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By H. J. Struth

The benefits of proration of oil production were perhaps more concretely realized in 1932 than at any time since the oil industry adopted nation-wide production control. Reduced output of crude petroleum, which brought the daily average of the United States down to approximately 2,000,000 bbl. from a peak in 1931 of more than 2,600,000, had a telling effect on the trend of oil prices. Mid-Continent crude was advanced in price from 776, for 36-gravity oil, to $1.04 a barrel. California crude, of 26-gravity at Signal Hill, moved forward from 736 to 976 a barrel. Pennsylvania crude, the only exception to the upward trend, rose in price from $1.82 per barrel to $2.02, only to react to $1.72. This was due to local conditions which necessitated an adjustment to overcome competition from other areas of the United States. East Texas continued to exert a far-reaching influence on the crude and gasoline market during 1932. Despite the fact that oil prices were advanced in most fields, large quantities of oil were produced in East Texas in violation of state proration orders, and sold in the market at prices considerably below official postings. This created competitive conditions in the gasoline market that were felt by all refining centers of the United States. The quantity of gasoline produced from cheap East Texas crude was not large, but the volume was sufficient to influence prices in practically all sections of the country. Thus, while the industry's' economic situation showed visible improvement statistically, the unreported and unseen statistics originating in East Texas proved to be an insurmountable obstacle to the economic betterment that was otherwise apparently justified. Somewhat surprising to many was the fact that gasoline consumption was maintained within 10 per cent of the preceding year. Domestic consumption showed only a net decline under 1931 of about 8.5 per cent; exports dropped in volume to the extent of about 23 per cent. As a matter of fact, domestic gasoline consumption was only about 1.4 per cent less than it was in the predepression year of 1929. Exports, however,

Jan 1, 1933

By E. H. Wells, A. Andreas

New Mexico retained its position as the sixth largest oil-producing state for the year 1937 with a total production of 38,484,630 bbl. This was an increase of 11,680,184 bbl. over the 1936 production of 26,804,446 bbl., or a gain of 43 per cent. The production for Lea County during 1937 was 35,961,056 bbl.; for Eddy County, 2,136,251 bbl.; and for northwestern New Mexico (San Juan and McKinley Counties), 387,323 bbl. The average daily non-marginal well allowable for Lea County on Jan. 1, 1937, was 92 bbl.; at the close of the year it was 67 bbl. The average daily pipe-line runs were less than the allocations of the New Mexico Oil Conservation Commission, but slightly in excess of the state allowables recommended by the United States Bureau of Mines. The average daily production for the year was 105,437 barrels. The total number of completions in the state was 742, of which 638 were oil wells; 19 hydrocarbon gas wells; 5 carbon dioxide gas wells and 80 dry holes. Of the dry holes, 46 were in proven fields. Of these 46 dry holes, 13 were in the Artesia-Grayburg-Jackson-Maljamar area, Eddy County, two in the Getty Extension field, Eddy County, 11 in the Red Mountain field, McKinley County, three in the Rattlesnake field, San Juan County, and nine in the Aztec-Bloomfield area, San Juan County. There were only eight dry holes in the proven fields in Lea County. Southeastern New Mexico Lea County.—The Monument field was the largest producing field in Lea County, with 10,945,788 bbl., closely followed by the Eunice field with 10,927,929 bbl. The Hobbs field, formerly the largest producing field in Lea County, was relegated to third .place, with 7,292,522 barrels. Drjlling during the year closed the gap between the northern part of the Eunice field and the southern part of the Monument field. The wells in this area were relatively small, because of decreased porosity in the lime. The greatest activity in Lea County was in the Monument pool, with 199 completions, 197 being oil wells, one a gas well and one a dry hole.

Jan 1, 1938

By Norman Weiss

Most papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sul-phidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthate by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridan and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1919 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1949

By T. A. Rickard

Our Transactions contain two notable papers descriptive of the stamp-milling practice of the Black Hills and of Grass Valley, namely, the elaborate and complete treatise of Prof. H. 0. Hofman, on " Gold-Milling in the Black Hills,"" and the paper describing the North Star mill, by E. R. Abadie, its superintendent. Having visited and examined the stampmills of both localities, I venture to offer here such comment as more recent information or a different point of view has suggested.†

Jan 1, 1896

[Abrahamson, Guy C., (5'43) Lt., 0-880861, Hammer Field Fresno Calif. Adamec, LAW, (8'42) c/o Braden Copper Co., Rancagua, Chile. Adams, Karl S., (9'43) Univ. of New Hampshire, Durham, N. H. Agnilar, Roperto Q., (9'43) Texas College of Mines, El Paso Texas. Ainge, B'onald Farra, (943) Otago University, Dunedin, New Zealand. Akaran, Cevdet A,, (9'44) Pennsylvania State College, State College, Pa. Albala, Americo, (5'44) School of Mineral Industries, The Pennsylvania State College, State College, PA.]

Jan 1, 1946

By William E. Ford, Edward Salisbury Dana

Normal phosphoric acid is H3P04, and consequently normal phosphates have the formulas R3PO4, R3(P04)2 and RPO4, and similarly for the arsenates, etc. Only a comparatively small number of species conform to this simple formula. Most species contain more than one metallic element, and in the prominent Apatite Group the radical (CaF), (CaCI) or (PbCI) enters; in in the Wagnerite Group we have similarly (RF) or (ROH).

Jan 1, 1922

By A. M. Gaudin

IN flotation lime is used to depress pyrite. For this purpose it is preferred to caustic soda. The low cost of lime and the widespread availability largely account for this preference. However, there is some evidence1 that pyrite is more readily depressed by calcium than by sodium ions at the same pH. To measure the difference in adsorption of calcium and sodium, which is thought to lie at the basis of the differences in depressing action, radionuclides of

Jan 2, 1953

By K. Osseo-Asare

LIX63 In combination with DNNS selectively extracts nickel and/or cobalt from acidic leach liquors with pH values as low as 10 Nickel/cobalt and cobalt/nickel selectivities are achieved by varying the relative concentrations of LIX 63 and DNNS Increasing LIX63 concentration retards both extraction and stripping rates while DNNS has the opposite effect. Slope analyses of equilibrium data Indicate that both LIX63 and DNNS are present in the extracted complexes. Examples of possible flowsheets are presented.

Jan 1, 1981

BOSTON SECTION ALFRED C. LANE, Chairman, GEORGE A. PACKARD, Vice-chairman, H. M. BOYLSTON, Secretary-Treasurer, R. L. AGASSIZ, FRED W. DENTON. The forty-ninth meeting of the Boston Section was held at the Boston City Club on Monday evening, Dec. 23, 1918. The meeting was preceded by an informal dinner at which 29 members and guests were present; three or four others came in later. The reading of the minutes of the previous meeting was dispensed with by consent.

Jan 2, 1919

EXECUTIVE COMMITTEES OF LOCAL SECTIONS Arizona E. P. MATHEWSON, Chairman W. V. DECAMP, First Vice-chairman F. W. MACLENNAN, Second Vice-chairman E. D. GARDNER, Secretary-Treasurer, U. S. Bureau Of Mines, Tucson, Ariz. MICHAEL CURLEY J. P. HODGSON HENRY F.1 ASTER CLYDE E. WEED Boston Meets first Monday each winter month GEORGE A. PACKARD, Chairman FRANKLIN B. RICHARDS, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Rooms 8-219 Mass. Inst. of Tech., Cambridge, Mass. G. W. METCALFE D. H. MCLAUGHLIN

Jan 1, 1932

By L. W. Saperstein, Y. J. Wang

The development of computer programs to solve complex ventilation networks has reached a point of refinement where these programs become a necessary tool of the ventilating engineer. Such a program is presented. This program has an increased efficiency over its predecessors; it also includes the important facility of fixed quantity branches. This is in addition to the earlier capabilities of free-splitting, internal or external fans, and natural ventilation pressures. The program is written in Fortran IV with double-precision arithmetic and is listed here. Sample problems with input and output are also given. The recent, and presumably continuing, official interest in mine safety is bound to result in more stringent control requirements for ventilation. Anticipating this requirement, the Dept. of Mining, The Pennsylvania State University, has developed a computer program for the solution of complex mine ventilation networks. It is the opinion of this department that the program has sufficient merit to warrant its use in normal industrial operating conditions. Although the undergraduate mining engineering students of this department are routinely trained to use the program, it was felt that this training did not present a fast enough means of dissemination; consequently, this paper was written. The conception of the program is not new;1; however, the present version incorporates features that changes it from a scientific endeavor to a useful operating tool. These features include those of earlier programs, such as free-splitting, external or internal fans, and natural ventilation processes plus the important ability of handling fixed quantity branches, and of increased efficiency giving reduced cost. The facility for fixed quantities will be discussed in more detail. The solution of any network depends upon satisfying Kirchchoff's laws. These state that the sum of flow at any junction is zero, and that the sum of the pressure drop in branches totals the pressure drop in the mesh constituted by those branches, that is that the pressure drop around any mesh is zero. The terminology is derived from Synge," and is, in fact, that used by Topologists. A branch is any airway of uniform characteristics; a junction is where two or more airways meet (the minimum number of two airways is useful for describing the point where a low resistance airway changes into a high resistance one due to some physical constriction); a mesh is a path, along some branches, that returns on to itself, but does not need to traverse the same branch twice in order to do so; and a tree describes all those branches in a network which, while connected through all the junctions, do not form any meshes. Obviously the branches-in-tree are open-ended and can be shown to be one less than the number of junction (J-1). The branches-out-of-tree, also called basic branches, are equal to the number of basic meshes and are M = N — J + 1, where M is the number of meshes and N is the number of branches. The major difference between this network and an electrical one is that the law attributed to Atkinson for pressure drop is utilized rather than Ohm's law. Atkinson stated that the pressure drop (potential) is equal to a resistance factor multiplied by the quantity squared. This is written H = RlQlQ where H is the head loss. Q? is written in this factored fashion so that H will always have the same sign as Q. A negative sign is used to indicate that flow in a branch is opposite to that of its containing mesh. A mesh takes the direction of its basic branch. Utilizing Atkinson's law in Kirchchoff's second law and bearing in mind that the first law must remain satisfied, the program will determine all quantities, or head losses as they are related, for the branches of the network. The program uses a Geuss-Seidel form of in-teration, starting from an arbitrary Q and using a correction factor of the type first suggested by Professor Hardy Cross' that will handle the nonlinear equation of Atkinson's law. A fuller description of the interative process is included in Wang and Hartman.' Iteration continues until the correction factor is less than or equal to a preset error (E) or until a maximum number of iterations (MAXIT) have been reached. Utilizing an E of 50 cfm, sample problems have had rapid solutions. Rapidity of solution is also ensured by the method of selecting meshes and basic branches. This is done by the computer, which chooses the highest resistance branches, fixed quantity branches, and those containing fans, as basic branches. Natural ventilation pressures are handled as fans of constant pressure and may be assigned to any branch. The computer will generate a fan characteristic by polynominal fitting if a few operating points from the desired fan are input. A fan may be placed in any branch of the network, except those with fixed quantities. The strength of the present program over its earlier versions is its ability to handle fixed quantity branches. This means that certain branches can have their quantity determined, or preset, by the ventilating engineer. Operating under this constraint, the program will analyze the network and output the pressure change necessary to achieve this desired quantity. A call for positive head loss would require an auxiliary fan; negative head loss would require a regulator. This represents a powerful tool for the ventilating engineer who must insure that certain quantities of air pass across the operating faces or through working stopes. McPherson6 suggested that a ventilation program would be useful for determining in advance which branches were receiving inadequate air, and that subsequent calculations would then indicate the necessary corrections. The present program makes these corrections. Thus the mine manager can know immediately the consequences of changes to his system;

Jan 1, 1971

United Engineering Trustees, Inc James L Head, '55, E C Meagher, '56, Gail F Moul¬ton, '57 Advisory Committee to Real Estate Committee Cleveland Dodge, Herbert Hoover, Paul D Merica The Engineering Foundation W M Peirce, '56, A M Gaudin, '58 Research Procedure Committee A M Gaudin, March '54 Engineering Societies Library Board Frank T Sisco, '54, E M Wise, '56, James L Head, ex officio Engineering Societies Personnel Service Board of Directors E J Kennedy, Jr, E H Robie

Jan 1, 1954

DR FRANK DAWSON ADAMS Montreal, Canada HENRY STURGIS DRINKER Bethlehem, Pa PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England HERBERT C. HOOVER Leoben, Austria ROBERT W. HUNT Chicago, ILL JAMES FURMAN KEMP New York, N.Y. PROF HENRI LOUIS LE CHATELIER Paris France EZEQUIEL ORDONEZ Mexico City, Mexico ALEXANDRE, POURCEL Paris, France RICHARD H, RICHARDS Boston Mass. JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia CHARLES D WALCOT Washington D.C.

Jan 1, 1923

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250' to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,' and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By Shozo Saito, P. A. Beck

Mettrllographic and X-ray diffraction study of Cb-Co alloys in the Composition range of 7 to 33 nt. pct Cb, after annealing at 1175 °', showed that near 25 al. pct Cb on MgNi,-lype hexagonal Laves Phaseexists in a narrow composition range, and that an MgCl- type cubic Laves Phase occurs between approximately 27 and 32.6 ut. pd Cb. Lattice parameter and density measures indicated that, in both phases. the deviations from proper Loves sloichimetry result from the substitution of cobalt atoms for some 0f the columbium atoms. Tlle same phases occurant 1000'C, together with an additional phase of unknown structure, which appears between the hexagonal Laves phase and the cobalt-bose terminal solid solutions KOSTER and Schmid' identified a phase corresponding to the composition VCo,, and more recently the crystal structure of this phase has been determined.' In the Ta-Co system Korchynsky and Fountain recently found two intermediate phases at the composition Taco,, one of them metastable. In contrast to the V-Co and the Ta-Co systems, in the Cb-Co system no intermediate phase has been found4 at the composition CbCo,. The present investigation was undertaken in order to reexamine the question of the existence of such a phase. EXPERIMENTAL PROCEDURE Twelve alloys were prepared by arc-melting in a water-cooled copper crucible under helium atmosphere. Electrolytic cobalt and 99.9 pct pure colum-bium powder have been used as starting materials. It was found that melting losses can be reduced by compressing the colunlbium powder in the form of thin pellets before melting. For the alloys used the melting losses were not higher than 1 pct. The intended compositions of all alloys and the chemical analyses of three of them are given in Table I. Specimens from all alloys were annealed in evac- uated fused silica tubes at 1175°C for 3 days and quenched in cold water. A second set of specimens of most alloys was annealed at 1000°C for 7 days and then quenched in cold water. The annealed and quenched specimens were examined metallographically, using the following etchant: 60 pct glycerine +20 pct H,NO, + 10 pct HF + 10 pct water. Powder specimens for X-ray diffraction were prepared by crushing annealed solid specimens in a mortar. Alloys containing 27.3, 28, 29.7, and 32.6 at. pct Cb annealed at either 1175" or 1000°C were very brittle and it was found unnecessary to reanneal the powders. However, alloys containing 24.8 at. pct Cb, or less, especially those annealed at 1000°C, were much less brittle and re-annealing was required to remove the strains present in the crushed powders. In each case reannealing was done at the same temperature at which the corresponding solid specimens were annealed and it, too, was followed by quenching in cold water. In many instances X-ray diffraction patterns were also taken of the polished and etched solid specimens and compared with the corresponding X-ray diffraction patterns obtained with powders. The X-ray diffraction patterns were taken with an asymmetrical focusing camera, using CrK radiation. For precision lattice parameter measurements some X-ray diffraction patterns were taken with a symmetrical focusing camera, again using CrK radiation. EXPERIMENTAL RESULTS A microscopic examination of the alloys annealed at 1175°C revealed that the alloy containing 25.5 at. pct Cb was composed of a single phase, but that the 24.8 at. pct Cb alloy did contain a small amount of a second phase, identified by means of X-ray diffraction as having a fcc structure, undoubtedly the terminal solid solution based on cobalt. Apart from the few very weak lines corresponding to this minor phase, the X-ray diffraction patterns of these alloys could be well interpreted in terms of a MgNi,-type hexagonal Laves phase structure. The indexing of the X-ray diffraction pattern, Table 11, yas based on the lattice parameter values a, = 4.740A and c,

Jan 1, 1961

By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S' Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath' This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0'03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965