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By Wolfgang O. Gluschke

INTRODUCTION Virtually all countries have general legislation covering most aspects of mining and mineral processing, including investment and tax laws, safety and health regulation, and specific rules applying to exploration reporting procedures. Yet most developing countries negotiate individual agreements with foreign investors for major mineral projects, in particular when all or part of the expected output is exported. Such agreements are known under several different names, as for example concession agreement; technical assistance agreement or service contract; management agreement; production sharing contract; joint venture; or contract of work. The objectives and conditions governing such contracts are as diverse as these titles are. While a mining project is only one among a large mumber of similar undertakings in industrial countries, in most developing countries such projects usually have a dominating position within the country's economy. The general legislation is often inadequate and insufficiently detailed to cover all aspects of large projects with extensive foreign inputs and international markets. Therefore, the need for specific arrangements. Specific arrangements may also become necessary due to the complexity of markets for mineral products, the large number of participants - equity partners, suppliers, financial institutions, buyers, etc. - or economic and political conditions in the host country and fiscal regulations in the home country of the investors. Most agreements are concluded between governments, or government agencies, in developing countries and private industry headquartered in developed market economies - Canada and the United States of America in North America, Western European countries, Japan, South Africa and Australia - or, in some instances, with state-owned firms in these countries. There are fewer agreements between developing countries and the centrally planned economy countries - Eastern Europe and the USSR - which cannot be considered here because of absence of adequate information. Agreements can be concluded at any of the different stages from exploration through closing of a mine. While most contracts are negotiated at the time when a potentially viable ore body has been delineated and investigated sufficiently to anticipate a realistic time for commencement of production, other agreements start with "grass-roots" exploration, during operation of a mine, smelter or refinery or, exceptionally, after a temporary shutdown. While several major provisions are included in all types of agreements, others are covered in much more detail (or not at all) in some contracts reflecting the specific work programme of each project. While it is realized that subdivision and classification of complex contractual relations is necessarily arbitrary to a certain extent, such grouping is useful in practical terms, especially for the non-specialist. The following discussion, therefore, will start with a description of the major forms of contractual relation - concession, investment contract, joint venture, management agreement, service and production sharing contracts. Major issues covered in all, or almost all, agreements will then be dealt with. These include stages of development, corporate structure and control, fiscal arrangements, infrastructure development and environmental law, and dispute settlement and renegotiation. FORMS OF CONTRACT RELATIONS There has been marked change in the type of agreement entered into during the 1960s (and before) and the early 1970s and the period thereafter. While straight "concessions" - granting of exclusive rights to foreign investors over a certain deposit or areas with little restriction or well-defined obligations - were the rule during the first half of this century, more complex agreements have evolved since. Some of these cover every conceivable aspect, foreseen or only possible, and define rights and obligations of all partners to the last detail. Over the years, agreements have without doubt become more beneficial for the developing host countries, in part as a result of well-publicized nationalizations, as for example in Chile, and in part due to changed attitudes in all countries

Jan 1, 1985

By H. C. Jennison

Two distinct types of defects occur at times in copper wire as a result of the use of dies of improper design or undesirable wire-drawing practice. The conditions under which these defects may be produced, as well as precautions to be taken in order to prevent them, have been known to The American Brass Co. for many years. The quality of the copper wire bars and rods has too often and unjustly been held responsible for these particular defects and it is to correct any such belief that this paper is presented. An extremely high quality of electrolytic copper has been supplied to the trade by all refineries for the last 20 years at least. The purity of the copper would average well above 99.900 per cent. The casting of the wire bars has been handled in a generally satisfactory manner. The bars have been cast sound, with a flat to slightly crowning set and have been free from sloppy edges, cold sets, etc. In other words, the wire bars have met A. S. T. M. specifications and have been generally satisfactory. For the most part, they have been everything that could be desired from a quality standpoint yet most of the wire mills in this country and in Europe have at times held the quality of the copper responsible for the two types of defects described in this paper. As a matter of fact, these defects are produced entirely in the wire mills. The author has visited many of the large wire mills in the United States and in Europe to investigate these defects. In some cases the trouble has been so serious that the wire mill has ceased operations. At times the wire mills are reluctant to believe that they are responsible for the defective product. The effect of die design, wire-drawing practice, etc., upon the quality of copper wire has received' little study on the part of wire mills, particularly those that have commenced operations in the last few years.

Jan 1, 1930

By W. B. Watson

IN the USSR considerable technical improvements have been made in hydraulic methods of mining coal. In New Zealand coal mining by these methods is still comparatively crude. The Russian techniques are closely studied in New Zealand, and this description is based mainly on translations of technical articles. Fundamentally the methods in both countries are the same-chief developments in the USSR are the use of high pressure water jets, capable of winning all but the hardest coal without prior blasting, and hydraulic pipeline transportation where the gradient is unsuitable for flume transport.

Jan 4, 1958

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By Henry R. Joesting

DURING the past year and a half, the Territorial Department of Mines in Alaska has conducted a modest experimental program for the purpose of determining the extent to which magnetic and resistivity methods can be used in interior Alaska in connection with prospecting, mining and geological studies. Since little information is available concerning previous work,1,2 and since conditions differ considerably from those in most other regions, it was considered advisable to make a general study of the possibilities and limitations of the two methods, rather than a detailed study of any single problem. PROBLEMS One of the most serious handicaps to prospecting and geological study in interior Alaska, especially in the mature regions, is a cover of unconsolidated deposits ranging in thickness from a few feet to several hundred feet. These deposits, some of which are permanently frozen, consist of silt with varying proportions of vegetation and windblown material in the valleys and of residual deposits on the hills.3,4 The problems treated here are caused by the existence of this overburden: I. Location of buried placers. 2. Determination of depth and areal distribution of permanently frozen and of thawed unconsolidated deposits. 3. Location of water-bearing beds under unconsolidated deposits. INSTRUMENTS AND METHODS Magnetic and direct-current resistivity methods were used because they are relatively simple, rapid and inexpensive and because generally they are well suited to the study of the problems indicated. The instruments used were a vertical Schmidt-type magnetometer and a direct-current resistivity instrument similar to those used by the Geophysical Branch of the U. S. Geological Survey.5 For placer surveys with the magnetometer, a sensitivity of about 25 gammas per scale division was found suitable. For resistivity studies of frozen and thawed overburden and of underground water, the Lee partitioning method6 was found to be most generally suitable. In the Lee method a central potential electrode is placed midway between the two potential electrodes of the Wenner four-electrode configuration.7 Nonpolarizable electrodes were made from unglazed porcelain pots about 10 cm. high and 5 cm. in diameter. In order to retard evaporation of the electrolyte the sides of the pots were glazed, inside and out, with clear Duco lacquer. For resistivity work in cold weather, a nonfreezing electrolyte consisting of equal parts of ethylene glycol and a saturated water solution of copper sulphate proved satisfactory. Stainless steel rods of 3/4-in. diameter made excellent current electrodes because their bright finish enabled good ground contacts to be made.

Jan 1, 1941

By Eugene Guccione

One of the world's most respected scientists, Dr. Hans A. Bethe (see box) has concluded that if anything can solve the energy crisis, it will be coal and uranium. "It is an illusion to think that we can solve our problem by energy conservation alone. For the next few years, conservation must play a very important role, but at the same time, we must see and develop all our alternative energy sources," he said. In his series of five lectures on the energy crisis, given at the University of Utah while he was visiting professor there during February 1974, Dr. Bethe examined all the existing and newly proposed energy sources. He very quickly ruled out solar power, wind power, and tidal power. Solar power, he said, would be 3% to 4 times more expensive than nuclear energy and would only make sense in tropical areas; wind power, which could at best produce one-tenth as much energy as solar, is "for the birds;" and tidal power, which can be exploited in only a very few coastal locations, is "for the fish."

Jan 5, 1975

By Frank Reiber

The study of earthquakes long ago developed the fact that by study-ing the travel .times of the various groups of waves from the same earthquake, as received on seismographs :it varying distances, major discont'inuities in the earth's crust, could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions Below the earth's surface. As an outstanding example of the applications of this work, we have the so-called " seismograph " exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we arc dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different', in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relativtly abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results. Development of Elastic-wave Method The success of this Gulf Coast work immediately suggested the advisability of attempting to extend elastic-wave methods to a point

Jan 1, 1929

By G. W. Jr. Jarman

THE purpose of this paper is to present briefly a description of some of the special methods of separation or concentration, either singly or in combination with others, and to give certain operating data and examples. Explanation of the usual methods of large-production mill treatment, such as flotation or wet tabling, or of chemically treating industrial minerals, is not included in the scope of this paper, although one of these methods might be, in certain instances, augmented by one or more of the special methods that will be enumerated herein. Description of these special methods will be centered on magnetic separators, electro-static separators and air flotation or air tables.

Jan 1, 1938

By G. N. Maniar

G. W. Healy (union Carbide Metals Co.)-The author's paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author's recently published one1 on the CaO-FeO-Fezo3 system will be most helpful to others learning to apply Schuhmann's method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fe2O3 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By J. F. Myers, F. M. Lewis

IN the mining and handling of sulphide ores, some degree of oxidation takes place on the sulphide surfaces, which are exposed to the atmosphere. It is, moreover, well known that the oxidation compounds formed are a factor when such ores are subsequently treated by flotation. Modern operating technique and reagents are capable of contending with this condition to a major degree, provided that the proportions of the reagents used are varied correctly. This is particularly true at the Tennessee Copper Co., where the ore treated contains pyrrhotite in addition to other sulphides. A number of soluble salts, some of which are unstable, can be formed during the oxidation of the sulphide ores. Those unstable salts, whose oxygen requirements are unsatisfied, are constantly changing to more stable forms because oxygen reacts with them during the crushing, grinding and other operations of ore preparation. We add no chemicals of any kind to the ore pulp in its preparation for flotation feed. Consequently the only compounds that are present in the flotation feed are those produced by the natural oxidation of the ore in the presence of air and water. The Tennessee Copper Co. ore is composed of from 60 to 70 per cent sulphides and from 40 to 30 per cent nonsulphide material. It is not the purpose of this paper to discuss the nature of these various oxygensulphur compounds nor their effect on flotation, but to describe a method for [ ] correcting the effect. Suffice it to say that we have found that the reducing sulphur and oxygen salts have a depressing action on our bulk flotation process.1 From long experience we find that the best means of correcting for this variation in our work is to increase or decrease the quantity of xanthate, the promoting agent, as the quantity of the reducing salts increases or decreases. It was, therefore, very desirable to provide the operators with some quick and

Jan 1, 1946

By Robert Mehl

THE Widmanstätten figures found in the steels have been long recog-nized and in some aspects carefully studied,1 especially as they occur in cast hypoeutectoid alloys. Aside.from the practical importance of the structures obtained in the steels by various heat treatments, a study of the characteristics of these figures is interesting because of the rich opportunity the system affords, to, obtain new data on the mechanism of segregation from solid solutions. This opportunity is twofold: first, by changing composition within the austenite range the proeutectoid precipitate may be changed from that of ferrite to that of cementite, thus offering the same opportunity for changing the type of precipitate while maintaining the same basic lattice as that afforded by the Cu-Zn alloys;2 and second, the eutectoid inversion leads upon drastic quenching to the formation of martensite, a Widman-stätten figure of unique interest from ;the crystallographic viewpoint, particularly in comparison with those formed on-slow cooling.3 We have, therefore, two types of structure to study: that formed on slow cooling of hypoeutectoid and hypereutectoid alloys, and that formed on quenching hypoeutectoid, eutectoid, and hypereutectoid alloys. For each of these types of structure we require the crystallographic plane in the mother austenite along which the precipitate forms (we shall see that the precipitates in these alloys are invariably platelike in form), and also the orientation of the precipitate upon this plane. Some of these

Jan 1, 1933

THE object of all classification is to group together things which are alike, and separate those which are unlike. This object is essentially a practical one, enabling us to apply past experience to new conditions: Many costly large-scale experiments lose half their importance for want of proper description of the coal used, and the consequent impossibility of predicting other coals will behave in the same way. I do not, therefore, make a fundamental distinction between "scientific" and "use" classifications, except in so far as use depends on conditions, such as size or impurities which are not related to the nature of the coal substance itself. The characters chosen to define the classes of coal must be such as are accompanied by as many other properties as possible. It is not to be expected that any system of classification will enable us to predict every property of coal, since all specimens have an individuality of their own. But specimens can be grouped by a number of resemblances into species. Further, species which resemble each other can be grouped into genera.

Jan 1, 1928

By J. J. Beeson

The second part of the paper includes a detailed account of the processes of secondary-enrichment which have been effective in producing the disseminated ores. While both parts present new features, it is hoped that the discussion on secondary chalcopyrite and bornite may be of interest to those who are engaged in the study of secondary processes in other districts. The excellent work' Economic Geology of the Bingham Mining District, by J. M. Boutwell, was published in 1905. Since that time the extensive development work-surface cuts and underground drifting-of the Utah Copper Co. has made possible the collecting of samples for more detailed microscopic study. The writer has taken advantage of this fact and presents the following work, not as a criticism, but as a' continuation of the work which was begun by Mr. Boutwell. b. Acknowledgments.-The present study was undertaken at the suggestion of Dr. A. F. Rogers; to him, and to Prof. C. F. Tolman and Prof. S. W. Young, the writer wishes to express his thanks for criticism in the preparation of this paper. The writer also expresses his thanks to D. C. Jackling, Vice-President and Managing Director of the Utah Copper Co., for permission to publish this paper, and to William Spencer, D. W. Wadleigh, T. S. Carnahan, J. A. Caulfield, Percy Dayer, and Edward Norsefall, for the courtesies extended to him while a co-worker in the mines.

Jan 11, 1915

By Gerald Edmunds, R. K. Waring, E. A. Anderson

Brass is liable to failure under the combined influence of stress, certain corrosion media, and time, a phenomenon commonly termed season cracking or stress-corrosion cracking. The consequences of this are serious in applications of brass generally, including the important field of cartridge cases. Cartridge cases (70 Cu: 30 Zn) that fail from this cause may allow the escape of gas from the gun breech, a hazard to the shooter, and may not eject, thus temporarily putting the gun out of action. In loaded cartridge cases, the stress present is partly residual from the, drawing and necking operations and partly applied by the insertion of the projectile. Ammonia, present as a decomposition product of smokeless powder, air and moisture constitute corrosive media. The prevalence of season cracking has been reduced considerably, but not eliminated, during the past quarter of a century by low-temperature annealing to relieve stresses residual from fabrication, a method suggested by Diegel 38 yr. ago(I).2

Jan 1, 1945

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By Rush Sill

THE processes of superficial alteration depend on physical conditions, environment, geologic history and chemical and mineralogical composition. Superficial alteration is confined particularly to the zone of shallow circulation, as this is the zone of solution; its rocks are open and the circulation within it is compara-tively rapid. The enrichment of ore deposits in this zone, therefore, is of special interest. The depth of the vadose, or zone of shallow circula-tion, is variable, because its lower limit depends on the variable level of ground water. In moist, hilly countries its depth varies from a few feet to several hundred feet. In arid regions where the rainfall is low and evaporation great, this zone may extend to much greater depths. Permeability of the deposits . is essential to the downward migration of metals. In rocks, that have been fractured since the primary ore was deposited, there is generally more extensive and deeper enrichment than in ore deposits that have been but slightly fractured. A warm climate increases chemical action and abundant rain fall is favorable to enrichment. Low relief and slow erosion give long periods of weathering and thorough leaching.

Jan 9, 1922

By H. Ries, R. E. Somers

Bodies of pyritic ore in schistose rocks have long been known in different parts of the world. The several occurrences resemble each other in being usually of more or less lenticular shape, inclosed in walls of schist or gneiss, and carrying pyrite, chalcopyrite, and pyrrhotite in varying proportions, as the chief ore minerals. The deposits differ, however, in that sometimes one, sometimes another, of the three sulphides mentioned may predominate. The orebodies in general are more or less closely conformable with the schistosity of the wall rocks, although in cases this may not hold true. The boundaries may or may not be sharp, but in general are fairly distinct. The lenses vary in size, may occur singly, or in groups; in the latter case they may be in line, overlapping, or occasionally parallel. Pinching and swelling of individual lenses is not uncommon. The genesis of these pyritic bodies has provoked much discussion, and they have been variously classed as sedimentary, igneous intrusions, hydrothermal replacements or impregnations, etc. Indeed, in some cases different geologists have most positively assigned widely diverse origins to the same deposit, as in the case of Rio Tintol and Rammels-berg.2 It is true that in the light of modern criteria, we have been able in a few cases to decipher clearly the process of origin and so there seems no. doubt now regarding the genesis of the deposits at Rio Tinto, Spain;3 Rammelsberg, Germany;4 Ducktown, Tenn.;5 southwestern Virginia;=

Jan 1, 1918

By T. Johnston, B. Cox

The results of oxidation and corrosion experiments on niobium in oxygen and steam at temperatures of 350° to 650°C, and in dilute sulphate solutions at 300°C are presented. The oxidation of niobium in oxygen can be explained in terms of a pre-transition period, which obeys an approximately parabolic rate law, and a post-transition period in which a more rapid linear rate is partially stifled by restriction of the gas flow due to the gvowth of the porous outer film. Due to changes in the porosity of the outer layers the restriction presented by the porous outel. film attains a limiting value. Subsequent oxidation obeys a linear rate law and shows an almost linear dependence of the rate on gas pressure. liltimately a second failure of the protective film may take place leading to a further acceleration in the oxidation rate. In water vapor the oxidation of niobium follows a parabolic rate law and does not show a transition to linear kinetics. The higher oxide, Nba05, was usually absent from the NbO/NbO2 film which was formed. The addition of a small partial pressure of oxygen to the water vapo3, resulted in accelerated oxidation according to the normal kinetics for oxidation in oxygen. The oxygen reacted preferentially with the niobium, and the protective oxide film was reformed when all the oxygen had been consumed. This behavior supports the theory that nucleation of Nb205 on the surface of the protective NbO/NbO2 film is the cause of the accelerated oxidation. After oxidation in steam at high-pressure Nb2Os was found in the protective film. The mode of formation of Nb2O5 under these conditions did not produce a change in kinetics, but was thought to explain the comparatively large dependence on pressure of the oxidation rate. The kinetics of oxidation in oxygenated aqueous solutions at 300°C were similar to those for oxidation in oxygen. A penetrating attack on niobium sheet may be related to the second breakaway observed by some investigators of oxidation in oxygen.

Jan 1, 1963

By S. C. Sun, John A. L. Campbell

The surface properties exhibited by bituminous coal and bituminous coal lithotypes were ascertained by using streaming potential techniques. The electro kinetic prop-erties wereascertainederties of bituminous coal were found to be similar to those of anthracite. The principle electrokinetic properties of the coal and lithotypes, zero-points-of-charge (ZPC), and potential determining ions, were established. The effects of indifferent electrolytes, hydronium and hydroxyl ion sources, and polyvalent ions (cationic and anionic) were also evaluated. Location of the ZPC's with respect to pH is discussed in terms of chemical and mineralogical composition of the respective surfaces. To account for the observed electrokinetic phenomena, a generalized surface model and adsorption mechanism are proposed. Surface-dependent processes, such as froth flotation and flocculation, are important or potentially important techniques for combating some of the current major problems in coal preparation. In order to correctly apply or improve a surface-dependent process, it is of paramount importance to understand the interfacial phenomenon, especially the double layer properties, exhibited by the solid. The specific objective of this research was to determine the properties of the bituminous coal/liquid interface by an electrokinetic method, streaming potential, and to relate the findings, wherever possible, to the existing unit operations of froth flotation and floccula-tion tion. The electrokinetic properties of both the whole coal and its lithotypes were investigated. As part of the total investigation, the role played in the double layer by the reagents commonly employed in the surface dependent process was also established.' These data will be presented at a later date. Experimental Procedures The coal samples used in this research and their designations are listed in Table 1. The classical description of humic coal lithotypes as developed by Stopes" was used for the delineation of the lithotype samples. The samples were taken from the working face of a producing deep mine of the Pittsburgh seam in the area of Ellsworth, Pa. To avoid oxidation, only freshly exposed areas were sampled. The normal precautions against contamination were also exercised. Two types of samples were taken, specimens rich in a particular lithotype and a representative channel sample. The latter sample was prepared for analyses by grinding it to —35 mesh. It was screened repeatedly during the grinding to provide the largest amount of 35 x 48-mesh (standard Tyler sieves) material possible. The screened fraction was passed over a magnet and then washed several times with distilled water and finally with conductivity water. The resulting sample now termed "whole coal" was stored under conductivity water in a glass bottle. Pure lithotypes were obtained from the lithotype concentrates by hand picking, and were processed in the same manner as the representative sample. Maceral analyses, employing standard petrographic procedures," were performed on the lithotype samples to determine the purity of the samples. The results are presented in Table 2. Reflectance measurements of the vitrinites and fusinites are also reported in this table. Proximate and ultimate analyses of the samples are given in Tables 3 and 4. The electrokinetic properties of the coal samples were determined by streaming potential methods.'-' All of the chemicals used in the investigation were reagent grade (Baker analyzed). The conductivity water was prepared by doubly distilling the water in a pyrex Yoe-type still and passing the distillate through a mixed bed ion exchange column. Results In general, the electrokinetic properties of the investigated bituminous coal were found to be similar to the results of a previous study of anthracite by Camp-bell bell5 and are in accord with the suppositions of Brown." The zeta potentials of the coal and all the lithotypes were found to be negative in conductivity water. Jowett? in a study of slime coatings on coal also found bituminous coal to exhibit a negative surface. Fig. 1 shows that the negative charges, at neutral pH's, for both fusain and the gangue are very small, almost zero, while at the same pH, vitrain has the largest negative charge, almost 30 mv. Durain has a negative charge of 17.5 mv. The determination of the affect of pH on the charge of the coal surfaces revealed that hydronium and hydroxyl ions apparently behave as potential determining ions; however, they do not appear to be potential determining for the gangue. These results are illustrated in Fig. 1. As the pH of the solution was decreased, hydronium ions were adsorbed, causing the surface of the coal to reverse polarity and become

Jan 1, 1971

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965