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By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922

By H. E. Wheeler

The work described was carried out during 1917 and 1918 at the testing laboratory of Watertown Arsenal at the instigation of the Nitrate Division and later with the concurrence of the Cannon Section of the Ordnance Department, U. 8. A. The experiments follow three principal lines of work: First, the effect of nitrogen under pressure on steel containers of various compositions at a red heat; second, the effect of decomposing ammonia on various alloy steels, iron, and non-ferrous alloys; third, a new theory of the erosion of guns in respect to the effect of nitrogen in steel. Part I In the Haber process for the manufacture of ammonia from its elcnlents, it is necessary to have nitrogen and hydrogen of 1500 lb. per sq. in. (105.5 kg. per sq. cm.) at a temperature of 500 to 600' C. The steel containers for these gases gave trouble by failing without apparent cause. When the General Chemical Co. began to develop its method for the production of ammonia, it experienced the same difficulty and, knowing that the Haber process had solved the difficulty by the use of alloy steels, it made several small steel bottles of different compositions and kept them filled with these gases at this pressure and temperature until they failed. The time of service varied from a few days, for the plain steel casting, to two years for a chrome-vanadium forging. Four of these steel bottles were sent to this laboratory for investigation; they were a plain carbon-steel forging, a nickel-stee1 forging, a chrome-vanadium steel forging, and a chrome-steel forging. The time of service was as follows: plain carbon steel, 4 mo.; nickel steel, 6 mo.; chrome-vanadium steel, over 2 yr.; chrome steel, 4 mo. When these containers were cut open and the cross-section surface polished, they showed an inside zone with a different luster from the rest of the metal. Upon etching, this zone was almost unaffected while the rest of the steel etched normally.

Jan 1, 1922

By Stanley Herold

Considerable interest has been shown, during recent years, in the possibilities of developing oil fields in the South American Republics, now that the exhaustion of our present fields can be seen in the not very distant future. The demand for fuel oil and its products has been increasing far more rapidly than our increment of production during the last few years. Increase of consumption has been largely curtailed by the lack of sufficient supply. The main factors that have contributed to our previous neglect of the southern fields have been as follows:, (a) Lack of sufficient demand for the product. (b) Competition with producing fields, having large production, low cost, and better geographical position, such as Tampico, Mexico. (c) Greater interest in home fields with ready market at hand. (d) Our ignorance of southern economic and geologic conditions, clue to the distance between those areas and our financial centers. (e) Economic conditions in the southern countries, necessitating high costs of exploration and exploitation of the fields.

Jan 9, 1918

By Thomas E. Leontis

INTRODUCTION THE importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication,1 attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne.2 The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Zn† alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-1Zn,†Mg-3Zn, Mg-4.4Zn, Mg-6Zn, and Mg-10Zn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. LITERATURE The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison.3 Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,4 Dumas and Rockaert,5 Haughton and Prytherch,6 and by Spitaler, the last being reported by Beck.7 A slight superiority in the tensile strength of chillcast Mg + 8 Zn alloy over the sand-cast alloy was noted by Maybrey 8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1948

By L. G. Jones

An approximate method of calculation is developed in this paper which allows duplication of radial unsteady-state gas flow computer results where Darcy's law applies, such as those reported by Aronofsky and Jenkins and Bruce, Peaceman, Rachford, and Rice. Moreover, the new calculation method can be used to obtain results for radial unsteady-state gas flow obeying the quadratic flow law proposed by Duwez and Green. Means are discussed for predicting well behavior at single or superimposed flow rates in finite or infinite reservoirs, determining reservoir rock properties from well-test data, reproducing and interpreting back-pressure test data, and determining the radial extent and reserves of gas reservoirs from well-test data. Example calculations are presented for gas flow following both Darcy's law and the quadratic flow law. INTRODUCTION Since the publishing of U. S. Bureau of Mines Monograph 7,1 most gas-well testing methods have been based on the equation q = y (pl2 - pw2)a, where q = production rate, pl and pw, are formation pressure and sandface pressure, respectively, and y and a are constants to be obtained from test data. These methods, used for predicting both deliverability and "open-flow" capacity of gas wells, have been useful and accurate in many cases but unsatisfactory in others. Even at best, however, they do not supply information about the formation or lead to an understanding of nonsteady-state gas flow in porous media. Many theoretically based studies2-4 of gas flow obeying Darcy's law have been made.' Since the partial differential equations which result from combining Darcy's flow law with the continuity equation are nonlinear, most of the published research consists of either numerical solutions or analytical solutions for linear approximating equations. Such solutions have been of limited value in field work due to their unhandy form and their failure to correlate most field data. There is evidence5,6 which indicates that Darcy's law is inadequate to describe gas flow at some flow rates of practical interest. A quadratic flow law: which reduces to Darcy's law at low rates, is more successful in accounting for experimentally observed behavior. This flow law has been applied successfully to a few hypothetical reservoir cases in work which has recently been published.10 However, these numerical solutions of the equations involved have been successful only on a special analog computer. Routine applications to field cases would be awkward and have not been attempted. The present paper describes an approximate method for computing nonsteady-state gas flow solutions which has been completely successful in predicting the results for both Darcy flow and quadratic flow obtained by elaborate numerical methods. The new calculation method allows determination of the observable variables in gas-well testing at constant rates. It is similar to the scheme of using a succession of steady states suggested by Muskat7 in that it makes use of steady-state and material-balance equations. It also is similar to the work of Aronofsky and Jenkins2 in that the new method includes Aronofsky and Jenkins' stabilized flow equation as a special case. It improves upon both of these calculation schemes in that it accurately describes all portions of reservoir history and suggests means of determining reservoir rock properties from well-test data. This paper deals only with production from a reservoir, in which case the rate is defined as being negative. The reservoir studied here is a homogeneous, disk-shaped porous body of uniform thickness, with all boundaries sealed except the inner radial boundary of the well.

By L. R. Mabson, F. M. Russell

INRODUCTION Roan Consolidated Mines Limited (RCM) operates five underground mines - Mufulira, Luanshya, Baluba, Chambeshi and Chibuluma (figure 1) . Associated metallurgical plants provide for the operations of milling, smelting two refineries for copper and a cobalt plant. Primarily a producer of high quality copper (242,000 tonnes during 1980) the Company is also the world's second largest producer of cobalt metal. RCM's remaining ore reserves at 31st March 1980 were 275 million tonnes at 2.84% copper. Monthly ore production is in excess of 1.2 million tonnes. Sublevel open stoping was the choice of mining method for the first underground operations on the Copperbelt for ore with dips steeper than 30 degrees. This was for use at the Roan Antelope mine, subsequently to be called Luanshya mine. The sublevel open stoping system was planned based on the methods used in many of the iron mines of Michigan and New York and in the copper mines of Tennessee. Peterson (Ref. 1) gave the following reasons for employing sublevel stoping, reasons which are still valid today: (1) the working place could always be barred and made safe, and the sublevel exit was always at hand; (2) the working conditions were similar day by day and drilling operations were repetitive; (3) pillar spacing can be varied as conditions demand; and (4) stoping operations could be shut down completely or opened up to full capacity at short notice, without affecting grade or causing wastage of reserves. Such was the success of the method that it was adopted as the basic mining method at all the RCM mines in their initial stages. Although cut and fill, block caving, and sub- level caving methods have been used, sublevel open stoping in its many variants still accounts for nearly 90% of total ore production in the Company. The following descriptions outline some of the applications of sublevel open stoping within RCM. LUANSHYA Geology There are two main ore deposits at Luanshya: the Roan (Luanshya Mining Area), in which mining began in 1930, and Baluba, in which mining production started in 1973 (figure 2). Both orebodies occur in synclinal and variably folded basins. These basins are underlain and completely surrounded by much older schists and granites. The ore formation, an argillite, lies near the base of the sediments and is underlain by conglomerates, quartzites and arkoses. Copper mineralisation is mainly found in two well defined zones, separated by a varying thickness of pyrite mineralisation. In the eastern part of the Roan deposit only the upper orebody is present, but west of 18 shaft and at Baluba the lower orebody predominates. Locally the subjacent quartzites of the footwall formation are also mineralised with copper. The copper mineralisation is found princi- pally as disseminated sulphides, mainly chalcocite, bornite and chalcopyrite. Near the surface the sulphides have been changed to oxides. At Baluba the cobalt mineral carrollite is found with the sulphides. Mining methods Sublevel open stoping is the basic mining method. In its standard form this method is best suited to steeply inclined orebodies, with simple structures and with a strong foot- wall and hangingwall. In recent years, as more complex folding and flatter dipping orebodies have been encountered, considerable variations have been introduced. Stope drilling is effected with drifters and extension steel.

Jan 1, 1981

By T. A. Rickard

The purposes of composition are various; one purpose, for instance, is to make a record for the writer's own use, as in a diary. That does not involve responsibility to others. There is also the writing meant to influence opinion-to be persuasive, and pleasing. With such writing we need not concern ourselves at this stage of our study. The prime purpose of technical writing is to be informative-to convey information; therefore it must" be clear beyond the chance of misunderstanding. Such clearness is impossible if meaningless or ill chosen, words are sprinkled through the text. Discard the trivial phrases that are constantly at your elbow. Brush aside a host of vapid superlatives. Metternich exclaimed:' "The superla¬tive is the mark of fools". It is a false emphasis, like the underlining in a school-girl's letter. For example, the little word `very' can be deleted nine times out of ten; it is an impediment to terse and perspicuous writing, as 'the multitudinous hand-baggage of the British tourist is to his travel. 'Very' supposes comparison. A mine with a 1000-ft. shaft is very deep to the scribe who writes from the Joplin district', in Missouri, but it seems a shallow hole to a man living at Calumet, Michigan. A vein that is 10 feet across may be considered very wide at Cripple Creek, Colorado, but it is only a `stringer' to the miner at the Homestake, in South Dakota. Ore assaying $20 in gold is very rich at Juneau, Alaska, where .10,000 tons of $1 ore is crushed daily, but it is relatively low-grade to the pocket-miner at Alleghany, in California. It is all a matter of comparison; unless the reader knows your standards of depth, width, or richness, your `very' has no significance. "Where erosion was very rapid or oxidation very shallow"

Jan 1, 1931

By C. W. Price, G. A. Wheeler

BERYLLIUM has always been a difficult material to prepare for metallographic examination. Severe surface deformation occurs during mechanical grinding and polishing, and a suitable bright-field etchant has not been developed. Certain electrolytic techniques produce satisfactory polishes, but these techniques have not yielded entirely consistent results. Furthermore, they have not provided satisfactory bright-field etches. The purpose of this paper is to describe an electrolytic polishing technique that can also provide an excellent bright-field etch. In addition to the bright-field etch, other advantages of this technique are excellent reproducibility, rapidity, and ease of polishing and etching. Experimental Technique. Specimen Preparation. Beryllium specimens may be either mounted or unmounted for the use of this technique, and the size of the specimens is not important. Specimens with surface areas up to 4 sq cm have been electrolytically polished and etched successfully with this technique. The most important requirement is to provide a good electrical contact to the specimens, preferably on the back of the specimens. When specimens are mounted, a hole is drilled through the back of the mount so that the specimen can be contacted with a probe. Conventional metallographic grinding techniques are used to prepare the specimens for electrolytic polishing. The specimens are ground on silicon carbide papers. Grinding through the usual series of papers down to the 600-grit paper is recommended to minimize the electropolishing time, although successful electrolytic polishes and etches have been obtained by grinding only through the coarser papers. A continuous flow of water is used during grinding to provide lubrication and to minimize contamination. Mechanical polishing is not required because high rates of material removal are achieved with the electrolytic polishing. Polishing. Most of the results reported in this paper were obtained with a "Disa-Electropol", manufactured by Struers Scientific Instruments of Copenhagen, Denmark. Satisfactory results have also been obtained with the conventional beaker technique of electrolytic polishing, however, the conditions applicable to both the Disa unit and the beaker technique will be described. Stainless-steel cathodes are used in both techniques. In the beaker technique, a flat cathode, with an area at least twice that of the specimen, is used, and the specimen is held parallel to the cathode. The distance between the specimen and the cathode affects the quality of the electropolish. This distance is set at about 7 mm in the Disa unit; the same distance produces the best results in the beaker technique. Specimen-cathode distances greater than about 20 mm produce considerable relief, while distances less than 7 mm cause high current densities that are difficult to control. An electrolyte of 2 pct HC1, 2 pct HNO3, and 2 pct HCIOl in ethylene glycol gives the most satisfactory results for both electrolytic polishing and etching. This electrolyte was developed by altering the composition of a similar electrolyte used for electrolytic lapping1 and adding HClOl to improve the etching characteristics of the electrolyte. Variations of from 0.25 pct to as much as 5 pct of each of the acids do not significantly affect the results, but the greatest amount of control and reproducibility can be obtained with the composition of 2 pct of each acid. Generally, lesser amounts of the acids produce lower polishing and etching rates, while greater amounts of acids cause high current densities that are difficult to control.

Jan 1, 1968

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968

By C. H. Mahoney, A. L. Tarr, P. E. Le Grand

Magnesium, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, 0' the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.' Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point, It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-hearing group by raising the temperature of the melt after the refining treatment to some 250°C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730°C. (I350°F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (I600°F.) and 930°C. (1700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to 'solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.' It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying Constituent—the binary alloy containing 1.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack

Jan 1, 1945

By R. H. Frazier, J. M. Hodge, F. W. Boulger

This paper reports the results of studies of the impact properties of quenched and tempered alloy-steel plates as a function of sulfur content. It was found that the impact energy levels decreased continuously as the sulfur content increased and that there was a straight-line relationship between impact energy and sulfur content when plotted on logarithmic coordinates. Cross rolling raised the level of these Lines for transverse tests and lowered the level for logitudinal tests proportionately to the amount of cross rolling. ALTHOUGH it has been generally recognized that, for applications in which notch toughness is critical, the sulfur content of the steels used should be held to a low value, quantitative information on the effect of sulfur on notch toughness has not been available. For such applications, it is a common practice to specify minimum impact values, and in order that these may be met consistently it is important that the steel producer know quantitatively the effect of sulfur on notch toughness so that realistic sulfur content limits can be applied to the steels they produce. In many instances, particularly in flat-rolled products, impact properties are specified in the direction transverse to the principal rolling direction, so that the factors affecting the anisotropy or directionality of impact properties are also of concern to the steel producer. For some applications, furthermore, it is a common practice to increase the sulfur content of steels in order to improve their machinability, and, in such instances, the effect of this practice on notch toughness may often be of concern. This paper reports on an investigation, carried out at Battelle Memorial Institute, designed to furnish this quantitative information on the effect of sulfur on notch toughness and also to furnish further information on the factors affecting the anisotropy of impact properties in wrought heat-treated alloy steels. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental steels were of intended base analysis: 0.30 pct C, 0.80 pct Mn, 0.25 pct Si, 2.5 pct Ni, 0.80 pct Cr, and 0.45 pct Mo. Steels were made with sulfur contents varying from 0.005 to 0.179 pct. The steels were prepared from 600-lb induction-furnace melts. Steels containing 0.020 pct or more sulfur (at meltdown) were melted from a charge of ingot iron (except for one heat): lower-sulfur steels were made from electrolytic iron. The charge consisted of ingot or electrolytic iron, ferrosilicon to give 0.10 pct Si, and ferromanganese to give 0.05 pct Mn. At meltdown, electrolytic nickel, ferromolybdenum, iron phosphide, and pyrite were added followed in sequence by ferrochromium, sili-comanganese, ferrosilicon, and ferromanganese. The slag was then removed and graphite added to give the desired carbon content. Bath temperature was adjusted to 2850°F and, when no other additions were to follow, 2 lb per ton of aluminum was added, immediately before tapping. Compositions of the experimental steels appear in Table I. Analyses are from single determinations, except sulfur which was analyzed in duplicate. A test sample (3 in. in diam by 6 in. long) and a 575-1b ingot were poured from each heat. The test sample was poured in a sand mold; the cooling rates of the test sample and the large ingot were approximately the same. Chemical analysis chips and metal lographic specimens were taken from the test samples. The ingot was 8 in. sq at the base and 9 in. sq at the top. A 5 X 5 X 6-in. sand mold hot top was completely filled in teeming the ingot. After solidification, the mold was stripped from the ingot which cooled to room temperature. Ingots were reheated to 2250"F and rolled to 1.9-in. slabs on a commercial mill. The slabs were box-cooled to room temperature. Sections of the 1.9-in. slabs were heated to 2250°F and rolled on a Battelle laboratory mill according to one of three schedules: 1) rolled straightaway to 0.5-in. plate; 2) rolled straightaway to 1.3-in. thickness, then cross rolled to 0.5-in. plate (29 pct cross rolling); or 3) cross rolled from 1.9-in. to 0.5-in.-thick plate (46 pct cross rolling). The 0.5-in.-straight- or cross-rolled plates were normalized at 1700°F for 1 hr and then water quenched from 1600°F. Plates were then tempered 2 hr at 1240°, 1170°, 1080°, or 860°F to obtain Rockwell C hardness of 25, 30, 35, and 40, respectively. Tempering was followed by quenching to room temperature to avoid temper embrittlement. Slack-quenched plates were isothermally transformed for 26 min at 800°F, quenched, and tempered 2 hr at 1170°F. Pearlitic microstructures were obtained by holding 168 hr at 1200° F, followed by quenching. Charpy V-notch specimens were taken both transverse and longitudinal to the main rolling direction, notched perpendicular to the plate surface, and tested. Slabs and plates which were to be homogenized

Jan 1, 1960

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By F. W. Luersson

High carbon, low phosphorus steel can now be made from pig iron containing 0.7 pct P or more, in a commercial sized open hearth furnace. No external heat is required for refining, and steel produced is identical with basic open hearth steel. THE classical Thomas process, which requires liquid pig iron containing over 11/2 pct P, yields a product relatively high in phosphorzs and nitrogen. Unless large quantities of recarburizers are added to the refined steel, the product is low in carbon content. Thus, the Thomas process is not well suited to American raw materials, and its product is often not acceptable according to the standards set by American industry. The shortcomings of the Thomas process have long been recognized; with the advent of low cost oxygen, studies were initiated to develop pneumatic processes which would conceivably overcome the inherent objections to Thomas steelmaking. Several such modified basic pneumatic processes have been tested experimentally in commercial trials during the past decade. Probably the most widely publicized of these developments has been the oxygen converter process as practiced in Austrial,2 and in Canada.8 n this process, oxygen is substituted for air and introduced above the liquid bath in order to increase the heat available to the metallurgical system. This avoids the need for high phosphorus raw materials and gives a product low in nitrogen. In this process, the phosphorus content in the final product depends, to a considerable extent, on the total amount of that element in the burden. The rotary furnace4 which is now in commercial operation at Domnarvet Steelworks, Sweden, is producing low phosphorus steel from iron containing 1.8 to 2 pct P. One or more early slags are removed and by this means high carbon steels of open hearth quality can be produced. At this stage of development there is some question as to the applicability of the rotary process to large heats. Another development has been the use of oxygen in combination with either steam6 or carbon dioxide yn the basic bessemer, thus avoiding the introduction of nitrogen gas into the refining system and giving a product relatively low in nitrogen content. A double slag process has been used in Europe7 in conjunction with a regular Thomas converter, by means of which it is possible to obtain a phosphorus content in the product approaching that obtained in basic open hearth steels. The Turbo-Hearth process:' which uses the side blowing principle so as to produce low nitrogen steel from normal American pig irons, has been developed experimentally in this country. A process fitted to U. S. raw materials All of the preceding processes, with the exception of the rotary furnace, suffer from the common shortcoming that they cannot be adapted to the production of high-carbon, low-phosphorus steels unless large proportions of recarburizers are added. In 1947, a program was initiated by the Inland Steel Company1' to study an oxygen steelmaking process specifically designed to utilize the full range of phosphorus analyses encountered in American pig irons and to give finai products with phosphorus and nitrogen contents comparable to steel produced by the basic open hearth process. Some of the objectives of the proposed process are: 1) the process should be able to accommodate molten pig iron conta;rl;rrg up to 1 pct P., 2) sne process should be subject to close control of carbon analysis, 3) the process should be capable of producing high carbon

Jan 1, 1958

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965

By James Kemp

PostScript to a paper presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 129 to 154. The writer looked over the quarry with care in the search for fossils, having in mind shells or corals of fairly large size. In the brilliant summer sunshine, none were observed on the glaring white ledges. The impression was gained that none were present and the statement to this effect was made in the edition of this paper published in the Bulletin' of the Institute for February, 1915, p. 136. On closer examination in the laboratory it has been discovered that the limestone itself is made up of minute organisms, which are clearly revealed by microscopic examination of thin sections. The principal component of the rock is a small foraminifer, 0.1 to 0.3 in. (2.5 to 7 mm.), of the genus Orbitoides, presumably an Oligocenic form. Figs. 1 and 2. illustrate it. The accompanying description has been kindly summarized by Marjorie O'Connell, M. A., Curator in Paleontology in Columbia University, who first detected the evidences of organisms in the rock. Orbitoides kempi O'CONNELL N. SP.1 The foraminiferan which makes up the Seboruco limestone is an Orbitoides of a Species new to North America. The only Orbitoides heretofore described from this country is 0. mantelli from the lower Oligocenic of the Gulf States. This form from Cuba, then, so different in all of its characteristics from the 0. mantelli, is of great interest as perhaps forming a basis of correlation over wide areas. The most closely related Species is 0. dispansa Sowerby, which occurs in the Nummulite limestone of the Eocenic of the Bavarian . Alps, in the Priabona beds of the lower Oligocenic of Massano, and elsewhere in Italy, as described by Gümbel.2 The age of the limestone in Cuba would thus Seem to be of upper Eocenic or lower Oligocenic age, probably the latter. The fossil has the form of a sphere Surrounded by a wavy rim of horizontal extent, the whole resembling two flat-brimmed, round-crowned hats placed base to base. The total extent of the Shell ranges up to 7+ mm., while the thickness of the central sphere is 2.5 mm. in one of the largest individuals. Like all of the other Species of Orbitoides, this form begins with a Single layer of chambers which multiply in one plane and assume a circular outline; but it is in the subsequent growth that the distinguishing specific characters appear, for the chambers at the central portion of the shell increase more rapidly than do those near the periphery and in consequence a Swelling is produced which finally gives the Spherical form which is so characteristic. The rim, on the other hand, shows little chamber-increase and remains thin. This is clearly Shown in the sections figured, where the central row of larger chambers forms the equatorial zone. Radiating from this row, in section, there appear, a number of solid cones alternating with broad reticulated ones. The solid cones mark the more dense structure forming the walls surrounding the reticulated or chambered cones. These appear upon the Surface as distinct pits, whereas the solid part appears as raised walls.

Jan 7, 1915

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941