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By Kira Mizell, James R. Hein, Tracy Conrad

"The Ninetyeast Ridge (NER) extends roughly N-S as a topographic feature for 5000 km, from 31° south to 10° north (Fig. 1) where it becomes buried beneath the Bengal Fan at its northern end. These two geographic characteristics make the NER an ideal natural laboratory for determining the influence of latitude and terrestrial input to ferromanganese (Fe-Mn) crust formation and composition. In addition to study of geographic controls on crust composition, the NER is the largest feature in the Indian Ocean that may host crusts of economic interest.Crusts were collected from 9 of 33 dredge sites from 1.4° north to 26° south latitudes during the 2007 R.V. Roger Revelle Knox06 cruise. Nineteen samples were analyzed for 69 elements each. Nine bulk crusts and 10 layers from four crusts were analyzed. Three of the crusts sub-sampled for layers did not have the bulk crust analyzed and the weighted means for those layers were calculated to obtain bulk compositions. One sample was left out of the statistical analyses because it is phosphatized and chemically quite different from the other samples (Table 1).In order to determine changes in composition with latitude, Pearson product-moment correlation coefficients were calculated for the chemical dataset and latitude of dredge sites, as well as water depth. At the 95-99% confidence level, the following elements increase in crusts moving north along the NER: Mg, Ti, S, Cd, Ni, Tl, Mn, Ba, Co, Cu, In, Li, and Zn; and the following elements decrease northward: Fe, Fe/Mn, P, As, Sc, the rare earth elements plus yttrium (REY), Bi, Ge, and Pb. These correlations indicate that the iron oxyhydroxide component and its associated elements are more prevalent to the south, and the manganese-oxide phase and associated elements increase toward the north end of the NER. This change occurs between dredges D20 and D14 (Fig. 1), with crusts from D20 and south having Fe/Mn !1.0 and those north of D20 ""1.2, with the exception of the phosphatized crust. Crust composition also changes with water depth: Th, Ge, Pb, and the middle rare earth elements (REEs) increase with increasing water depth. Thorium commonly increases in deeper water crusts, which explains the higher Th concentrations in Atlantic and Indian ocean crusts in general compared with Pacific crusts (Fig. 2 and Hein et al., 2012), including the samples analyzed here with a mean water depth of 3584 m. However, water depth does not explain the latitudinal changes because the mean water depths of samples along the northern and southern segments of the NER are roughly comparable. Surprisingly, Si and Al, representing the aluminosilicate/detrital phase, do not correlate with latitude; that is as the ridge approaches and is buried by the Bengal Fan the Si and Al contents do not increase. However, overall, Si and Al have higher concentrations in NER crusts than in central Pacific crusts. Ba can be used as a proxy for primary productivity and statistically does increase to the north along the ridge in the direction of the equatorial zone of high biological productivity. Correlations of Mg, Li, and Zn with latitude may also reflect increased primary productivity at lower latitudes."

Sep 1, 2014

By Charles Pol Vuillier

Piling work for modification to the Charles Grimes Bridge in Melbourne, Australia required piles to be installed through 15 to 20 m thickness of very soft to soft silty clay overlying 10 m of stiff clays and sands in turn overlying siltstone. The presence of an old sewer founded at depth in the soft clays demanded that vibrations be kept to a minimum. Two pile type were used by Vibro-pile (Australia) to provide the client with the most economical piling price. The two pile types were CFA piles of 750mm diameter founded in the weathered rock and a full displacement concrete injected screw pile developed by Vibro-pile called the "Z" pile, founded on the rock. The development and features of the "Z" pile are briefly discussed, including the perceived applications and advantages of the pile type. On board instrumentation comprising a computer was used to monitor all aspects of the construction. The rig instrumentation provided an important quality control measure that gave confidence in the pile installed. Pile performance was proved on the cast in situ piles by dynamic load testing methods. Initially tests performed with a 120 kN drop hammer, which was not capable of mobilising the required loads. The performance was then satisfactorily proved by using a drop hammer of 20 tonne mass delivering blows drop heights of 1.5m. Low strain integrity tests on a number of piles were also used to confirm the structural integrity of the piles.

Jan 1, 2000

By J. H. Hamilton, J. R. Lewis, J. H. Dismant, W. M. Fassell

RECENTLY this laboratory undertook the task of preparing some low carbon metallic cobalt by the carbon reduction of precipitated cobalt oxides. The oxides came in two lots and had the compositions given in Table I. Industrially, cobalt rondels' are made by the carbon reduction of cobalt oxide in small reverberatory furnaces at temperatures near but not above 1050 °C. This is a slow and tedious small batch process but does give cobalt metal which is low in carbon (1 pct C). Inasmuch as these cobalt oxides were relatively low in copper and iron it was decided to reduce them with petroleum carbon in a small three-phase electric arc furnace of about 3 to 5 Ib of metal capacity. It was hoped such a procedure would save considerable time and perhaps also indicate an improved commercially feasible process. The furnace was preheated by using small pieces of carbon electrodes to maintain the arc until a temperature of 1500°C was reached. The broken pieces of electrodes were then removed and 500 g of the cobalt oxides and 60 to 100 g of petroleum coke added. At the end of the reduction reaction, a high lime flux was added to the furnace to facilitate the removal of sulphur. Due to the fineness of the cobalt oxide powder used and also to the presence of chlorides there was considerable dust lost in charging the furnace. This was overcome by preparing briquettes composed of the cobalt oxides, charcoal, and a little bentonite to serve as a binder. The results obtained are summarized in Table 11, which shows that the cobalt metal produced in the arc furnace was high in carbon varying from 2.5 to 3.5 pct. This, of course, is much too high. For certain uses, such as in the preparation of permanent magnets, the carbon content of cobalt must be low. It was necessary therefore to find an effective method of reducing the carbon content of the cobalt that had been prepared in the arc furnace. Van Arkel3 recommends the use of Co2O3 as a means of removing carbon from cobalt. Experiments by the authors indicate that carbon is removed with difficulty by this method. Other methods used, including lancing of the molten high carbon cobalt with a jet of oxygen, proved to be ineffective. The method finally used makes use of the fact that cobalt metal is decarburized by carbon dioxide at the temperature of the molten metal. Two methods were used: 1—carbon dioxide was bubbled up through the molten cobalt, and 2— molten cobalt was maintained in a carbon dioxide atmosphere. In the first method the gas was introduced below the surface of the molten metal by means of a quartz tube. A high frequency induction furnace was used to keep the cobalt molten in both of these experiments. This kept the metal somewhat agitated and no doubt was an important factor in hastening the decarburization 'process by the second method. Both methods gave satisfactory results as shown in Table 111. An interesting observation in connection with this 'work was that a small sample of carburized cobalt metal could be decarburized by heating it with an acetylene torch adjusted to give an oxidizing flame. This may have been due to the presence of carbon dioxide in the products of combustion. Samples of molten high carbon steel were decarburized by the same method and it is suggested that nickel and perhaps manganese can be decarburized in a similar manner. Additional work, including rate studies and other theoretical aspects of this problem, is in progress in this laboratory.

Jan 1, 1953

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By Anna H. Connard

SUMMARY The discussion focusses on developments in the debt/equity swap market since the Marte project was negotiated in early 1988. It emphasises carrying forward the recent market trends to anticipate the breadth and scope of debt/equity conversions for mine development in the 1990s. Secondary market prices of LDC paper, conversion values and political influences in the host countries and the use of near debt and commodity-based instruments as components of mine financing in debt/equity deals will be placed in the perspective of recent trends and expectations for the future. THE MARTE PROJECT The Marte mine is a gold porphyry deposit in Chile's high Atacama, for which financing was put together at the beginning of 1988. The Marte project was financed by a combination of common equity and loans. It was unusual that the equity infusions were made under different programs. Some of the international equity was infused with fresh funds via DL 600. Other common foreign equity was provided through the conversion of Chilean bank debt under Chapter XIX. On the loan side,. export credits for the import component of machinery and equipment were sought. Local bank financing was negotiated for the remainder of ' the project's anticipated cost. The debt conversion market in Chile was at its apex in terms of interest, activity and government support when the mine financing was arranged. The price of Chilean paper in the secondary market hovered about 62 to 66 cents per U.S. dollar of face value. Meanwhile, the Chilean government was negotiating conversion redemptions significantly closer to full face value. The government differentiated between debt paper exchanged for corporate investors who had sourced that paper in the secondary market, and debt paper held by bank investors who would incur a transaction loss in the conversion. The use of a combined DL 600lChapter XIX equity financing created different yield calculation bases for the various investors. Chapter XIX prevents remittance of profits before year 5 and capital repatriation before year 11. Investors choosing this vehicle have either for a corporate policy in the target project not to declare dividends until repatriation is allowed, or they have to seek uses for the peso liquidity that would be generated through dividend declarations in the early years. However, DL 600 investors face no such waiting period on dividends, nor do they have restrictions imposed on cashing out of the investment before the 11th year. Therefore, any equity structure with components of both investment mechanisms will have inherent differences in cost basis and future income flows for the various participants. This equity imbalance is defensible if the investment motivations of the parties are analyzed: a mining investor using fresh funds looks for a hurdle return on equity calculated at conservative commodity prices, with as much flexibility to reap upside benefits as possible; a mining investor choosing to invest through a debt conversion mechanism will realize a modest short term gain on the conversion, reducing his effective cost basis, but sacrificing some return because of the waiting period on repatriation of dividends. INVESTMENT OBJECTIVES A bank investor exchanging his own paper for an equity participation in a mining project realizes a conversion loss on the transaction. He seeks a risk adjusted acceptable hurdle rate of return to recoup that loss over time. Motivation for the bank investor to take that loss may be derived partly from a strategy to diversify its existing portfolio by internal policy and externally regulated guidelines. The bank will compare yields on its loan portfolio to that country with anticipated dividend flows discounted back at a risk adjusted rate. It will analyze the project with return objectives of yield enhancement over time and with

Jan 1, 1990

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor's original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By E. Steel, V. S. Znamensky, A. Wylie

The asbestiform habit is most commonly developed in certain amphiboles and chrysotile, but other minerals also may crystallize with this unusual habit. The habit may be characterized by (1) a fibril structure, single or twinned crystals of very small widths (generally less than 0.5 pm), which have grown with a common fiber axis direction, but are disoriented in the other crystallographic directions; (2) anomalous optical properties, primarily parallel extinction; (3) unusual tensile strength; (4) high aspect ratio; and (51 flexibility. In addition, there is evidence to indicate that some amphibole asbestos may have unusual surface properties. ASBESTOS AND THE ASBESTIFORM HABIT Asbestos is defined as a group of highly fibrous silicate minerals that readily separate into long, thin, strong fibers of sufficient flexibility to be woven, are heat resistant and chemically inert, and possess a high electric insulation, and therefore are suitable for uses where in- combustible, nonconducting, or chemically resistant material is required (Gary, et al., 1974). The most common minerals that may occur with the asbestiform habit are chrysotile, grunerite (amosite], riebeckite (crocidolite), actinolite, anthophyllite, and tremolite; although the development of this habit among these minerals is rare. Other minerals, most notably other amphiboles, can occur in this habit, but no others have been mined commercially as asbestos. All asbestos is confined to metamorphic rocks, even though other habits of the amphiboles are common in igneous rocks. Slip fiber veins are the most common deposits (South African amosite, Canadian chrysotile, etc.), but mass fiber deposits also may occur such as California chrysotile or mountain leather. Field relations and experimental data support the hypothesis that metasomatism is the dominant process in the formation of asbestos fibers, amphibole as well as serpentine. The crystal habit of a mineral is the shape or form a crystal or aggregate of crystals take on during crystallization. The asbestiform habit has a number of characteristics that differentiate it from other habits. Chief among these is the fibril structure.Afibri1 is a single or twinned crystal with a very small width, generally less than 0.5 pm, and an extremely high aspect ratio; bundles of fibrils may have lengths reaching into the cm. Fibrils share a common crystal growth direction along the long axis of the fiber, but appear to be disoriented with respect to one another in the other crystallographic directions. The structure of the individual fibrils, and the organization of fibrils within a fiber may differ among the various types of asbestos. The fibril structure of asbestos is probably a factor in controlling a number of secondary properties that include high tensile strength, flexibility sufficient for weaving, and anomalous optical properties. The high tensile strength of asbestos is quite remarkable, exceeding that of the ordinary varieties by a thousand fold (Zoltai, 1978). In part, this may be attributed to the lack of defect on the fibril surfaces (Zoltai, 19781, but some contribution also must come from the existance of bundles and the nature of the ordering of and forces among the fibrils. The flexibility is not only enhanced by the fact that the fibrils may slip past one another, but by their small widths and extreme aspect ratios. However, structural defects parallel to the fiber axis also may contribute to this property. Among the common commercial asbestos types, the greatest flexibility is found in chrysotile and the least in grunerite asbestos (amosite), varying inversely with fibril thick- ness. In addition, at least for chrysotile, composition also may affect the flexibility of the fibers. Finally, most asbestos minerals are mono- clinic, but optically display parallel extinction (Heinrich, 1965, and Wylie, 1978). This also must be due, in part, to the ordering or lack of ordering of the fibrils. The fibril structure is probably a random

Jan 1, 1986

At present the feasibility of developing underground facilities for the storage of a number of products including toxic waste, oil, nuclear waste and low pressure gas is under investigation in e number of countries. A possible method of storage is in large excavations, Preliminary ventilation design work has identified that the climatic conditions encountered within these large excavations are a limiting ventilation pollutant within the ventilation system. This paper examines the design of a variety of sizes of excavation from a ventilation viewpoint. The main phases of an excavations lifetime can be divided into four main phases, these being construction, civil and mechanical fitting, storage, full and sealed. The paper details ventilation design options for the first two phases of e vaults lifetime, giving climatic simulations to assess the likely climatic conditions within the excavations for e number of facility depths. The options for climatic control are given and analyzed by means of climatic simulations techniques. l. INTRODUCTION The feasibility of developing underground facilities for the storage of a number of products is under investigation at present in a number of countries. This paper details a possible design for such a facility where the product is to be stored in large underground excavations. A facility layout has been designed with the aim of allowing concurrent construction and storage operations. Thus from a ventilation perspective the facility consists of two circuits , a construction ventilation circuit and a product ventilation circuit both of which are served by an intake and a return surface connection The construction and storage circuits are considered as independent of each other , any interaction in the form of leakage must be from the construction to the storage circuit. From the facility design a ventilation network was developed to assess the ventilation requirements of the facility. In analyzing the pollutant loads for the construction circuit two pollutants were recognised to be critical to the ventilation design , these being diesel exhaust fumes and heat end humidity. In this paper ventilation design options for the construction and civil and mechanical fitting phases of the excavations are analyzed by means of climatic simulation and options for climatic control within the vaults are outlined . 2. FACILITY DESIGN A schematic diagram of a facility design is illustrated in Figure 1. There would be two distinct ventilation circuits , one to service the construction operations and the second to serve the storage operations which occur concurrently with construction , the circuits are separated by ventilation bulkheads . Access to the facility for intake air is provided by two drifts, one to serve each circuit. Two shafts act as returns to surface. The facility consists of two distinct zones for the storage of two types of product. One type is to be stored in smell linear excavations. The second zone is for the storage of a second product in larger excavations. The maximum cross-sectional area and perimeter for the smell linear excavations are 456.25 m2 and 83.2 m, while for the larger excavations they are 440.1 m2 and 86.4 m. Excavation construction consists of three phases: 1. Initial pilot tunnel development between main intake and return to provide through flow ventilation. 2. Enlargement to produce the required finished cross-section. 3. Civil and mechanical engineering work to fit out the excavation ready for storage. It is proposed to excavate the excavations using drill and blest methods utilising diesel equipment. Spoil is to be transported to surface by a conveyor belt system. At any one time the maximum number of working places requiring ventilation will consist of ; 3 storage sites, 2 excavations under construction, 2 excavations undergoing civil and mechanical fitting. [ ]

Jan 1, 1993

By Dennis Peterson

INTRODUCTION The business arena has dramatically changed for most producers and consumers of commodities. International debt, currency shortages, political upheavals, etc., require corporations today to be sophisticated and flexible enough to change their purchasing and sales techniques in order to maximize returns. Many external factors, such as interest rates, trading partners, currency changes, and government edicts, can have an adverse effect on a company's bottom line. Totally out of a company's ability to control or predict, these. factors force the commodities based corporation to constantly re-evaluate its operating scope and domain. The principle of back-yard only operations and the laissez-faire with blinders style of management is no longer a viable way to run a business. The industrial world has been operating for the past 10 to 15 years as though there were no commodity nor raw material crisis. For developed countries the primary products sector has become marginal, whereas it was central in the first half of the century. A radical change in the method of doing business is necessary to offset a depression in the industrial economy. The risk of collapse may be heightened by a banking crisis caused by massive defaults on the part of commodity producing debtors, whether in the third world or in our own farm producing sector. The raw materials economy has become divergent with the industrial economy. This is a major change in the world economy with tremendous implications in both developed and developing countries for economic and social policies and economic theories. Basic competition issues, such as low labor costs, are likely to become less of an advantage in international trade. In developed countries these costs are going to account for a smaller portion of total costs. The total costs of automated processes are lower than those of traditional plants with low labor costs. Automation in the commodities sector eliminates the hidden but high cost of not processing at capacity created by poor quality, rejects and maintenance for product change-overs. The cost of capital will become increasingly important in international competition. Over the last ten years the U.S. has become the highest cost country in this area. Reversing the U.S. policy of high interest rates and costly equity capital should be a priority for management decision makers. In the rapid industrialization of this century, Japan developed by exporting raw materials, (principally, silk and tea), at steadily increasing prices. Germany developed by leap frogging into the high-tech industries, mainly in electricity, chemicals and optics. The United States did both. Both avenues are blocked for today's rapidly industrializing countries because (a) the deterioration of the terms of trade for primary products, and (b) it requires an infrastructure of knowledge and education far beyond the scope of a poor country. Many explanations exist for the explosion of international money flows. The shift from fixed to floating exchange rates in 1971 may have given initial impetus by inviting currency speculation. The surge in liquid funds flowing to petroleum producers after the oil shocks of 1973 and 1979 was definitely a major cause. There can be little doubt that the U.S. government deficit also played a big role. The American budget deficit has become a massive void, sucking in liquid funds from all over the world and making the U.S. the world's major debtor country. In reality, a trade and payments deficit is actually a loan from the seller of goods and services to the buyer, that is, to the U.S. From now on, the global ramifications of business will have to be treated in economic theory and business policy alike. Economic theory teaches that the comparative advantage factors of a real economy determines operative and financial policy. These comparisons -- labor costs, productivity, raw materials cost, energy costs,

Jan 1, 1990

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI' Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By Fernando A. Buttazzoni, Jorge C. Munita

INTRODUCTION To provide a background for discussing long-range financial and operational planning in the mining industry, we would like to begin by describing the role of planning in Codelco. Having taken part in Codelco's planning process since its inception in 1976, we believe that useful conclusions may be drawn for the experience we shall relate. Although Codelco is a state-owned copper producer with an important role in the Chilean economy, and is consequently very much at the core of national economic planning, the following discussion is not related to government planning but to planning in an operationally and commercially autonomous business concern with all the characteristics of a private enterprise. The only way in which Codelco differs from private business is that its financial successes or failures have a more direct impact on the countryls ability to participate in international trade, to meet its international financial commitments and to achieve economic and social growth. Thus, what follows is a presentation of the conceptual features of the planning process at Codelco and a description of the current state of planning in the company. It is understood that certain conceptual components are basic to any formal strategic planning process, and that the components of Codelco's planning process are therefore generally applicable in similar companies. First, the mission and scope of operation of the company must be defined, and goals must be set to achieve leadership in the business activities in which it engages. Having set this framework, the company must constantly scrutinize those internal elements and conditions that are essential to fulfill its mission and achieve leadership. In Codelco this means considering the actions which can best serve to define future capacities, taking into account declining ore grades and determining optimal production levels; watching over the productivity and skills of its labor force, and; keeping abreast of technological developments in non-ferrous mining and processing. If the company is proficient in these three areas, it will be cost efficient and there- fore competitive. Codelco must also watch over the business environment in which it operates. The company sells concentrate, blister and fire-refined copper, wirebar, cathodes and wire rod and must study the behavior of the market to attune its product mix to the demand existing for these various commodities in the international market and the copper consuming industries in general. By examining the internal and external environment in which the company conducts its production and commercial operations, it is able to diagnose its strengths and weaknesses, to identify the hazards it must overcome to stay ahead in the copper trade, and to take full advantage of business opportunities as they arise. CHARACTERISTICS OF CODELCO-CHILE Although our subject is Codelco, readers should keep in mind that there are many other copper producing operations in Chile, all in the private sector, and many valuable deposits that may be exploited in the future. Codelco is the only public sector copper producer, although there is one other state enterprise that operates smelting and refining facilities principally to serve a large number of very small producers of copper concentrate. In the mid-19801s, Codelco is the largest copper mining company of the world and the largest producer and exporter of copper with yearly sales totalling close to US$ 1.8 billion in 1983. Moreover, it is a highly profitable copper company at a time when the world copper industry as a whole has reported losses for several years. Codelco-Chile is a fairly new organization. The history of the four mining operations it manages is much longer: El Teniente was opened in 1912, Chuquicamata in 1915, Salavador in 1959 -- with installations of the old Potrerillos mine dating from 1927 -- and Andina in 1970. Having had separate owners, the management systems of the

Jan 1, 1985

By B. Ancker, E. R. Parker

The small-angle dislocation-boundary density of nickel and some of its alloys was investigated as a function of strength. It was found that the strength is a linear function of the density for pure nickel and for Ni-Ti alloys, but not for Ni-Co alloys. The results are interpreted in terms of dislocation theory. THE processes by which metals deform are still poorly understood, even though there has been a concentrated research effort in this field during the past fifteen years. Single crystals and individual grains in polycrystalline aggregates often develop a subgrain structure when deformed. Substructure formation occurs as a result of local plastic bending and its development is augmented by annealing at moderate temperatures.' Investigations made to date, largely qualitative in nature, have shown that the substructure is composed of a network of small-angle boundaries. The purpose of the present paper is to present some quantitative data on substructure (obtained by X-ray techniques) and to correlate the results with the strength of the metal in which the substructure existed. Nickel and some of its alloys were used for the experiments. The presence of certain kinds of foreign atoms greatly alters the formation and effect of the substructure. Polycrystalline tensile specimens were prepared from high purity nickel, two Ni-Ti alloys, and two Ni-Co alloys; the composition of these materials is given in Table I. Tensile specimens having a reduced section 1/4 in. diam by 3 in. long were machined from materials which were refined, cast, forged, and swaged in the authors' laboratories. The specimens were annealed for 1/2 hr at 1150°C, a treatment which produced grains having a diameter of approximately 0.5 mm. This rather large grain size was used to facilitate later examination of the substructure. Duplicate specimens of pure nickel and of each alloy were strained various controlled amounts in tension at room temperature and recovered for 1 hr at 800°C. (This strain induced prior to recovery will be referred to hereafter as the "prestrain.") One of each of the recovered specimens was pulled in tension at room temperature to obtain the stress-strain curves. The other bar was cross-sectioned in the gage length, carefully polished, and deeply etched to remove all cold-worked material. This specimen was then examined by the X-ray microscopic technique2 to determine the nature and magnitude of the substructure. The use of duplicate specimens permitted a direct correlation between tensile properties and substructure characteristics. X-ray microscopic studies were made with an apparatus constructed to have an average resolving power of about 4 microns. The monochromatic radiation reflected from grains which were oriented favorably was recorded on fine-grain photographic plates. These were examined at Xl00 which represents the true magnification, since there was essentially none in the X-ray system. This permitted detection of angular differences between subgrains of as little as 10 min. A very large number (over 100) of grains for each specimen was examined at this magnification and the number of substructure boundaries per grain was tabulated. An accurate relative measure was obtained under fixed experimental conditions, e.g., same grain size, resolving power, magnification, etc. The greatest source of error lay in counting the subboundaries, but this proved to be surprisingly small when repeated counts were made by different investigators. Furthermore, as the subsequent analysis indicates, whatever human error was introduced was not significant. Analysis of the Substructure Data When the number of substructure boundaries per grain was plotted against the frequency, skew (asymmetrical) distribution curves of the type shown in Fig. 1 were obtained. These are smoothed curves for the 1 atomic pct Ti in nickel alloy subjected to various prestrains and are representative of the curves obtained with all the metals. Since skew-distribution curves cannot be analyzed by elementary statistical methods, detailed investigations were undertaken in order to 1—test the consistency

Jan 1, 1955

By John L. Walter

A sintered compact of iron containing 0.007 vol fraction of glass , prepared 6). powder rnetullurgtcal lechniques, was rolled lo foil, 0.001 in. /hick. The foil sullrples were anneuled a1 650° to 850°C in hydrogen. Pri,narj recryslullization prodtnced large grains which Lc3ere highly elongnled in the rolling direclion und which had an unusual prgferred orientation. The glass parlicles assumed a stringerlike dispersiorz on working; llie slrinyers were parallel lo the rolling direction and to the long axis of the grains. The same unusual grain structure, preferred orientation, and stringerlike dispersion of purticles are found in heal-ily rolled and annealed foil of tungsten which has heen doped wilh small amounts of aluminum, silicon, and polassiutvt. Both the proper dispersion of the particles and severe working (reductions in excess of 98 pct) are necessary to produce the elongzcted grain structure. RECENTLY, the author reported on the origin of the elongated or "nonsag" grain structure in tungsten foil which was doped with aluminum, silicon, and potassium.' It was observed that particles, identified as mullite (Al6Si2Ol3), were present in the doped ingot (as sintered) and at all stages of processing from ingot to sheet or wire. It was shown that the particles, being plastic at tungsten working temperatures (up to 1550"C), underwent a "stringing out" parallel to the working di-direction. It was concluded that these strings of particles were responsible for the formation of the highly elongated interlocking grains observed in doped tungsten wire or sheet. To give further credence to this explanation of a long-observed but not understood phenomenon, it was decided to design a new system, one which was analogous to the doped-tungsten system. Thus, a bcc metal, iron, was chosen to be doped with glass which would be plastic at reasonable working temperatures for iron. The glass chosen was a #0080 Corning lime glass which melts at about 810°C. This is approximately the same fraction of the melting point of iron (0.6) as the melting temperature of mullite is of tungsten. It will be shown that all the observed unusual features of the doped tungsten are duplicated in the glass. doped iron, even to the preferred orientation of the grains in the recrystallized sheet. In the tungsten sheet the preferred orientation consists of two components, (1i3)(691) and (013)(362), neither of which has been observed as a component in textures of primary recrystallized bcc metals. EXPERIMENTAL PROCEDURE The glass, in the form of fine powder, was added to high-purity electrolytic iron powder and mixed dry. The particular composition chosen was 0.007 vol fraction of glass. After mixing, the powder was mechanically pressed to a disk 0.5 in. diam and 0.15 in. thick at a pressure of 5000 psi. The pellet was sintered, in pure dry hydrogen, for 2 hr at 8 50°C. The sintered pellet was then heated to 750°C and rolled to 50 pct reduction of thickness in two passes, with reheating between passes. The rolling temperature was then reduced to 600°C and the slab was rolled to a thickness of 0.050 in. Rolling to 0.010 in. was accomplished in several passes at 300°C. Final reductions to 0.003 and 0.001 in. were taken at room temperature. This rolling temperature schedule was similar, in terms of the fraction of the melting point, to that used in the rolling of the doped tungsten. The total reduction of thickness was in excess of 99 pct. Samples of the rolled foil were lightly electro-polished and annealed for 1 to 6 hr at temperatures of 650" to 85O°C in hydrogen. Samples for transmission electron microscopy were thinned on a Disa Electropol using AC-1 electrolyte.

Jan 1, 1968

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By Eugene F. Broome, Hugh A. Walls

Self-diffusion coefficients were measured using the modified shear cell technique over a temperature range from 31" to 401°C. These data agree within experimental error with those of Petit and Nachtrieb, which were determined from 30°to 99°C. LIQUID self-diffusion behavior in gallium has been studied previously by Petit and Nachtrieb&apos; using their shear cell technique.&apos; Data were obtained in that investigation over temperatures ranging from 30.6 to 98.7"C, and these comprise the only published data for liquid gallium. In the work reported here, diffusion data were obtained from 30.8 to 400-9.Cusing a shear cell technique different from that of Petit and Nachtrieb. This modified shear cell method and the mathematical analysis for diffusion in a finite capillary geometry have been previously described.3 PROCEDURES AND ANALYSIS The segments of the modified shear cell were fabricated from types 304 and 316 stainless steel. No corrosion problems with gallium were encountered until attempts were made to obtain data at 500°C. The diffusion capillary diameter was 1.59 mm and capillary lengths for the four sets of cell segments used are given in Table I. Gallium with a purity of 99.999 wt pct was obtained from Var-Lac-Oid Chemical Co. The gallium-72 isotope used to measure the self-diffusion coefficients was produced from this inert gallium by irradiation in The University of Texas Reactor Facility, and was checked for radiochemical purity. Following a period of isothermal diffusion controlled to within 0.0l°C, the contents of each capillary section were emptied into a counting planchet, weighed to assure that gallium had not been lost during handling, and the radioactivity determined by windowless gas-flow proportional counting. Great care was taken to obtain a reproducible counting geometry for the samples. Diffusion coefficients were obtained from the solu-tion3 to the diffusion equation for the modified shear cell problem, viz.: in which B2= C2(t)Li + L2)- CSL1-COL2 P* (C0-Cs)(L1+ L2) and L, and L2 are the capillary segment lengths. The step-function initial concentration distribution was expressed as C(x,O) = C, for -L1 = x < 0 and C(x,O) = Co for 0 < x 5 L?. Also, C2(0 = ^- fcix,t)dx Computation of the diffusion coefficients was done numerically as described in our earlier paper.3 Because of the short half-life of gallium-72 (14.1 hr) and the relatively long counting times taken to give a precise value of the diffusion coefficient, it was necessary to account for the radioactive decay both during the actual count and between counts for different samples (before and after diffusion). Thus, the average count rate Cz(t) for a second sample counted from times t3 to t4 can be made consistent with the average rate Co determined for a first sample counted from times t1 to t2 by the relationship: N(e-»i-e-M») , , C2(f) " &-«,)(*-«.-«-»«) [21 in which N is the total number of counts taken and is the decay constant. RESULTS AND DISCUSSION The self-diffusion coefficients determined in this investigation are listed in Table 11. Values of the parameters used to calculate the coefficients are given in the table, as are values of the random counting error &apos; for the concentration ratio pz and the corresponding expected random variation AD in the diffusion coefficient. The quantity is calculable from: &apos;Cg — C2(t)} , „ ,2 .-„¦, M co-csl(ACs)J W in which AC is the error in the individual count rate. The mean values of the diffusion coefficients within each temperature group are also given in Table 11. Such temperature groupings of data are reasonable because of the small variations between the temperature~.~

Jan 1, 1970

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty&apos;s theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.&apos; The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By P. Stanley Jacobsen, Hemant B. Gala, Richard E. Hucko

Coal is the nation&apos;s most abundant fossil energy resource. However, its use is limited because of the nature and amount of associated impurities, such as mineral matter, sulfur, trace elements, and moisture. The moderate-to high- sulfur content of many U.S. coals is of particular concern as current and newer, potentially more stringent, regulations require reduction in sulfur oxide emissions. Release of particulates, NOx, and other pollutants during the coal-use cycle is also of concern. The current practice of controlling sulfur oxide emissions in the major steps of the coal- use cycle is limited mainly to coal preparation by physical beneficiation and, to a smaller extent, to post-utilization cleanup (flue gas desulfurization). Approximately two-thirds of the coal from states east of the Mississippi river is physically cleaned, whereas only 15% to 20% of the operating boilers in the utility industry are equipped with scrubbers to desulfurize the flue gas (Henzel, 1988). Physical beneficiation methods can be very effective in removing mineral matter, including pyritic sulfur, from coal. These processes take advantage of the differences in physical proper- ties between coal and mineral matter to achieve the separation. In a typical physical cleaning operation, raw coal is crushed to about a 50-mm (2-inch) top size. It is then screened into coarse, intermediate, and fine sizes. Crushing the coal liberates some of the ash-forming minerals, including a portion of the sulfur that is not chemically bound to the coal. The per- centage of impurities freed from the coal matrix generally increases as the coal particle size decreases. The coarse- and intermediate-sized coals are typically subjected to a cleaning pro- cess based on differences in specific gravity between coal particles and the associated impurities. Such cleaning processes used include jigs, dense-medium baths, cyclone systems, and concentrating tables. The fine-sized (typically less than 0.5-mm) coal, if beneficiated, is typically cleaned using a froth flotation technique based on the differences in surface proper- ties between coal and its associated impurities. At fine sizes, greater cleaning potential exists because a greater portion of the impurities is released from the coal matrix. However, this potential is not fully realized owing to inefficiencies in separating fine particles using state- of-the-art flotation technology. Overall, current commercial coal preparation processes are estimated to remove up to 60% of the ash and 10% to 30% of the sulfur, depending on the coal characteristics, with product weight recoveries rang- ing from about 60% to 90% and thermal recoveries of about 85% to 98% (Versar, 1985; Science Applications International Corporation, 1987; Hoffman- Muntner Corporation, 1978). For many U.S. coals, grinding to sizes finer than those used in current coal preparation plants is required to liberate most of the physically bound impurities from the coal matrix. As noted, conventional coal-cleaning methods are not very effective at these fine sizes. Accordingly, the expanded use of domestic coal requires the development of advanced coal cleaning technologies that can provide economic performance while reducing environmental impacts. Program Goals and Objectives The overall goal of the U.S. Department of Energy (D0E)&apos;s Coal Preparation Program is to provide the scientific and engineering knowledge base that industry can utilize to produce economically competitive and environmentally acceptable clean-coal products for introduction as market conditions warrant. The coal preparation process(es) should remove undesirable components from coal and improve its handling characteristics, thus making the product coal technically, as well as economically, viable as a competitor with petroleum-derived fuels and natural gas, and with alternative environmental control technologies. The coal preparation process must be applicable to a wide variety of bituminous and low-rank coals. The cleaning process should reduce the variability among clean-coal products from various raw coals, thus significantly increasing the range of potential end uses for each raw coal. To the extent that deeply cleaned coal products have greatly reduced levels of

Jan 1, 1988