawesi, and is based on a very large, world class nickel laterite orebody located 60 km inland from the Gulf of Bone. Construction of a single furnace line plant started in 1973. Complete supporting infrastructure of townsite, hospital, schools, shopping centres, road systems, and an airport, all had to be built. Prior to completing the first phase, the decision to expand the plant to a three kiln-furnace line was made. A major factor in the decision was the ability to develop the hydroelectric potential of the nearby Larona River. This involved construction of a 30 m high dam, and a 7 km surface canal to the generating station. The penstocks drop 150m to three 55 Mw turbines. The power generated is sufficient to supply the entire electrical load for the complete smelting complex and town site. The unique capability to supply the high smelting energy requirements for a lateritic nickel ore by fully captive hydro power, has, over the past decade insulated PT Inco from the large upward swings in oil prices suffered by other lateritic nickel producers.Wet ore is first partially dried to 20% moisture in two co-currently fired rotary driers, screened on an internal trommel, and delivered to two dry ore storage buildings. The partially dried ore is calcined at 750°C and partially reduced in three large 100 m by 5.5 m kilns. Reduction is accomplished by lancing bunker C oil onto the ore bed at the discharge end of the kiln. The kilns are equipped with five air pipes with onboard blowers to gradually bum the combustible gases generated by the lance oil. The kilns were also originally equipped with two side burners to supply additional heat close to the feed end of the kiln. Calcined ore is transferred by 20 ton refractory lined containers to the furnace feed bins at the top of the smelter. Smelting is carried out in three 18 m diameter furnaces powered by 45 Mw transformers. Slag is skimmed at 1550°C through water cooled breast plates and removed to the slag dump by Haulmaster Carriers. Matte of 25% Ni, 1O% S, 65% Fe is tapped at 1350°C into the converter aisle. The iron is slagged in converters to produce a nickel sulphide matte at 80% Ni. Three rotary Kaldo converters were initially installed. The product matte is granulated, dried, and shipped in returnable rubber bags to Japan. Most of the matte is fluid-bed roasted to nickel oxide and then directly reduced in a second reducing fluid bed reactor at our facilities in Japan.The smelting complex was designed to smelt two million tonnes of dry ore per year, equivalent to 34 000 tonne nickel production at an ore grade of 2% Ni. The cost of the entire project including working capital was $900 million."

Jan 1, 1990

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By C. B. E. Douglas

The following analysis was stimulated by a previous article on evaluation of the water problem at Eureka, Nev., which describes a method using formulas especially devised to calculate flow potential of extensive aquifers characterized by relatively even porosity and permeability throughout. The present discussion submits that the method was unsuitable for solving the kind of problem occurring at Eureka, where the amount of water available, rather than the flow potential, may have been the vital factor. IN an interesting article on evaluation of the water problem at Eureka, Nev.,1 W. T. Stuart describes how a difficult water problem, or one phase of it, may be evaluated by means of a small scale test. Test data are plotted by a method rendering, under certain conditions, a straight-line graph that can be projected to show how much the water table will be lowered by pumping at any specified rate for a given time. A formula is then used to determine the size of opening, or extent of workings, necessary to provide sufficient inflow to enable pumping to be maintained at that rate. At first glance this might seem the answer to a miner's prayer, but a word of caution is in order. It may not be the whole answer. Moreover, results obtained by the method described are reliable only for conditions approximating those assumed. Even where conditions do not meet this requirement, however, it may be possible to draw helpful inferences from the results, perhaps enough to facilitate another approach to evaluation of a problem. The two formulas Mr. Stuart used, the Theis formula and the one developed from it by Cooper and Jacob, were given field checks a number of years ago in valley alluvials by the Water Supply Div. of the U. S. Geological Survey and found to be reliable when the aquifer is very large in horizontal extent and sufficiently isotropic for the test well and observation wells to be in material of the same average permeability as the saturated part of the aquifer as a whole." Extensive valley alluvials, sands, and gravels can be evaluated in this way, and there are even cases in which the method could apply to porous limestones, such as flat beds of very large areal extent that have been submerged below the water table after extensive weathering. These are sometimes prolific sources of water for towns and industries. It is necessary for them to have been above the water table for some geologically long period of time in a fairly humid climate before submergence because the necessary high porosity and permeability, and large reservoir capacity, are the result of weathering, that is, of solution by the carbonic acid (H,CO3) in rainwater formed by the absorption of CO, from the air by raindrops, and this dissolving action must cease when all the H2CO3 has been consumed by re- action with the carbonate to form the more soluble bicarbonate. Consequently this weathering process is largely restricted to a zone that does not extend much below the water level, and submergence is necessary after the weathering to provide large reservoir capacity and good hydraulic continuity. On the other hand, water courses tend to form along faults and fractures in limestone, and to become enlarged by solution, well below water level when, as often happens, fresh meteoric water is circulated rapidly through them to considerable depth by hydrostatic pressure, as through an inverted syphon. Although the reservoir capacity of such water courses is relatively small they may extend far enough to tap more prolific sources. Cavities, and sometimes caves of considerable size, are found in limestones where the acid formed by the oxidation of sulphides has attacked them. This action can take place as deep below water level as surface water is carried by syphonic or artesian circulation, because the oxygen it carries in solution will not be consumed until it reacts with some reducing agent, such as a sulphide. Moreover, the formation of acid and solution of limestone in this way is not confined to the immediate vicinity of the sulphide. Oxidation of pyrite, for example, results in formation of acid in several successive stages, each taking place as more oxygen becomes available, as by the accession of fresh water into the circulation at some place beyond the sulphides. When the acid thus formed attacks the limestone, CO, is liberated and the ultimate effect of the complete oxidation of one unit of pyrite will be the removal of six times its volume of limestone as the sulphate and bicarbonate, both of which are relatively soluble. The reaction may be continued or renewed along a water course far from the site of the sulphides, where the small electric potential produced by contact with the limestone helped to start the reaction. Mr. Stuart refers2 0 caves in the old mining area in the block of Eldorado limestone southwest of the Ruby Hill fault at Eureka, Nev., and to the cavities encountered in drillholes in the downthrown block on the other side of the fault. Although he interprets these cavities as evidence that this formation was sufficiently isotropic (evenly porous and permeable) to give reliable results by the method he describes, they may, in fact, be entirely local conditions. There is reason to think they were probably formed

Jan 1, 1956

By P. T. Chiang

Chemical etching methods for the simultaneous revealing of the tellurium or selenium Phase and the chalcogenide grain boundaries of the alloy systems are given. A tellurium eutectic was found Present in zone-melted ingots. Similarly, a selenium monotectic was present in ingots. In general, the second phase (tellurium or seleniumn) occubies three different sites; viz., along the chalcogenide grain boundaries, as inclusions within the chalcogenide grain, and on the undersurface of the ingot. The detection limit for the tellurium phase is about 1 u in width. THERMOELECTRIC materials based on Group V (bismuth, antimony) and Group VI (selenium, tellurium) elements have aroused considerable interest in recent years in the practical application of thermoelectric cooling. In many cases, a small amount of excess tellurium (or selenium) was added to the material to optimize its thermoelectric properties. Then the question immediately arises as to the number of phases present in the resultant alloy. In the binary systems of Bi-Te, Sb-Te, and Bi-Se, the congruent melting compositions have been reported to be non-stoichiometric and are represented by Bi~Te respectively. It is to beexpected and known that Bi2Te3 and SbzTe3 crystallize from the melt with an excess of bismuth and antimony in the lattice and that tellurium forms a eutectic.~' The same could be assumed to take place in the pseudo binary systems of (Bi,Sb)zTe3 and Bi2(Se,Te)3 as well as in the system studiedby puotinen5 and other workers. Likewise, BiaSe3 crystallizes from the melt with an excess of bismuth in the lattice and selenium forms a monotectic.~ Therefore, in practice, alloys solidified from the melt often contain a second phase (tellurium or selenium) in one region or another of the solid mass even without the addition of excess tellurium (or selenium). ~u~~recht' studied the thermoelectric properties of (Bi,Sb)2Te3 alloys with excess tellurium and simultaneous additions of selenium. He mentioned that the materials show two phases because of the considerable excess of tellurium or selenium. However, he did not report as to how the tellurium or selenium phase was identified. It is generally believed that the presence of an excessive amount of tellurium or selenium phase in the alloy would adversely affect its thermoelectric properties and its uniformity. Consequently, there is a need for a simple method for the identification of the tellurium and selenium phase. The quantity of the second phase present is usually too small to be detected either by chemical analysis or by normal X-ray techniques. This investigation was therefore carried out, first, to devise a simple metallographic method for the identification of the tellurium or selenium phase coexisting with the chalcogenides and, second, to determine the distribution and specific location of the tellurium or selenium phase in the ingots. EXPERIMENTAL PROCEDURE The starting materials used for the alloy preparations were 99.999 pct pure bismuth, antimony, and tellurium and 99.997 pct pure selenium. The bismuth and antimony were obtained from Consolidated Mining and Smelting Co. of Canada Ltd., while the selenium and tellurium were obtained from Canadian Copper Refiners Ltd. The tellurium was purified further in the laboratory by zone refining. The elements were pulverized in a stainless-steel pestle and mortar. The amounts for the desired composition were weighed out each time on an analytical balance to make up a 100-g sample. Then the sample was introduced into a Vycor ampule (19 by 150 mm), pumped down to a vacuum of 10"5 Torr for 15 min, and sealed off. The ampule was then heated in a horizontal resistance furnace at 800" to 900°C for about 20 hr. During this period the assembly was rocked back and forth several times to ensure good mixing. At the end of the heating period, the ampule was quenched in cold water and then transferred to the zone-melting apparatus described in a previous publications to grow large-size aligned polycrystals. The background and ring-heater temperatures were adjusted to make the freezing solid-liquid interface slightly convex to the liquid. The recorded temperature gradient in the vicinity of the freezing solid-liquid interface was around 15°C per cm. The ampule was moved horizontally at a speed varying from 0.4 to 2 cm per hr so that the ring heater would cover the whole ingot length from end to end. A single zone-melting pass was used for the Bi-Te, Sb-Te, and Bi-Sb-Te ingots. Two passes in the forward and reverse directions were carried out for the Bi-Se and Bi-Se-Te ingots. Six passes in the forward and reverse directions were performed for the Bi-Sb-Se-Te ingot. The zone-melted ingots were found to contain several large crystals, with their basal planes (0001) approximately parallel to the growth axis. Samples of bismuth and antimony tellurides coated with a layer of tellurium, and bismuth selenide coated with a layer of selenium, were prepared for comparison in phase identification. These coatings were made by dropping a piece of the zone-melted ingot into some molten tellurium or selenium under argon atmosphere and allowing them to cool slowly to room temperature. The metallographic specimens were prepared by

Jan 1, 1969

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By Joey R. Kish, Shooka Mahboubi, Hatem S. Zurob, Gianluigi A. Botton

The kinetics of the Cr2O3-based scale oxidation and volatilization were studied in the presence of water vapour (H2O). A commercial Cr2O3-based scale forming Type 310S stainless steel was examined at the ambient pressure (0.1 MPa) and 550ºC in relatively low and high H2O containing environments of air- 10% H2O and air- 70% H2O, respectively. The increase in the partial pressure of H2O (pH2O) from 10% to 70% resulted in transition of the oxidation and volatilization kinetics from the parabolic rate law for air-10% H2O to the paralinear rate law for air-70% H2O. The kinetics transition was attributed to the increase in the Cr loss rate from the base scale after coupons exposure in air- 70% H2O. The significant role of the Mn alloying element in the base scale protectiveness was also discussed in the context of the Cr2O3-based scale stability.

Jan 1, 2017

By D. B. Dreisinger, A. A. Gunaratnam

A pressure oxidation (POX)-hot cure (HC)-lime boil (LB) process is used in industry to recover silver from refractory gold sulfide ores containing minerals such as pyrite and arsenopyrite. Pressure oxidation is used to oxidize minerals and liberate occluded gold particles. As such, iron goes into solution and under acidic and high temperature conditions often precipitates as basic iron sulfate (BFS). BFS consumes excess lime during neutralization prior to cyanidation. Therefore, a hot cure stage is required to re-dissolve BFS back into solution. BFS re-dissolution consumes acid and produces ferric sulfate. In the presence of silver, these conditions favor the slow formation of silver jarosite. Silver jarosite is refractory to cyanidation, and must be broken down prior to cyanidation. This is done in the lime boil to produce a cyanide-soluble silver hydroxide. A study was conducted to investigate parameters that affect the precipitates that form in each stage of the POX-HC-LB process.

Jan 1, 2017

By S. Castro

Hydrolysis of metallic ions depends on pH and the products of hydrolysis either activate flotation or can lead to inadvertent activation of gangue particles, but can also depress flotation of valuable components. One of the most recently studied topics is the use of seawater in flotation. Seawater is a concentrated NaCl solution (about 0.6 mol/L) that also contains considerable amount of Mg2+ and Ca2+ ions. The hydrolysis products of Mg2+ strongly depress flotation of molybdenite over the pH ranges over which they form in the process water. This effect can be eliminated by removal of hydrolysing ions from the process water or by carrying out the flotation at the pH over which such a hydrolysis can be avoided. The former can be exemplified by prior precipitation of the harmful hydrolysing ions as, for example, in the University of Concepcion Patent. The latter can be exemplified by the use of metabisulfite to depress pyrite in the flotation of Cu-Mo sulfide ores in seawater, the process that is carried out at much lower pH, which avoids formation of Mg2+ hydrolysis products.

Jan 1, 2017