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By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 4, 1917

PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER,1 NEW YORK, N, Y. WILLIAM L. SAUNDERS,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W.. RAYMOND NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 6, 1916

By James E. Little

Of the several extensive deposits of brown iron-ore in Cuba, including those of Mayari and Moa, that of Mayari was the first to be systematically explored, and was selected as the scene of the first operations in the development of this class of ore. Construction-work, begun in the spring of 1907, involved the building of 16 miles of stantlard-gauge railroad and two large double-track inelines, the installation of milling-machinery, a nodulizing-plant, power-plant, shops and shipping-facilities, and the dredging of an extensive basin for deep-draught vessels. Unusual weather-conditions delayed the completion of portions of this work so that the entire plant was not in operation until December, 1900.

Jan 1, 1912

By Sidney Powers

Discussion of the paper of SIDNEY POWERS and ALFRED C. LANE, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 535 to 548. N. L. BOWEN, Washington, D. C. (communication to the Secretary*). -This detailed study and. complete demonstration of differentiation as a result of the sinking of crystals has a great general significance in petrogenesis. If this action can be demonstrated in an effusive body, even though a very thick one, how can one doubt its possibility in large intrusive bodies? The authors speak of the sinking of augite and the rising of plagioclase but I should consider that they should depend entirely on the former action to obtain their results. It is true that in my experiments, to which the authors refer, a floating of crystals was in one case obtained, viz., in the case of tridymite crystals, but it must be remembered that tridymite has an exceptionally low density. Plagioclase crystals, on the other hand, are of nearly the same density as basaltic liquid. Under magmatic conditions they might be a little heavier than the liquid or a little lighter, we do not know which, but the margin would be exceedingly small and any motion resulting, whether upward or downward, would be correspondingly small in the usual case. For this reason I should think that the sinking of pyroxene should be considered probably the sole factor in producing the observed result, for which purpose it appears to be entirely adequate. The measurements of grain have also a certain significance in this connection. In the experiments referred to a difference of grain was obtained in different parts of the charge, which was entirely independent of the rate of cooling but connected with the fact that a sinking crystal does not depend entirely upon diffusion for the collection of its material from the surrounding liquid. The crystals which sank a considerable distance were therefore exceptionally large. Now in the Cape Spencer flow the augite crystals are normally (top and bottom) somewhat smaller than the plagioclase crystals, but in the layer somewhat below the middle,

Jan 5, 1916

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS, NEW YORK, N: Y. L. D. RICKETTS NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1918

By E. Maltby Shipp

WALLACE MCKEEHAN, Douglas, Ariz. (communication to the Secretary*).-In going over this report, which I have done very carefully, I find that the summary as composed deals with the various problems almost entirely from the employer's standpoint and that practically no consideration is given to the employee's point of view. An experience of 3 ½ years as safety inspector, and almost 30 years as workman-and official, has convinced me that any plan for the betterment of working conditions which will achieve any degree of success must give the workmen their share of responsibility and allow them full participation. The company may finance and direct the movement, but its ultimate success depends upon the support given by the workmen. The cooperation of the men doing the actual work is so essential that all writers insist that this must he secured, but they do not agree as to how this can best be done.

Jan 3, 1917

By G. L. Oldright, Henry de Rycker, S. F. Ravitz

The upper limit of richness of concentrates that can be smelted by means of the blast furnace without added diluents is fixed by the operation of sintering. A sinter feed with normal gangue constituents, containing more than about 50 per cent of lead, tends to fuse; as a result, air does not come sufficiently into contact with the sulphides at roasting temperatures, and sulphur elimination is poor. Since most lead concentrates now contain 55 to 80 per cent lead, it is necessary to add diluents to lower the grade of such sinter feed to about 50 per cent or less. This not only entails the expense of providing barren diluents when adequate diluents containing precious metals are not available but also appreciably lowers the capacity of the blast furnace to produce lead and increases slag losses. Attempts to desulphurize rich lead concentrates by methods other than sintering have not proved successful. Flash roasting, for example, converts much of the lead sulphide to lead sulphate rather than to oxide. However, this suggested the possibility that deliberate flash roasting of the concentrates to sulphate, followed by sinter roasting of the resulting product, might prove promising, particularly inasmuch as the elimination of sulphur from lead sulphate requires heat alone and not contact with atmospheric oxygen. The sintering of lead sulphate products has additional interest because important amounts of such products are now treated by lead smelters. Considerable quantities of lead sulphate are present in rich lead flue dusts and other by-products; lead-chamber sulphuric acid plants and other

Jan 1, 1944

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORE, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 12, 1917

On August 22, 1966, just 20 months after writing sales agreements with Japanese steel mills, Hamersley Iron Pty Ltd made its first contractual shipment of 52,000 tons to Yawata Iron and Steel Co Ltd. As world news, the event was not spectacular. But to mining men it represented an astonishing achievement. Twenty months of feverish effort and the expenditure of more than $100 million had created a large open-pit iron ore mine, a crushing plant, storage and load-out facilities for sized ore, and a supporting township at Mt Tom Price; a 182-mile standard gauge railway; and port and loading facilities for a nominal loading capacity of 6000 tph as well as a port town, Dampier, on King Bay. The project was executed in the sparsely inhabited, arid, dissected-plateau country of the Hamersley Range in the northwest sector of Western Australia. Hamersley, 60% owned by Conzinc RioTinto of Australia Pty Ltd and 40% by Kaiser Steel Corp, holds sale contracts for ore and pellets valued at $770 million. The main contracts are with the Japanese, who are to be supplied with 65.5 million tons of ore during the 16 years from August 1966 to August 1982 and 18 million tons of pellets over a 10-yr period beginning in early 1968. Of lesser importance at this time, but presaging trends, are contracts for a total of nearly 1.5 million tons to be shipped to England and Western Europe during the years 1966-68. A pellet plant with a capacity of 2 million tpy is now under construction at Dampier and is to be on stream early next year. Another interesting project for which the plans are set, is a desalination plant for sea water to supply industrial requirements and potable water for the town of Dampier.

Jan 5, 1967

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE, ST. LOUIS, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS, NEW YORK, N. Y. L. D. RICKETTS, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 2, 1918

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE, ST. Loves, Mo. PAST PRESIDENTS , WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS, . NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 10, 1917

By Richard H. Sillitoe

Gold is an important byproduct and, locally, coproduct of porphyry copper deposits, and possesses potential for discovery as the major metal in porphyry deposits in either island arcs or Cordilleran belts. Tungsten and tin occur as major components of several potentially bulk-minable porphyry deposits, as well as being byproducts from the Climax porphyry molybdenum deposit. Whereas porphyry tin systems are localized in Cordilleran back-arc settings, their tungsten counterparts appear to span a range of geotectonic settings, from Cordilleran principal arcs through back arcs to rifts. Although silver is a common byproduct of porphyry cop- per deposits, it tends to be preferentially concentrated with lead and zinc on the fringes of all types of porphyry deposits and/or as late-stage superpositions; the latter situation could be of some interest in the higher parts of porphyry systems. As byproducts, rhenium, uranium, platinoids, and magnetite are exploited occasionally, and rutile and the rare metals, such as tantalum and niobium, merit consideration.

Jan 1, 1983

By Arne Westgren

ONLY in exceptional cases can the ordinary methods of chemistry be used for determining the constitution of compound metallic substances. Recourse has therefore been taken to special methods, the main expedients of which are, as we know, thermal analysis and metal microscopy. To these may be added-though more accessory-the determination of electric conductivity, specific volume, hardness or other properties. The information obtained by these methods has been compiled in equilibrium diagrams. Naturally, the technically most important alloys, such as steel, bronze and some others, have been subjected to very close study, and many investigators have devoted themselves to the solving of their problems of constitution. The equilibrium diagrams of these systems are therefore known today with a comparatively high degree of accuracy, even though it must be admitted that many details regarding their transformation reactions still remain to be completely explained. The equilibrium diagrams of the other alloys as a rule have not been determined so accurately. Most of them are based only on approximate determinations of the homogeneity ranges of the various phases. Thus extensive, detailed studies remain before these diagrams may be considered as established. Unfortunately, it must also be admitted that many of the alloy diagrams given in the present handbooks are as a whole very dubious. As a matter of fact, many of them may really only be viewed as the results of rather superficial, orientating investigations. In fact, there also seems to be a general opinion prevailing in our day that much work still remains to be done before the equilibrium conditions of the alloys may be considered as fully explained. At present, in almost all institutes for research on metals, as well as in many university laboratories, investigations to this effect are being carried out. As a rule, the classical methods of metallography, the thermal analysis and metal microscopy are applied.

Jan 1, 1931

Jan 1, 1922

Jan 1, 1879

By C. D. Gilpin, Franklin Moeller

The application of electric power for driving mine hoists handling heavy loads at high speeds has recently been extended by the installation of what is probably the largest electrically driven hoist in this country at the Granite Mountain shaft of the North Butte Mining Co., Butte, Mont. While the weight of rock which is hoisted by this machine is not the largest now being handled by electric mine hoists, the speed of hoisting is so, and the combination of the high speed with the heavy load has resulted in a machine of considerable interest to all those actively engaged in mining. Aside from mere considcration of size, this installation deserves attention because of the careful attention given, not only to the question of economy of operation, but to the details of construction and installation of the entire equipment. The conditions to be met in this installation were as follows: Weight of rock to be raised per trip, 7 gross tons........... 15,680 1b. Weight of skip.......................................... 8,000 1b. Weight of cage.......................................... 1,800 1b. Maximum depth of hoisting.............................. 4,000 ft. Diameter of rope.......................................... 15/8 Total weight suspended on one rope from drum............. 42,000 1b. Normal hoisting speed.................................... 2,700 ft. per minute. Maximum hoisting speed.................................. 3,000 ft. per minute. Desired capacity-200 tons per hour from 4,000 ft. depth. The ore is mined in several levels and hoisting is carried on from the 800-ft. level down to the 2,700-ft., which is at present the maximum depth from which the ore is raised regularly. Development is proceeding and a depth of 2,900 ft. has already been reached. The rock is handled underground in cars holding % ton, and about 10 cars are the usual load for a skip. All of the ore is dumped into underground bins, which are of diffcrent capacities varying up to 250 tons. From the bins the ore is fed into the skips without passing into measuring pockets. At the surface the

Jan 1, 1916

By John S. Marshall

The purpose of this paper is to present to the profession data and experience obtained over a period of 5 years in the operation of 87 shaker-conveyor units, and the production of 2,169,638 tons of run-of-mine anthracite coal. The data are not generally available and should be of interest to those concerned with the operation of anthracite and bituminous mines. To simplify comparison, a ton of 2000 lb. of raw run-of-mine coal has been used as the production unit throughout this paper. Mining Methods and Equipment The mine is in the vicinity of Wilkes-Barre, Pa., in the Buried Valley area of the Susquehanna River. Seven veins were mined, varying in thickness from 18 in. to 8 ft. The cover overlying the veins varied from 200 to 800 ft. Three-fourths of the 1200 acres of property was covered with from 100 to 200 ft. of water-bearing gravels and clays, which prevented first mining under rock cover less than 50 ft. and pillar removal under rock cover less than 100 ft. The property was opened by two shafts sunk on the mountainside to avoid the sand and gravel present in the river valley. The veins dipped an average of 5" from the shafts. In certain areas the veins were practically flat and in some places a reverse pitch as high as 5" was encountered for short distances. A daily output of 3800 tons was hoisted on a two-shifi; hoisting operation. The mining consisted of 75 per cent pillar removal, and of the total production in the later years of operation 80 per cent was loaded by shaker conveyors, chain conveyors and scraper loaders. Shaker conveyors accounted for 70 per cent of the total output; chain conveyors and scraper loaders for 10 per cent. All conveyor work was double-shifted and 25 per cent was triple-shifted. A total of 87 shaker-conveyor units were on the property, of which 75 were kept in operation at all times.

Jan 1, 1940