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By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios (K values) were obtained for nitrogen, methane, carbon dioxide, ethane and hydrogen sulfide in two natural gas-absorber oil mixtures and in two natural gas-Elk Basin crude oil mixtures. For each mixture of constant over-all composition, data were obtained at 100°, 150° and 200°F and at various pressures in the range 200 to 5,000 psia. Some effects of composition on the K values were obtained to serve as a guide in choosing K's for engineering calculations on other mixtures. The pressure cell used to obtain the data is a new type and is described here for the first time. INTRODUCTION The phase equilibria of complex hydrocarbon mixtures such as natural gases, crude oils and their mixtures have been studied previously for the purpose of finding equilibrium vaporization ratios for the hydrocarbon constitutents. In a few cases, such non-hydrocarbon.: as nitrogen, carbon dioxide, and hydrogen sulfide were included in the mixture. studied because they occur. in the fluids obtained from petroleum reservoirs. The increasing occurrerce. of these non-liydrocarbon.; antl their growing economic importance. make it necessary to account for them more accurately in engineering calculation.: than is now possible using the meager published data. The available data for non-hydrocarbons may he classified into two groups: namely, binary mixtures of a hydrocarbon and a non-hydrocarbon. and mixtures containing three or more components, only one of which is a non-hydrocarbon. Amon: the former. phase analyses are available for two nitrogen-HC mixtures, tve carbon dioxide-HC mixtures and three hydrogen sulfide-HC mixtures. Data for more complex mixtures are available as follows: Nitrogen-Methane-Pentane'; Nitrogen-Methane-Hexane,'; Nitrogen-Methane-Heptane'; Carbon dioxide-Natural Gas-Natural Gasorline": Carbon dioxide-Natural Gas-Crude Oil". These data have been used generally lor engineering calculations, often with little regard for their precise applicability because data for the non-hydrocarbons in the complex mixtures being dealt with were not available. The use of K values from binary data for calculation:; involving complex mixtures is open to criticism because such K's are not a function of composition and very often show large differences from the K's for the same components in a complex mixture. Thus the effects of composition must be evaluated when obtaining K's for components in complex mixtures. Poettmann and Katz " varied the carbon dioxide content of their mixture.; from about five to ten mol per cent and found substantially no effect on the K values due to this change. This was not surprising since one might expect that changing a minor com-ponent by * three mol per cent would have little effect. It is more important to find the composition change which have the largest effect on the K values. For example. varying the methane or heptanes — plus compositions over a wide rangr may have a large effect on the K'. of all components in the mixture. Interesting data to this effect were obtained by Eilerts and Smith." It was toward these problems that the experimental data presented here were directed. EQUIPMENT The pressure cell used to obtain the data i:. somewhat dif-ferent from those which have been described in the past. Photographs of the equipment are shown in Figs. 1 and 2. Fig. 1 Shows. the front panel: from a .rated position at the right the

Jan 1, 1952

By David J. Mack

A survey and critical appraisal of published information about Young's modulus was originally made by the writer because of a complete lack of information about this very important quantity in works on. mechanics, physical metallurgy, physics, and other sciences. It was felt that a comprehensive summary of such information about Young's modulus might be of general interest and may suggest new problems or lines of attack on other problems that involve E. Hence this paper has been prepared even though it is only a review, with no new ideas or experimental data. The references are only those used in assembling the paper. No attempt was made to compile a complete bibliography on the subject of Young's modulus. CalculatioX oP YouNg's Modulus from Theoretical or Empirical CoNsidera-tions Many attempts have been made to compute E from theoretical considerations. The earliest calculations were probably those of Tomlenson (1883) and Souther-land (1891), but Fess'enden4',~ made extensive calculations a few years later and arrived at the relationship: £ = 78.TOw(i)* where V is the atomic volume. In 1923, Peczalski, working from the same standpoint but with more information available on atomic structure, arrived at an identical relationship, which he expressed as: where B is a constant of value about 8 . 107, p is density and mis atomic weight; the atomic volume, of course, being ml p. Portevind4 immediately pointcd out that while the equations of Fessenden and Peczalski were true of the common metals, they gave low values for the refractory metals with high moduli (Fig. I). He showed (Fig. 2) that much better concordance was obtained by means of an empirical equation of the form: F- KT" where K is a constant; T the absolute melting point; V, atomic volume, and a and b constants of value approximately I and 2 respectively. This constant K in the Portevin equation is not necessarily the same for all elements, as shown by Thompson. Other equations for E based upon theoretical considerations have been derived by Honda and Yamada49 and Lasareff.50 The most recent calculations of elastic moduli based upon quantum mechanics are probably those of Fuchs He extended the method of Wigner and Seitz for calculating the lattice energy and compressibility of monovalent metals and computed the elastic constants of lithium, 18

Jan 1, 1946

By A. M. McQueen

Activity in the oil industry in Peru was somewhat above normal in 1928. Probably the most significant feature was the interest displayed in the oriental region in the northeast part of the country (Fig. 1). This region, though little known, has long been considered potentially rich in oil! gold, coal and other minerals, lacking only transportation to make it the country's most valuable source of income. The Standard Oil Co. of New Jersey, through its recently formed subsidiary the Standard Oil Co. of Peru, has acquired various tracts along the Maranon and Ucayali rivers in the neighborhood of the Brazilian border. Standard Oil Co. interests have had geological and surveying parties in this part of Peru since 1921, and as a result of the work done, we understand they have under lease at the present time some 2,500,000 acres of prospective oil lands. Development in the coastal region continued along normal lines during the past year. Production figures for both the International Petroleum Co. and Lobitos Oilfields show a small increase over the last few years. Total production figures since 1924 for the International Petroleum, Lobitos Oilfields and Zorritos companies, only in a minor degree estimated, are as follows: 1924, 7,924,700 bbl.; 1925, 9,138,042 bbl.; 1926, 10,750,676 bbl.; 1927, 10,110,696 bbl., and 1928, 11,969,677 barrels. International Petroleum Co., Ltd. Operations on the La Brea-Parinas Estate during 1928 continued with satisfactory results; nearly all branches showing improvement over the previous year. The average daily production for 1928 was 25,966 bbl., compared with 21,282 bbl. for 1927, an increase of 22 per cent. During the last two or three years, production methods on the company's property have been improved in line with the advance in scientific technique throughout the oil fields of the United States. Extensive investments were made in compressor equipment for handling surplus gas with the result that the gas-lift and repressuring operations are in no small way responsible for the increase in the 1928 production. In addition, the company's three casinghead plants produced 24,847,708 gal. of gasoline compared with 17,240,865 gal. in the previous year.

Jan 1, 1929

By George W. Riter

Discussion of the paper of H. 0. Hofman and C. R. Hayward, presented at the New Haven Meeting, February, 1909, and printed in Bulletin No. 30, June, 1909, pp. 513 to 529. GEORGE W. RITER, Salt Lake City, Utah (communication to the Secretary*).-In their paper, Messrs. Hofman and Hayward deal with a branch of silver metallurgy that is on very uncertain ground, both as a commercial process and as a metallurgical science; moreover, its field is limited to few localities and to peculiar conditions. The literature on the subject is incomplete and full of conflicts. The paper under discussion clears u p no disputed points; on the contrary, because of hasty generalization, its tendency is towards further confusion. In Table I., the authors assume that each test-lot of 1,800 g. of ore contained exactly 5.499 g. of silver, that any variation in the quantity of silver recovered, however slight, should be ascribed to variation in the time of grinding. It is barely possible that the ore was mixed so uniformly as to justify this assumption; but those of us who know how difficult it is to get uniform samples of any ore in which silver mineral is present in rich particles will have a doubt on this point. The unlikelihood of getting absolutely uniform test-lots of ore also reflects on the data in Table II., on the effect of varying the amount of salt in a pan-charge. The authors say " The salt series was the last one that was investigated." This again raises a question as to whether the ore was split into test-lots at the time of sampling, or whether it was kept in bulk in such a way as to permit mechanical concentration of values before the end of the experiments. The conclusion following Table II.: " There is no reason, therefore, for going beyond six per cent. of salt," is hardly to the point. If we assume that salt is of benefit only when in solution, it follows that the relation between the quantity of salt

Mar 1, 1910

By W. S. Ayres

I. Introduction. This cavern was discovered Oct. 32,1904, by Mr. Charles 8. Deutschman, in company with whom I made, May 29 to June 3,1905, at the request of Mr. Howard Douglas, Superintendent of the Canadian National Parks, the first exploration of it for the Canadian government. The results were stated in a paper, orally presented, with lantern-views from my photographs, at the British Columbia Meeting of the Institute, Victoria, B. C., July 5, 1905.* The present paper embodies also the results of a second examination, made Oct. 25 to 29, 1905. The accompanging map, Fig. 1, will serve as a guide to the following description. 11. Location. The cavern is situated at snow-line, at the head-waters of Cougar creek, on the west slopes of the Selkirks, about 2 miles north from Ross Peak water-tank, and 5.5 miles west from Glacier station, on the main line of the Canadian Pacific Railway. It was then reached by an arduous climb from the water-tank, up the ravine of Cougar creek, for 8,000 ft. (2,000 ft. of altitude) over rock- and snow-slides, and through a thick tangle of alders. But an easy and very picturesque trail has, during the past summer, been opened by the government from Glacier station, which is also a hotel of the railway company. Figs. 3, 3 and 4 represent views, not heretofore published, of the grand scenery of this region, so rapidly becoming the object of attraction to thousands of tourists from all parts of the world. These views, as well as those shown in Figs. 5, 6, 7, 8

Jan 1, 1908

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By Albert L. Toenges

COAL mining technique progressed slowly until the advent of mechanized mining. The cutting machine was a forward step, but had only a limited effect upon improving the percentage of coal recovery. Previously, the physical fitness of the loaders and the total output of the miners fixed mine production. The miner was an independent contractor and supervision over his working place was superficial. Rising costs and the inroads of substitute fuels demanded increased output per man to lower the unit production cost. Therefore, the amount of coal loaded mechanically in underground bituminous mines has risen from 0.3 per-cent in 1923 to 7.4 in 1929, to 20.2 in 1937, and to 48.9 percent in 1943. When loading devices were introduced it became necessary to adapt them to existing systems of mining, or to alter the mining system to fit the machine. An increased amount of supervision was required as output depended upon proper operation of the machine rather than on the physical fitness of the individual.

Jan 1, 1946

By Raymond D. Daniels, Frank E. Rizzo, James D. Gerber

ThIS discussion describes a method for the addition of small amounts of oxygen to columbium (niobium) in an accurate and reproducible manner. The method is based on the complete reduction by columbium of a carefully weighed amount of another metal oxide. The equilibrium Pq associated with Cb-CbO mixtures is extremely low, e.g., 10"25 atm at 100O°C, and the pressures over Cb-0 solutions are even lower. The equilibrium Pq associated with a given metal-metal oxide mixture can be easily obtained, with the aid of a Richardson-Jeffes chart.' Although columbium should effectively reduce almost any metal-metal oxide combination, the proper choice of a metal-metal oxide system is complicated by the low rate of oxygen transport in the gas phase at low oxygen pressures and the difficulty in reducing any columbium suboxide formed during the reduction of the oxygen source material. Thermodynamically, oxide formation on columbium will be avoided so long as the oxygen partial pressure over the columbium is below the equilibrium pressure associated with the mixture Cb-CbO. The logical choice of a source for oxygen would appear to be a mixture of Cb-CbO, since oxide formation would be precluded by nucleation difficulty. But calculations using the kinetic theory of gasses indicate that, for a temperature of 900°C, the reaction would proceed too JAMES D. GERBER, formerly Research Assistant, University of Oklahoma, Norman, Okla., is Research Metallurgist, Air Force Weapons Test Laboratory, Kirtland Air Force Base, N. Mex. FRANK E. RIZZO, Junior Member AIME, formerly Assistant Professor of Metallurgy, University of Oklahoma, is Associate Professor of Metallurgy, University of Texas at El Paso, El Paso, Tex. RAYMOND D. DANIELS, Member AIME, Professor of Metallurgical Engineering, University of Oklahoma, is an NSF Fellow, Institute de MBtallurgie Structurale, Universite de euch:tel, Neuchitel, Switzerland. Manuscript submitted October 28, 1968. IMD

Jan 1, 1970

By T. R. Wright

IN few mining regions in the world are the ores so varied and complex as in the Andes of central Peru. Consequently, in few localities is one company engaged in so many and such diverse metallurgical operations as the Cerro de Pasco Copper Corp. Concurrent with the mining of complex lead-zinc ores in Peru, and the consequent expansion of the Corporation's metallurgical activities, a department of metallurgical research was established in 1927 at La Orova. Facilities were provided for research in ore dressing, hydronivtallurgy pyrometallurgy, electrometallurgy, and analytical chemistry. In addition to laboratories. various pilot plants were built, including a concentrator, leaching plant, "by-product" smelter, and electrolytic refineries. These pilot plants are not diminutive units; they are designed and equipped as semicommercial plants for operation on a continuous 24-hour basis thus assuring the duplication of pilot plant results in actual practice. In general, the sequence in the development of metallurgical operations hasbeen as follows: (1) investigations in the laboratory to determine the most effective and economical method of treatment; (2) continuation of the research project on a pilot-plant scale when the evaluation of the laboratory

Jan 1, 1945

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister's technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By D. M. S. Bhatia

The intimate association of iron formation and massive sulfide deposits has been documented by many investigators (McAllister, 1960; Hutchinson, 1972). In a classic example of such an association, four distinct facies (oxide, carbonate, silicate and sulfide) were identified in an Algoma-type iron formation occurring in Paleozoic rocks, but exhibiting physical features (banding) and chemical composition (SiO2 + A1203 + Fe2O3) typical of Precambrian iron formations. The geochemical variation of the iron formation was studied by analyzing 62 samples for Si, Al, Fe, P, S, and Cop. Following a model proposed by James (1954), the geochemical and mineralogical variation of the iron formation can be used as an excellent tool for the exploration of massive sulfide deposits.

Jan 1, 1982

By Svend Rordam

THE development of a cement that will resist the destructive action of sea water and other corrosive waters is a problem that has occupied cement chemists for the past one hundred years. It has been found that of the various salts that commonly occur in corrosive waters, sodium sulphate, magnesium sulphate and magnesium chloride are most destruc-tive to cement. Many investigations have been carried out in the United States, in Canada, and in Europe to solve the problem of what constitutes a sulphate-resistant cement, and during the past 10 years some of the findings give definite information in this respect. COMPOSITION OF CEMENT Portland cement is composed of four major compounds: 1. Tricalcium silicate 3CaO.Si02 (C3S) 2. Dicalcium silicate 2CaO.Si02 (C2S) 3. Tricalcium aluminate 3CaO.Al203 (C3A) 4. Tetracalcium aluminoferrite 4CaO.Al203.Fe203 (C4AF) The two calcium silicates are the main contributors of strength. The tricalcium aluminate contributes some to the early strength of the cement but has the least resistance of the four compounds toward the attack of sulphate waters. The tetracalcium aluminoferrite does not contribute very much to the strength, but is far more resistant to sulphate waters than the tricalcium aluminate. When hardened cement is exposed to water containing sodium or magnesium sulphates, these salts will react with the hydrated tricalcium aluminate in the cement and form compounds that will cause a swelling, disruption and crumbling of the hardened cement.

Jan 1, 1939

By S. P. Ray, B. D. Sharma

THE activation energy values for self-diffusion in pure metals have been correlated with a number of physical properties such as melting points,1 valences,' Debye temperatures,3 and cohesive energy densities.4 Extending the melting point correlation, the self-diffusion activation energy values for the alloys can be similarly correlated with the solidus temperatures. For metals and alloys which exhibit phase transformations, such a correlation is not feasible because of the uncertainty of various physical properties of the corresponding phases. Using thermodynamical approach, Ardell5 calculated the hypothetical melting points of the low melting phases of the polymorphic metals. However, these calculated melting points do not show reasonable correspondence with the activation energy of self-diffusion. Recently, a new approach treating metals and alloys as electron concentration phases has been developed by Engel6 and Brewer.7 These workers have attempted to correlate the crystal structures with the electron configurations of the atoms existing either in ground state or in an excited state of low promotion energy. The basic postulate of this theory is that whereas the contribution to the bonding of the metal comes from the interaction of both d and (s-p) electrons existing either independently or in hybridized states, the existing crystal structure is controlled by the (s-p) electrons alone. Specifically, a metal is supposed to crystallize in bcc, hcp, or fcc phase provided the metal has one, two, or three valence electrons per atom in the (s-p) configurations. The diamond, or ZnO and ZnS structures, occur with four (s-p) electrons per atom. Secondly, the contribution of d electrons to bonding is supposed to increase with atomic number

Jan 1, 1970

By P. H. Lindon, J. C. Billington

Fe-O melts containing 0.045 pct 0 were deoxidized with Mn-Si-A1 alloys. Product compositions were reluted to the melt and alloy compositions and were found to be most sensitive to the aluminum content of the alloy. Low residual oxygen contents could be obtained when aluminum oxide was present in the Products because of the reduction of silica and manganese oxide activities. Flotation of the Products from a quiescent melt was followed both by analysis of the oxygen content and metallographic measurement of inclusion concentration. MnO-SiO2-A12O3 products were found to float most rapidly when their composition was such that their viscosity may be expected to be low. Changes in the particle size distribution indicates that particle coalescence occurred and differences in the degree of coalescence are thought to be responsible for the different flotation rates observed between products 0f differing composition. Measured flotation rates were slower than those Predicted from a model based on Stoke's Law, although alumina flotation might be reasonably accounted for by this model. Interfacial effects between oxide particles and the melt are believed to be responsible for the discrepancy. It has been recognized that deoxidation products constitute a large proportion of the nonmetallic inclusions present in killed steel. The amount of oxide inclusions which originate as deoxidation products depends largely upon three factors. These may be summarized, according to P16ckinger1 as: 1) Amount of primary products remaining in the steel prior to cooling. 2) Residual dissolved oxygen content of the steel after deoxidation. 3) Amount of secondary products, formed during cooling and solidification, which remain entrapped in the solid steel. In a well-deoxidized steel containing residual aluminum and/or silicon, the equilibrium dissolved oxygen content is usually very low and so the maximum amount of oxide which may be produced as secondary deoxidation products is small in comparison with the amount of primary products. It may be seen, therefore, that the amount of indigenous nonmetallic inclusions may be minimized if a low dissolved oxygen content is achieved by deoxidation and if the primary deoxidation products are efficiently removed. Oxides which originate by reaction of the metal stream with the atmosphere during teeming are not considered in the present study. It is known that two or more deoxidizers may result in a lower equilibrium oxygen content when used in conjunction with one another than when any of the individual deoxidizers are used alone. Equilibrium studies by Hilty and crafts2 and by Bell3 have shown that manganese increases the effectiveness of silicon as a deoxidizer, and Walsh and Ramachandran4 relate this to a reduction in the activity of silica in the products as the manganese :silicon ratio in the steel increases. It was also shown by Herty's work on deoxidation of steel by silico manganese alloys,5 that there existed an optimum ratio of manganese to silicon which gave a minimum inclusion content. This ratio was in the range 4:l to 7:l and the (FeO-MnO-SiO2) products formed by such deoxidation practice were found to lie in a composition range having very low liquidus temperatures (1170 to 1250°C approx). The optimum manganese:silicon ratio was then explained by postulating that these fluid products were able to coalesce and that the larger particles formed floated out of the steel very quickly as predicted by Stoke's Law. The present work examines the effectiveness of various Mn-Si-A1 alloys as deoxidizers and their effects on the composition and removal of primary deoxidation products from a quiescent melt. EXPERIMENTAL TECHNIQUE Approximately 250 g of prepared Fe-O alloy, containing 0.045 to 0.055 pct O, were melted in an alumina crucible and deoxidized at 1550°C by plunging a thin steel cartridge containing the deoxidizer below the melt surface. A high frequency induction furnace supplying current at 8.5 kHz was used to heat a graphite susceptor, the interior of which had been machined to give a wall thickness of 0.85 in. to form a receptacle for the alumina crucible. The iron melt was essentially quiescent as the induced current was concentrated at the external surface of the graphite susceptor by the skin effect. A nonoxidizing atmosphere was maintained over the melt by passing a continuous stream of argon through the lid of the susceptor. The melt temperature was measured before deoxidation, and again at the end of an experiment by means

Jan 1, 1970

By F. H. Spedding

CONSIDERABLE confusion exists in the literature concerning the phase transformations exhibited by the lighter rare earth metals; namely, lanthanum,1-8 cerium,1,3,5,8,9-15 praseodymium,8 and neodymium.1,8,16,10 To obtain further information

Jan 1, 1958

By F. R. Cattoir, R. W. Kimball, C. T. Anderson, V. V. Donaldson

THIS paper is the second of a series on the effect of various elements on hot-working characteristics of Fe-C alloys to be issued by this laboratory. The investigations being conducted at the Ferroalloy Research Branch of the U.S. Bureau of Mines, Redding, Calif., involve fundamental research on the effects of various alloying materials and impurities on the physical properties of high purity Fe-C alloys. This paper deals with the determination of the limit of forgeability of steels containing varying amounts of manganese and sulphur. A paper discussing the hot-working characteristics and the physical properties of the forgeable alloys is being prepared. One of the principal impurities in all steels is sulphur.. The phenomenon, hot-shortness, commonly attributed to sulphur, has long been a source of expense and inconvenience to both the maker and user of steels. In steelmaking practice, this effect of sulphur has been overcome by the addition of manganese which, apparently, acts as a desulphurizer. Manganese is also used as a deoxidizer and alloying material. The critical and strategic position of man- ganese gives added importance to research which may contribute to its conservation and more effective utilization. It is not the purpose or intention in the present paper to give any explanation of the mechanism of either hot-shortness or its prevention but rather to report the results of forging high purity Fe-C alloys of the range of compositions near the limit of hot-forgeability. Temperatures for each phase of reduction were duplicated within 20" to 30°F for all tests. The starting material was sponge iron, which, after melting and purification, gave a high purity iron containing about 0.001 pct each of silicon and phosphorus. Scrap iron was not considered suitable because of its high percentage of contaminants and wide variation in analyses. The sponge iron was melted and refined for melting stock in a three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating as described in the preceding paper. Additives were carefully selected to avoid addition of contaminants. The sulphur was added as resublimed flowers of sulphur or purified roll sulphur of analytical grade. The manganese used was dehydrogenated high purity electrolytic material produced by the Bureau of Mines plant at Boulder City, Nev. High purity aluminum in the form of wire was used for deoxidation. The limestone was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2,3.0; and P2O5, 0.014.

Jan 1, 1955

By E. C. Burke, W. R. Hibbard

G. B. Craig (University of Toronto, Toronto, O,nt., Canada)—The advent of pyramidal slip at room temperatures in a magnesium crystal (M2,) and the very low value reported for the critical shear stress are puzzling. Table I1 shows the calculated values (approximate) for sin x cos I in this specimen if all the (10l) planes are considered. If So is the shear stress resolved in the direction of glide, on the glide plane, and U, is the stress operative in yield point tests, then: S,, — 325 (0.169) 55gpersqmm (approximately) for 1101: S,, = 325 (0.465) = 151 gpersqmm (approximately) for (0001): S,, — 325 (0.101) - 32.8 gpersqmm (approximately) Thus, we see the pyramidal plane in which the minimum shearing component operated. Barrett"' stated: "Experiments have repeatedly shown that, when there are several crystallographically equivalent slip systems in a crystal, the one having the greatest resolved shear stress will become active. ..." It does not appear to me that the measurements given are conclusive proof that pyramidal slip operated. E. C. Burke and W. R. Hibbard, Jr. (authors' reply) —Although the low value for the critical resolved shear stress for pyramidal slip may be puzzling, there does not appear to be any basis for questioning the validity of the measurements. Under the influence of constraints, slip systems having decidedly lower shearing components may become operative, e.g., "cross-slip" or the "forced glide" in magnesium reported by Bakarian. Since we believe that pyramidal slip occurred in the specimen because basal slip was inhibited, it is not too surprising to find an operative plane with a lower shear stress. -7 C. S. Barrett: Structure of Metals U94jl p. 2J6. New York. McGraw-Hill Book Co.

Jan 1, 1953

By R. K. Matheson

THE Nivloc mine is 9 miles west of Silver Peak, Esmeralda County, Nevada. It has been operated by Desert Silver, Inc., since the summer of 1937. The cyanide mill treats 19o tons of silver-gold ore per day. In March of this year the main operations were about 2000 ft. west of the main shaft, which served as the downcast air passage for the mine. The mechanical blowers in use were sufficient to ventilate the west end at that time, but it was foreseen that as the mining area was extended ventilation would be an increasingly difficult problem, especially during the summer months. It was decided, therefore, to continue a raise from a point 100 ft. above the highest mining level (440-ft. level) to the surface; a distance of 443 ft. at approximately 65° From this point 40 ft. of drifting would be necessary to connect with a shallow shaft on the surface. (Fig. I.) All the raise was serviced from the 440-ft. level; costs and progress obtained in the initial 100 ft. are included in the following pages. CHOICE OF RAISE A raise in this locality would have four objects: (I) to provide an ample supply of fresh air to the working places; (2) to explore the vein from the highest mining level to the surface; (3) to provide waste fill for stopes in the area, and possibly provide a transfer for waste from the surface; (4) to provide an emergency exit in the west end of the mine. Before the mining of an ore shoot in the eastern part of the mine, a similar raise had been driven for purposes of ventilation and exploration. This raise and subsequent mining showed the vein to be noncommercial for a distance of about 250 ft. below the surface. However, in the area under operation, old surface workings showed occasional values. Thus from a development standpoint the raise was an excellent prospect. The raise chosen was a three-compartment, stulled raise having two chutes and a manway. The manway inside timber measured 4 ft. 8 in. by 4 ft. 6 in.; it carried air and water pipes, a ladderway and a slide for a timber skip. The two chutes would be used for drawing off the muck and the cleaning of the bulkhead, as well as for ore and waste passes, which would be especially useful for lateral exploration from the raise. The fairly large cross section of the raise (6 by 15 ft.) would provide a large quantity of waste for backfilling, and more could be obtained from a glory hole on the surface. TIME SCHEDULE As speed in completing the raise was the main requisite, three shifts were considered, but two shifts were decided upon when it was found that three would necessitate considerably larger fans than those available for clearing the raise. The main diffi-

Jan 1, 1942