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By James Malcolmson

(New York Meeting, February, 1913.) THE Tigre Mining Co. of Mexico, owned by the Lucky Tiger Combination Gold Mining Co. of Kansas City, decided early in 1910 to enlarge its mill, which consisted of a concentrator milling 3,000 tons of ore per month. The enlarged plant was designed to crush and concentrate 6,000 of ore and to cyanide 7,500 tons per mouth. The extra tonnage cyanided was to be obtained from tailings which were stored below the old mill. Power was supplied to the old mill from four boilers; a 150-h-p.. Corliss engine and two Weber 60-h-p. gas-engines using producer-gas made from charcoal. The total horse-power required, including 60 h-p. used for machine-drills in the mine, was approximately 275. Cord-wood cost $4.32 per cord, 8 by 4 by 3 ft., and charcoal $15 per ton. The fuel supply in the surrounding country was approaching exhaustion; more than 150 mules and 50 men were engaged in cutting and transporting this fuel, and the unsettled political, conditions in Sonora were such that it would be practically impossible to keep an organization of this kind together. The price of fuel was steadily rising and at times it became almost impossible to get sufficient fuel to operate.

Jan 4, 1913

By Edgar S. Cook

The Warwick furnace at Pottstown, Pa., constructed for anthracite fuel, is, as may be remembered, 554 feet high, with 15; feet bosh. The actual working height from stock-line to bottom is only 474 feet, the bell-and-hopper taking up 8 feet. During the year 1886 we used mixed fuel, in the proportion of three-fourths anthracite and one-fourth coke. The total product of iron was 30,6299 tons of 2280 lbs., being a weekly average of 589 tons, including all ordinary and extraordinary stoppages. Deducting the latter, the weekly average would be about 600 tons. The fuel-consumption for the year was 1.2 tons per ton of iron, while the ore-mixture yielded 52 per cent. of iron. For about two months during the summer of 1887 we were obliged to run on anthracite exclusively, owing to the Connellsville coke strike. In the fall of 1885, in relining the furnace, the crucible had been built 8 feet 9 inches in diameter, with the view of using regularly one-quarter of coke (the largest previous diameter having been 7 feet 5 inches), and we felt somewhat apprehensive of the results when compelled to use anthracite only. The average of seven weeks' run on coal, as compared with the average of the seven corresponding weeks of 1886 (using one-quarter coke), was as follows:

Jan 1, 1889

By Eifu Moriyama

In 1953, Akita Plant, having a capacity of 560 tons per month, was built at Akita city by Mitsubishi Metal Mining Co., Ltd. for the purpose of treatment of the Ikuno and Akenobe Mines's zinc concentrates. Akita city, in whose neighborhood the black ore has been discovered, is located about 500 Km north of Tokyo and faced with the Japan Sea. This plant has been continuously expanded to have the capacity of 7,500 tons per month by the end of 1969. Efforts have been made to mechanize installations and to achieve continuous process. One of the characteristics of Akita Plant is the recent establishment of the residue treatment process. Many processes had been investigated, and finally commercial sulphate roasting of the residue has been carried out since 1965. At Akita Plant, special high grade electrolytic zinc, zinc alloy for die-casting (MAK brand), cadmium, cement copper and sulphur dioxide gas are produced. Sulphur dioxide gas is sent to the next door fertilizer plant to make acid. Table 1 shows production and the average assay of the electrolytic zinc and cadmium in 1969. This plant is divided into four main sections, two subsections, and residue treatment sections: Main sections are: (M-1) roasting section, (M-2) leaching and purification section, (M-3) electrolysis section, (M-4) melting and casting section,

Jan 1, 1970

In accordance with the requirements of By-Law LX,- I beg leave to submit herewith the report of the Library Committee for the year 1916. The activities shown by the sale of the Institute's publications during the year are somewhat larger than last year, due principally to the increased sale of special editions on account of the larger sale of the Posepny and Emmons Volumes, owing to increased advertising and to the reduction in price of the Emmons Volume. The sales were distributed as follows: Sale of Transactions $3,237.07 Sale of Special Editions 1,722.50 Sale of Bulletins and Pamphlets 2,263.95 Total $7,223.52, The Institute library has now been merged with the libraries of the. other three Founder Societies and is known and administered as the Library of the United - Engineering Society. When this merger, was effected, a proviso was made that the books contained in the Institute library up to the date of the merger were still to be considered as the individual property of the Institute, and this arrangement applied also to the libraries of the other two Founder Societies. At the time that the American Society of Civil Engineers joined as a fourth Founder Society, they immediately turned over their entire library to the United Engineering Society, relinquishing all property rights in the books entirely.

Jan 2, 1917

By Frank Firmstone, Kenneth Robertson

Peculiar crusts having appeared on certain irons made at Glendon and Pequest, which, in our experience, were entirely new, some analyses of them were made; and these analyses, together with an account of the manner of appearance of the crusts, are herewith submitted to the Institute. At Pequest the ores mere: & Peters, from Ringwood, N. J.; + roasted sulphurous ore, from Charlotteburgh, N. J.; and + red ore (decomposed magnetite), from Chester, N. J. The fuel was 7/8 Lehigh anthracite and + Connellsville coke, and the limestone a dolomite from Andover, N. J. The resulting iron varied in silicon from 0 84 per cent. in No. 1 foundry to 0.51 per cent. in gray forge; in phosphorus, from 0.81 per cent. to 0.55 per cent.; sulphur, 0.035 per cent.; manganese, 0.375 per cent. It was highly "chilling" in its properties, and very strong. In running, it invariably appeared to be of a lower grade than it really was; the higher grades scintillating as much as hard iron usually does. After getting into the moulds, and beginning to cool, a black crust began to show itself, seeming to exude from the pigs, till finally, when the iron was cold enough to break, it completely covered the face of the pigs. At this time it was dense black, but after some exposure to the air it ac .

Jan 1, 1884

By Robert Hunt

(New York Meeting, February, 1913.) I HAVE frequently stated that while the chemical composition of steel is important, yet even greater importance is connected with the mechanical and heat treatment of the metal. During the past year I encountered such a positive example of that fact that I deem it worth putting upon record. A prominent railway system divided an order for open-hearth steel rails between two steel works, both of which are under the control of the one corporation; giving to one about 18,000 tons, and to the other 7,500 tons of the same section and to be made under the same specifications. The rolling results obtained in the two mills varied so widely that a study of the figures is intensely interesting and serves to illustrate the advantages obtained by careful ingot casting, and, quite as pertinently, the possible benefits of careful subsequent heating and rolling with moderate reductions in the rolling process. The smaller order was rolled complete in four installments during the same months that the larger order was being made in six separate installments; but, to permit of exact comparisons, the totals of the four installments (completing the order with the mill which I will call A) are given with the totals of the first four installments of the larger order, made by the mill designated as B. These rolling results are:

Jan 5, 1913

By AIME AIME

COMPLETION of the Rainbow Bridge across the Niagara River and Gorge this fall marks a new page of achievement in the annals of bridge- building. Symbolic of the amity between two great nations, the new bridge provides an additional gateway across the most peaceful border in the world. Ground was broken for the project May 16. 1940, at a site close to that formally occupied by the Falls View Bridge which was destroyed by a record ice jam in 1938. At this point, about 2000 ft. deep and 1000 ft. downstream from the American Falls, the gorge is about 200 ft. deep and 1000 ft. wide. The great steel arch of the bridge has a span of 950 ft. and rises from its supporting abutments on the American and Canadian sides of the river to the level of the top of the gorge. This is said to be the longest hingeless arch in the world.

Jan 1, 1941

By E. P. Whittemore

Experience with the ASC multipoint gas lift system was obtained in Colonia zone of the West Montalvo field near Oxnard, Calif. The wells in this pool produce from depths varying from 10,500 to 12,000 ft. Oil gravity is generally 14 to 15' API with a few extremes of 12 and 20" API. Some salt water is produced which causes some very viscous emulsions. Viscosities at 150F (which is the approximate wellhead temperature) vary from 5,000 to 100,000 SSU. Most of the production is by gas lift, although a few wells are produced by rod and hydraulic pump. About half of the gas-lift wells are on continuous flow and the remainder are on intermittent lift using large, ported, pilot-operated valves for single-point transfer of gas from casing to tubing. Gas-liquid ratios vary from about 6 to 10 Mcf/bbl of gross fluid lifted. Wells are produced to a 450-psi trap system. The following remarks will be confined to intermittent lift only, since this is the type of lift which has been achieved with the ASC valve system. The maximum gross fluid which has been produced by single-point intermittent lift is about 350 B/D in 3-in. tubing and 200 B/D in 21/2-in. tubing with gas-liquid ratios of approximately 7 to 9 Mcf/bbl. Some design changes could reduce this ratio. The ASC multipoint system has provided production as high as 480 BOPD in 21/2-in. tubing with gas-liquid ratios just under 4 Mcf/bbl. To be able to apply the multipoint system, it is recommended that a detailed explanation be obtained concerning transition-point pressure and stabilizer setting—what its significance is to the string design, how it may work for or against the operation of the well, how it is related to tubing sensitivity and how it affects the unloading operation. The unloading operation may only be of academic interest in a technical paper, but to the production foreman, unloading and setting the valves in operation is a very real problem and should be understood in detail. One item touched lightly in the paper was the unloading valve. This valve controls the maximum pressure at which the well can be operated. When lifting heavy viscous fluids, it is most important to set this valve for the maximum possible realistic operating pressure at the surface. If the well lifts easily, it is simple to set the ASC valves at a lower operating pressure and the unloading valve will remain closed; but if the well happens to be heavier to lift than anticipated, it may be desirable to operate on the unloading valve itself and use all the energy obtainable at the bottom of the hole. In the Colonia pool very heavy wet-gas gradients are experienced due to the viscosity of the liquid and the dense mist which is left behind a slug of fluid. There are many combination strings of 3- and 21/2-in. tubing. This aggravates the wet-gas gradient problem and provides wet-gas gradients of about 50 to 70 psi/1,000. An advantage which multipoint lift has provided is increased slug efficiency through better maintenance of pressure under the slug and decreased fall back as the slug passes up the tubing. By using multipoint injection, wet-gas gradients have been reduced to about 30 psi/1,000. This has reduced bottom-hole operating pressure and given a production increase. The ASC valve is not a simple device. It's operation is difficult to understand, and it must be understood to be used efficiently in gas-lift design. Operating problems are difficult to diagnose—whether they be caused by the fluid lifted, valve malfunction, lift gas rate, or operating pressure. Calculations and reasoning are required to find out what is causing the problem. Inherent in the ASC valve is the inability to create large pressure differentials across a slug. Large differentials may be required to overcome the inertia of very viscous fluid as it is being accelerated in the bottom of the hole. This is tied back to the design of the unloading valve and is one reason for the importance of setting the unloading valve for the highest possible operating pressure. ~u; to the narrow spread the ASC valves provide, it is impossible to cycle slower than about 24 cycles/day on choke control. If small production of 150 BOPD and less is expected, a surface time-cycle controller will be required if the most economical operation is to be achieved. To achieve a satisfactory operation, the operator must keep a record of any changes made in the operating pressure of the ASC valves. Anything which may cause changes in casing pressure in excess of the stabilizer setting will change the valve operating pressure, and if this is not noted from daily inspection of the well casing-tubing pressure recorder charts, the operator will lose control of the well. Significant results can be achieved using ASC valves; however, considerable knowledge is required to design with them, and attention to detail is required for satisfactory field operation.

Jan 1, 1965

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By J. E. Coyne, L. E. Tanner, J. E. Boyd

In recent investigations of the isothermal transformations of the retained 0 phase in a titanium alloy having 13 pct V, 11 pct Cr, and 3 to 4 pct Al, there have been indications that the w transition phase is the initial decomposition product at temperatures below about 950°C (510 c).' This metastable phase, found in a number of titanium-base alloys rich in stabilizing elements and known to have an adverse effect on their ductility and toughness, is not easily observed by the usual experimental techniques. Since wis coherent with the /3 matrix,495 distinct interphase boundaries are not revealed metallographically. However, in some cases, an etching effect (i-e., a "mottled" /3 surface) poorly resolved by light microscopy has been found to correspond with the presence of w.6 X-ray diffraction examination has generally been the most suc- cessful means for identifying this phase and crys-tallographic determinations have been made.4'5 Dynamic elastic modulus7 and electrical resistivity measurementse have also aided in the identification of w. In the current study, the electron microscope was utilized to examine microstructures in aged Ti-13V-11Cr-3A1 that were unresolvable by light microscopy techniques. Using negative parlodion replicas (shadowed with chromium at 27 1/2 deg) examination was made of various transformation

Jan 1, 1962

By J. J. Scott

During 1967 wage settlements and strikes ran at a high rate and it has been estimated that union gains of 4 ½ % to 5% per year have been attained in many instances. When these events are coupled with the need to operate on lower grade and deeper deposits the need for technological advances in underground mining becomes obvious. Emphasis has been on ways to reduce the number of manshifts required per ton of product. Most significant advances have been made in rapid advance of primary mine openings, development of mobile, rubber-tired, front-end loaders and hauling units, high-speed drilling with rotary and rotary percussive units and a serious look at nuclear devices to break large volumes of ore cheaply. Boring Developments in bit manufacture and metallurgy have allowed continuous boring-type machines to be used on harder formations than was deemed feasible in the past. Hecla Mining Co. has been using raise boring equipment for drilling 9 7/8 in. diam pilot holes in raises which are later reamed in an upward direction to 48 in. diam. The machine used is a J. S. Robbins model 42R raise borer which has been used successfully to drill two relatively long 48-in. diam holes. The first was 520 ft in length at a dip of 76º, and the second was a 785-ft vertical hole.

Jan 2, 1968

By R. W. Raymond

The important question of the metallurgical value of the coals of the Rocky Mountains and the Pacific Coast is to be settled, of course, by practical experiment. Meanwhile, as I have had occasion to point out, the proximate analyses of these coals throws little light upon it, and is, indeed, likely to mislead the metallurgist, if he compares it with the results of similar analyses upon bituminous and semi-bituminous coals. With the view of showing how large a proportion of the material usually classed as(" volatile matters " consists of combined water, or oxygen and hydrogen presumably in chemical combination, I have collected a number of ultimate analyses from various sources, in the following tables. The numbered analyses in the first table are as follows: No. 1. Monte Diabolo coal—Analyst, H. S. Munroe, Col. School of Mines. 2. Weber Canon, Utah, " " " 3. Echo Canon, " " " " 4. Carbon Stat'n, Wyoming, " " " 5. " " " " " 6. Coos Bay, Oregon, " " " 7. Alaska, " " " 8. " " " " 9. Canon City, Colorado, " Dr. T. M. Drown, Philadelphia. 10. Baker Co., Oregon, " " " 11. Blockcoal,SandCr'k,Ind., " Prof. E. T. Cox. This table affords some suggestive comparisons, to facilitate which a remark or two, explanatory of its construction, will be useful. In the ultimate analysis of coals, the proportions are frequently calculated (as, for instance, in the report for 1872 of Prof. Cox, State

By H. A. Schwartz, A. F. Gorton, H. R. Payne

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By H. R. Payne, A. F. Gorton, H. A. Schwartz

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By J. F. Nester, J. B. Schroeder

COMPOUNDS of rare-earth and iron-group elements are of technical interest because of their unusual magnetic properties. To date, however, all magnetic measurements1-4 have been made with polycrystalline, often polyphase, samples. For the measurement of anisotropic properties, single-crystal samples are necessary to avoid the averaging effect of randomly oriented grains. The purpose of this note is to describe a technique with which we have grown relatively large single crystals of YCo5, NdCo5, DyCo5, and "YFe9". Crystal growth of these materials is complicated because: 1) the binary equilibrium diagrams are, in general, not well-established; 2) in those cases where phase-equilibrium data are available, the compounds of interest are generally formed by peritectic reaction; 3) the molten component metals are chemically very reactive, making contaminaticn of the melts by the crucible material a serious problem. Techniques such as arc or levitation melting followed by strain annealing have been tried5)' in the past with these materials, but with little success because of the peritectic reactions and the inherently poor process control. For this reason we chose to use the zone-melting technique of Mason and cook7 for our work, since past workers8 have had some success in preparing single crystals of peritectic compounds by this method.

Jan 1, 1965

By C. G. Dunn, F. W. Daniels, M. J. Bolton

Recent observations on grain boundary movements in sihcon iron have indicated the possibility of studying grain growth phenomena in two-grain specimens in which several variables affecting growth are readily controlled. These variables are (1) the energy per unit area (?) in the grain boundary, (2) the orientation relationship of the two grains, and (3) the radius of curvature (7) of the moving boundary. Ideally, one grain A should be a narrow rectangular parallelepiped adjacent to a second grain ß as shown two dimensionally in Fig 1. Such a two-grain group becomes unstable when one end of grain A is shaped according to the dotted line. Since the width w of grain A remains constant during growth of grain B, T should also remain constant. The other vari- ables mentioned above can be controlled in the preparation of each two-grain specimen.l,2,3 For a parLicular orientation of each grain, is not necessarily fixed; ? may also depend on the orientation of the grain boundary, but this may be controlled to some degree. The energy relationships for the gowth of grain ß may be derived from the more simple arrangement of two grains A' and B' shown schematically in Fig 2. Here B' largely surrounds A'. Assume these grains are oriented with a common plane parallel with the flat

Jan 1, 1950

By Kenneth L. Ancell

This paper traces the history and performance of a coal degasification project in the Black Warrior Basin of Central Alabama. The primary coal beds being degasified are the Mary Lee and Blue Creek. The area being developed for gas production is also scheduled for underground mining in two to seven years. The paper discusses the early data collection and evaluation. The coals are extremely gassy with some measurements in excess of 500 SCF/ton. Five experimental wells were drilled and produced. Geologic heterogeneities were encountered which affect the performance of the project. Drilling and completion practices together with well design considerations compatible with under- ground mining are discussed. Finally, the gas gathering and sales system together with the early production history is illustrated.

Jan 1, 1982

By Edward J. Way

+1KLEINFONTEIN GROUP CENTRAL ADMlNISTRATION, BENONI, TRANSVAAL, S. AFRICA. The cost and the speed of sinking a shaft are factors of so great importance in operating a mine, that the data given in Table I., herewith published, will be of interest and value to all engaged in practical mining; and for this reason the data are communicated for permanent and accessible record in our Transactions. The figures 'of cost cover the period from January 1, 1903, to May 31, 1903, during which time the total depth sunk was 858 ft. So far as I know, the cost of sinking per foot (£13,15s., 11.04d.) of a shaft of the dimensions 21 ft. by 6 ft. in hard rock, is the cheapest yet on record; and the speed of 213.5 ft. per month, which was attained during May, 1903, is also the best record for speed in sinking in rock so hard as that of this shaft. During the period from January 1 to May 31, 1903, there were 144 rounds worked, involving 4,032 holes, of a total depth of 28,963 ft. 2.4 in., which is equivalent to an average depth of 7 ft. 2.2 in. per hole bored. These data are of added interest from the fact that the work was done practically by native labor.

Jan 1, 1905

By J. L. Stokes, L. J. Demer

It has recently been shown' that epitaxial films of silicon carbide deposited on silicon single crystals possess desirable properties for semiconductor applications. There is one apparent disadvantage to such a system, however; since epitaxial deposition is a high-temperature process, it can result in plastic deformation of the silicon substrate. The accompanying Berg-Barrett X-ray diffraction photographs reveal plastic deformation in two silicon semiconductor crystals which occurred when the crystals were coated with an epitaxial layer of silicon carbide at 1150°C. Due to differences in thermal expansion between the silicon substrate and the epitaxial silicon carbide, the silicon was subjected to stresses while still in the plastic temperature range. Both crystals shown were 0.7 in. in diam and 0.0055 in. thick. The crystals were sliced from a larger crystal so that their polar axes were parallel to the [ill] direction. After cutting, the crystals were polished with diamond paste, and etched in HC1 vapor to remove surface damage re- sulting from the cutting and polishing operations. This provided clean, damage-free surfaces on which to deposit the silicon carbide. Figs. l(a) and l(b) are reflection and transmission photographs, respectively, of the same crystal. A smaller portion of the crystal is shown in the transmission geometry, because a vertical slit was

Jan 1, 1965

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