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By E. Gybbon Spilsbury

(Pittsburg meeting, March, 1910.) THE recovery of gold and silver from their ores by means of the cyanide process has been so successful in the last few years that any radical improvement would seem impossible; yet the appliance to which I wish to call attention in this paper is really a radical departure from the methods now in general use. The most modern and approved of these, known as the all-sliming method, depends for its success on the grinding of the. ore so fine that practically 90 per cent. of it will pass through a 200-mesh screen. The slimes thus produced are then agitated and aerated in tanks of various types. The main object of this treatment is to insure such a thorough admixture of the pulp and solution that every particle of the ore is surrounded by a volume of solution sufficient to insure the dissolving of the whole of the gold- and silver-content. In addition, in order to expedite the action of the cyanide, and to oxidize such elements as would, if left in their active state, become cyanicides, air is blown in under pressure. In the Pachuca tank, this air is the active and sole means of agitation. The chief objections to all the methods off agitation used heretofore are the expense of operating and maintaining the mechanical devices for keeping the pulp in suspension, and the length of time required to obtain a fairly complete extraction. of the values. These objections are inherent to any method of agitation effecting a circulation of the pulp and the solution together, by giving the whole mass a circular movement, as in the low-tank system, or a vertical circulation, as in the Pachuca-tank system. In both methods, the particles of ore are kept traveling in the same direction as the solution, and with very little difference of speed; so that, while the whole mass is in

May 1, 1910

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By Reginald Williams

THE amount or value of the precious metals consumed in dentistry is probably amazing to most people. It falls very little short of that which is consumed in jewelry. Inasmuch as the ultimate destination is in the human mouth, dental alloys enjoy some importance because life and health depend upon restorations made with them. Prosthetic dentistry has made wonderful progress in the last few years. The manufacturers who supply the metals also deserve commendation. This industry which deals with metals to go into people's mouths is comparatively new. There is no literature on the subject, and little or no precedent by which to be guided. It was only by close cooperation with the dentist or prosthetic technician that desirable physical properties were produced, as nearly as possible, in the metals which were available and permissible. It is true that there were and still are conflicting opinions among the dentists as to the physical properties they require. Sometimes they request the impossible, such as alloys which are exceedingly stiff and springy, yet will bend or adjust easily. Even in this latter instance, progress has been made by supplying methods of heat-treatment whereby metals may be softened or hardened at will. (Figs. 1 and 2.) The demands made upon manufacturers are extremely varied. They must supply metals of tensile strengths ranging from approximately 30,000 to 100,000 lb. per sq. in. and over. The latter metals must be workable and in many instances capable of extreme deformation. They must not be affected by mouth conditions, nor should they oxidize greatly when molten, at red heat, or during a soldering operation. In addition to physical specifications, color demands must also be met. The firm of which I have the most knowledge manufacturers 11,553 standard stock articles of precious metals, taking into consideration formulas, finenesses, grades, colors, gages, lengths, sizes and weights. If special demands are taken into consideration, the number would be in excess of 25,000. Wrought metals are manufactured in a great many alloys of different sizes and shapes, such as plate, bar, rod, wire, sheet, strip, mesh and foil. There are also other products of importance.

Jan 1, 1928

By John D. Morgan, Sylvain J. Pirson

An instantaneous and continuous analysis of a mineral suspension should be of great value in controlling various mineral preparation processes. Described herein is a method of analysis based on the use of high-frequency alternating current, which, under certain restrictive conditions, could be of use. Theoretical Considerations In a suspension of conductive minerals, the electrical effect primarily responsible for the variations in electric conductivity is the capacitance. In Fig Ia, let an alternating voltage E be applied across two electrodes F and F', between which are two rows (S and T) of mineral particles, all of approximately the same size, immersed in a fluid. Let the number of rows of particles between the electrodes be R and the number of particles in each row be N. If A is the area of a particle, D is the distance separating two particles, and k is a constant depending on the fluid, the capacity, CO, of the particle system will be given by: KRA C°= ND Referring now to Fig Ib, let R, the number of rows, be held constant, but let N, the number of particles in each row (S and T), be increased X-fold. The capacity, C1, of

Jan 1, 1949

By Charles W. Bloomquist

The profitability of miscible flooding in a hypothetical target oilfield is examined. The major costs, including Windfall Prof it Tax, are identified and their re1ative importance are discussed. The sensitivity of profit to important physical and economic variables is evaluated and discussed, including variance in oil recovery, oil price, injectant requirements, injectant cost, and capital requirements. Economic sensitivities to important development and operating decisions such as timing, Spacing, Slug size, and gas recycling are also analyzed. The Windfall Profit Tax (WPT) as it applies to gas miscible EOR projects is reviewed. The effect of WPT on each of the various project cases is analyzed and the effect of reduced WPT on remaining production from existing operations is evaluated. Tax implications are compared for integrated vs. "independent" controlled projects and the alternative of expensing vs. capitalizing tertiary injectants is also evaluated. The impact of the Net Income Limitation in reducing WPT. during early and late project life is determined and discussed.

Jan 1, 1982

By Sandford S. Cole, John S. Breitenstein

The recovery of over 80 pct of the vanadium values in titaniferous magnetite from Maclntyre Development,Tahawus, N. Y., was accomplished by an oxidizing roast with Na2O3-NaCI addition. Process description is given for leaching of roasted ore and precipitation of V2O5 and Cr2O8 from leach liquor. THE exploration and development of the Mac-Intyre orebody at Tahawus, N. Y., by the National Lead Co. provided a source of vanadium. Analyses of various composite sections of the drill cores of the MacIntyre orebody were made to establish whether or not the vanadium was constant throughout. Ten drill cores were sampled as 50 ft sections, crushed, and a portion magnetically concentrated. The head and concentrate were analyzed for total iron and vanadium. The results on the concentrates indicated that the vanadium is associated with the magnetite and maintains a close ratio to the iron content. The nominal ratio of 1:25:140 of V: TiO2:Fe was found to exist in the concentrates. Typical value for the vanadium in the magnetite both from laboratory concentration and mill production is 0.4 pct. The recovery of vanadium from the magnetite was investigated in 1942 to 1943. The research program encompassed both laboratory and pilot-plant work on sufficient scale to provide adequate data to establish the feasibility of a full scale plant. The recovery of vanadium from various ores has been reported in the literature and has been the subject of many patents. The literature dealing with recovery from titaniferous ore by roasting is quite limited. Roasting with alkaline sodium chloride, sodium chloride or alkaline earth chlorides, and sodium acid sulphate have been claimed in various processes as effective means.1-8 The reduction of the ore, followed by acid leaching, was another method proposed.'-' "he use of various pyrometallurgical processes for recovery of vanadium in the metal or in the slag has also been extensively investigated, but the results had little application to the problem."-" The separation of vanadium values from subsequent leach liquors and vanadium-bearing solution has been the subject of a considerable number of papers and patents. The most practical is by hydrolysis at a pH of 2 to 3 by acidifying a slightly alkaline solution. Data on solubility of V²O5 and V2O4 in water and in dilute sulphuric acid indicated a solubility of 10 g per liter in water.'" Laboratory Results Magnetite Analysis: Adequate stock of magnetite was provided so that the laboratory and pilot-plant operation was on ore representative of the mill production. The ore was analyzed chemically and examined by petrographic methods to ascertain whether the vanadium was present in combined state or as an interstitial component between grain boundaries. No evidence was obtained which would indicate that the vanadium was in a free state as coulsonite.15 The analysis of the ore was as follows: Fe²O³, 47.4 pct; FeO, 29.1; TiO,, 10.1; V, 0.40; and Cr, 0.2. The screen analysis of the ore on the as-received basis was: -20 +30 mesh, 28.8 pct; —30 +40, 18.9; -40 +50, 9.7; -50 +60, 15.1; -60 4-100, 5.9; -100 + 200, 11.2; -200 +325, 3.7; and -325, 7.2. Roasting Conditions: The prior practice indicated that a chloridizing roast with or without an alkaline salt had been effective on other titaniferous magnetites. On this basis roasts with additions of sodium chloride, sodium carbonate and mixtures thereof were investigated varying the roasting temperature between 800" and 1100°C. Since the ore had shown no segregation or concentration of vanadium, the influence of particle size on the freeing of vanadium by the reagents during roasting was determined. The initial work was on silica trays in an electric resistance furnace with occasional rabbling of the charge. Subsequently, the roasting was carried out in a small Herreshoff furnace to establish the influence of products of combustion on the recovery of the vanadium. The laboratory tests showed that this ore required an alkaline chloridizing roast, in conjunction with a reduction in particle size to less than 200 mesh. When roasted in air at 900 °C with 5 pct NaCl and 10 pct Na2CO³, over 80 pct recovery of the vanadium was attained as a water-soluble salt. The presence of alkaline earth elements gave detrimental effects and care had to be exercised to avoid any contamination of the ore or roast product by such materials. The solubilization of vanadium under the various conditions is given in a series of curves in Figs. 1 to

Jan 1, 1952

In any earth-moving operation, more profit may be earned or lost by equipment scheduling than by any other single facet of the project. Many now-defunct earth movers would have survived the cost-profit squeeze had they followed an efficient, cost saving, equipment scheduling program. The ideal program would have every item of the equipment fleet working all of the time. In practice this ideal situation is not possible. Several basic methods of equipment scheduling, with an infinite number of minor variations, are used. The first approach is the use of a "minimum equipment fleet," of which all items or equipment are scheduled each working shift.

Jan 10, 1967

By Fred C. Bond

IN crushing and grinding the larger particles are more exposed to the work input. They absorb most of the work and protect the smaller neighboring particles from destructive contact with the crushing surfaces or grinding media. The importance of this exposure differential upon the reduction efficiency and product size distribution has long been recognized. Unfortunately, there has heretofore been no direct method of evaluating it, and such indirect methods as observing the slope of the plotted product size distribution line have been used as an indication. In this presentation the Third Theory of Comminution' has been used, together with the exponential formula for size distribution, to evaluate the ex- posure ratio and exposure constant and to illustrate examples of their utility in crushing and grinding applications. The exposure ratio Er varies from zero to unity. It is zero when the product particles are all of one size, and it is unity when the work input has been equally distributed among all particle sizes. It can readily be found from screen analyses plotted according to the Third Theory. The exposure constant K is derived from the reciprocal of the exposure ratio Er. It permits more consistent predictions of size distributions and evaluation of many factors concerned in size reduction operations. The Third Theory1 states that the specific work input required for size reduction is inversely proportional to the square root of the product size less the work required to form the feed. When P represents the diameter in microns which 80 pct of the product passes, F is the size 80 pct of the feed passes, Wi

Jan 1, 1958

By John A. Mathews

RESEARCH in the steel industry, as in other lines of manufacturing, has for its principal purpose the increasing of profits. That is what manufacturing companies are for, and all departments of the organization must be so coordinated as to lead to profitable operation. To divide a payroll into productive and non-productive labor is misleading. Productive labor, in fact, is necessary labor, and non- productive labor is the labor we can get along without. One might as well say that the steering wheel is not a part of an automobile as to say that the directing minds of an industry are non-productive. Legitimate manufacturing profits in a steel company or any other company are the reward that the public pays for service rendered or risk taken. The desire for profits is the impelling motive that leads investors .to take risks and build up industries that give employment to others. Every department of a company, be it executive, manufacturing, financial, sales, or research, must contribute to the one end which brings success-profits.

Jan 1, 1921

By Y. A. Rocher, J. E. Dorn, L. A. Shepard

Creep activation energies for single aluminum crystals favorably oriented for shear by (010) [101] glide were detemined over the temperature range from 78" to 900°K. Observations of slip bands on the specimen surface were made in conjunction with the investigation. From 78" to 780°K, the activation energies obtained in this imestigation agreed closely with those previously found for creep by (111) [101] slip. Between 78" and 140°K, the activation energy was identified with the Peierls process, while between 260°and 780°K the activation energy was close to that for cross-slip. The coarse wavy slip bands nominally parallel to the (010) plane observed above 260°K were attributed to fine cross-slip. From 800" to 900°K, unusually high apparent activation energies ranging from 28,000 to 54,000 cal per mole were obtained. These apparent activation energies were attributed to re crystallization. AS illustrated in Fig. 1, a recent investigation1 has shown that creep of aluminum single crystals by the (111) [i01] mechanism is controlled by three unique processes, each of which is characterized by a single activation energy which is independent of the applied stress and the creep strain. A comparison of the observed activation energies with theoretically calculated values permits a fairly clear identification of the three operative creep processes. Below 450°K, where the activation energy for creep is 3,400 cal per mole, the deformation is controlled by the Peierls process, the activation energy for creep agreeing well with that calculated by seeger2 for the energy required to nucleate the motion of a dislocation loop against the atomic forces of the lattice. Between 590° and 750°K, the observed activation energy for creep of about 28,000 cal per mole agrees well with the energy necessary to induce cross-slip. Seeger and schoeck3 estimate that the activation energy is about 24,000 cal per mole whereas Friedel4 recently calculated this activation energy to be 28,000 cal per mole. Above 800°K the activation energy of 35,500 cal per mole that was observed for creep agrees well with that estimated for self-diffusion in aluminum.= In this range the operative rate-controlling slip process has been clearly identified as that arising from the climb of edge dislocations. The objective of this investigation is to ascertain whether a single crystal of aluminum favorably oriented for simple shear in the [loll direction on the (010) plane might exhibit uniquely different activation energies for creep from those obtained previously for (111) [101] slip. Whereas the exis- tence of such unique activation energies would constitute incontrover table evidence for new mechanisms of slip, the absence of any new activation energies might suggest that slip of aluminum is confined to the (111) [loll mechanism. Several factors prompted the selection of the (010) [101] orientation for study. First, there are more reported observations of (010) [loll slip than of any other nonoctahe-dral mechanism.8-10Secondly, Chalmers and Martius1l have concluded from considerations of the energies of dislocations that (010) slip is the second most favored mechanism in face-centered-cubic metals. Finally, favorable orientations for simple shear by the (010) [loll mechanism provide the least favored orientation for slip by the (111) [101] mechanism. EXPE-RIMENTAL PRO-CEDURE The high-purity aluminum stock, specimen preparation, shear fixture, extensometry, and experimental technique used in this investigation were the same as those previously reported.' Single-crystal spheres grown from the melt of 99.995 pct pure Al* were _ *The high-purity aluminum used in this investigation was graciously given by the Aluminum Company of America. oriented, carefully machined into dumbbell-shaped shear specimens, annealed, and chemically polished. The finished specimen had a central reduced section 0.190 in. wide and 0.590 in. in diam and 1/4-in. grip sections at both sides, 0.690 in. in diameter. The specimen was oriented in the stainless steel grips of the shear fixture with the (010) plane perpendicular to the dumbbell axis and the [loll direction parallel to the stress axis within 2 deg. Creep activation energies were calculated in the previously described manner1 from determinations of the instantaneous change in shear strain rate produced by an abrupt 15 to 20 deg increase or decrease in test temperature. If is the instantaneous strain rate at strain y and temperature T1, and ?2 the instantaneous rate at y and T2,

Jan 1, 1960

By Matti J. Saarivirta

The relative machinabilities of the precipitation-hardenable Cu-0.9 pct Cr, Cu-0.25 pct Zr, and Cu-0.9 pct Cr-0.25 pct Zr alloys are improved from 18 to 80 pct by 0.75 to 1.25 pct Pb. The Lead also improves the tensile strength, hardness, ad resistance to softening of the Cu-Cr and Cu-Cr-Zr alloys. When the alloy containing 0.7 to 2.2 pct Cr, 0.10 to 0.25 pct Zr, 0.75 to 1.25 pct Pb, and balance copper is solution-annealed at 1000°C (1830°F) and then aged at 525°C (Y75°F), tensile strength of 65,000 psi, 16 pct elongation, 62Rb hardness, and 84 to 87pct IACS electrical conductivity are obtained. The copper base Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys have high electrical and thermal conductivities, high strength and resistance to softening at elevated temperatures, but their machinability is poor, i.e., close to that of the pure copper. In the manufacture of various components such as welding electrodes or electrical and thermal conductors it is ofter desirable that the alloy have good machinability for high production rates and long tool life. Thus, alloys that combine these properties may be used not only for existing applications, but for new ones where good machinability is a requirement. This investigation was undertaken to improve machinability without impairing other desirable characteristics of the Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys. These commercial alloys contain about 0.4 to 1.2 pct Cr, 0.10 to 0.25 pct Zr, and balance copper. Lead was selected as an element that should improve the machinability and possibly other characteristics of the alloy. WORK PROCEDURE This investigation began with a study of the effect of lead on the hardness, tensile strength, electrical conductivity, and machinability of the binary alloy containing 0.10 to 1.30 pct Cr and balance copper. This was followed by an investigation of the effect of lead on the Cu-0.1 to 0.4 pct Zr and Cu-Cr-Zr alloys. The alloys were made from initially oxygen-free copper and for comparison some castings were made from phosphorus-deoxidized Lake Copper. Commercially pure chromium, zirconium, and lead were used for alloying. In melting the chromium was added to molten copper at 1400°C (2550°F), the heat held for 15 min at temperature, and the temperature then lowered to 1350°C (2460°F) when the other elements were added. The alloys were held for 15 min at this temperature and cast into a cast-iron mold. One-kilogram, 3-in.-diam castings were made. An argon cover was maintained during melting and casting to prevent oxidation. The chemical compositions of the alloys are shown in Table I. The micro structure and properties of the alloys were studied in the cast and wrought conditions prior to and after various solution-annealing and heat-treating cycles. The relative machinability was determined as a function of the lead content and compared with the free-machining Cu-lpct Pb alloy. To determine the machinability, 13/16-in.-diam cast specimens were cut by a machine hack saw using a constant cutting speed of 50 fpm, a fixed feed force, and a new blade for each alloy specimen. Molybdenum highspeed steel saw blades, 0.032 in. thick with 14 teeth per in., were used in all tests. No cutting fluid was used. Five tests were made on each specimen and the average elapsed time per test was taken as a measure of the relative machinability for that alloy. The variation of cutting time for each alloy was less than 110 pct.

Jan 1, 1969

For the benefit of those of our members who are considerable holders of securities,but owing to their isolated situations are not in close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are furnished through the courtesy of the financial department of the New York Tribune.

Jan 11, 1919

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

Jan 1, 1903

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By C. S. Barrett, A. Smigelskas

There have been no publications of the deformation and recrystallization orientations of the metal beryllium, yet pronounced textures would certainly be anticipated since it is close-packed hexagonal in structure. Having an axial ratio approximately that of magnesium, beryllium probably deforms by nearly the same slip and twinning mechanisms that operate in magnesium, and the textures are likely to be similar or but slightly different from the magnesium textures. In the tests reported below this is found to be the case; the textures are found to differ from those of magnesium only in the details of the scatter from the average orientation. This report covers not only samples rolled at room temperature, but some rolled at elevated temperatures. Since magnesium has been suspected by some investigators of altering its crystallo-graphic deformation mechanism at elevated temperatures, it was considered possible that beryllium might do so and alter its textures accordingly. No pronounced alterations were found, however. Unfortunately, the theory of deformation textures is not in a state of development that permits one to deduce the deformation mechanism from a knowledge of the textures, which means that the similarity of textures at different rolling temperatures, reported here, cannot be taken as definite evidence that the deformation mechanism is actually the same at all temperatures. The general similarity of the deformation textures of magnesium and beryllium also extend to the recrystallization textures of the two metals, judging by the pole figures for recrystallized sheet presented in this report. Samples were prepared in the form of composite sheets made up of small pieces stacked in a pile. Each piece was trimmed with scissors so that an edge was parallel to the rolling direction, dipped in paraffin, and assembled into the pack by aligning it under the cross hair of a microscope. As the desired orientation was obtained on each piece it was secured in place by touching with a hot wire to melt the paraffin. A stack of ten or fifteen pieces was built up in this way, then trimmed to the shape of a T; the portion to be X rayed was then etched to the shape of a wire about 0.045 in. diam with 6N HCl. This method of shaping the sample is a modification of that used by Bakarian on magnesium.' The absorption of the rays in the sample was so slight that it caused no difficulty in interpreting the films. Exposures were made with a 0.030 in. diam pinhole, using molybdenum radiation (40 kv, 25 ma, Type A film at 5 cm, 2 to 3 hr exposures). With the recrystallized specimens it was found necessary to oscillate the specimen so as to reduce the spottiness of the lines. A range of oscillation of 5" was SUB- cient to produce reasonably satisfactory patterns, though the quality was somewhat inferior to that of the deformation texture patterns, and only two degrees of intensity were read from the arcs on the films. Typical photo-grams for each of the deformation textures and the recrystallization texture are assembled in Fig 1. The pole figures were plotted in the usual way with the intensity of the various portions of the diffraction rings estimated by eye. Seven to nine films were made of each sample and each was carefully read in plotting the pole figures. Typical series included exposures with the beam normal to the rolling direction and at 11, 26, 41, 56 and 71" to the cross direction, plus two exposures with the beam normal to the cross direction, and at 11 and 79" respectively to the rolling direction. The rolling was in each case considered sufficient to develop the final texture: the reduction by cold rolling was 84 pct (from 0.0045 to 0.0007 in. thickness), following prior hot rolling in longitudinal and transverse directions and recrystallization; the reduction by hot rolling at 800°C was 90 pct (0.010 to 0.001 in.), following similar prior treatment; the reduction by rolling at 350°C was 88 pct (from 0.005 to 0.0006 in.) after similar prior treatment. The recrystallization texture was determined on a sample rolled at 350" to a reduction of 88 pct (0.0165 to 0.002 in.) after similar prior treatment, then mounted between steel strips to keep it flat and annealed at 700" in an atmosphere of argon. Discussion of Results The results of the X ray determinations are assembled in the pole figures of Fig 2, 3, 4 and 5 for rolling at

Jan 1, 1950

By Jack C. Haptonstall

Abstract-Minas de San Luis, S.A. operates the old Tayoltita mine located in the Sierra Madre Occidental in Durango, Mexico. Yearly production is 55 000 kg (1.7 million troy ox) of silver and 1000 kg (31,000 troy ox) of gold from milling 165 000 t/y (181,900 stpy) obtained from fissure veins. A 4.4 km (2.75 miles) adit, to intersect the veins below existing workings, was completed in 1974. The adit and ancillary projects facilitated extensive mechanization of the mine, ramp development of it, integration of duplicate facilities and elimination of obsolete facilities. It provided a deep-level access for exploration and development of the veins, and resulted in a 25% increase in production with the same labor force. The cost of the in-house financed project was $3.4 million.

Jan 2, 1978

By W. F. Flanagan, D. H. Polonis, S. D. Dahlgren

Rotation diffraction patterns of Cu-4.84 wt pct Si polymystalline samples were taken during the course of isothel-ma1 affing of the suPersaturated a phase, a diffraction spots were obserzled to streak during the initial stages of aging, and this streaking was similar to the streaking of a spots observed earlier by Barvett with deformed super saturated samples of the same composition. Although it was suggested that stacking faults were the sole cause of styeaking in the deformed samples, the present study has shown that plates with one small crystallite dimension can also contribute to the streaking when there is lattice coherency across close-packed planes. THE decomposition of the supersaturated a phase in Cu-Si alloys has been reported to occur by means of both thermal and stress activation.1-4 According to the Cu-Si phase diagram,3 Fig. 1, the supersaturated a phase (fcc) is expected to transform during aging by the precipitation of the y phase. The results of earlier studies2,4 have indicated that metastable k phase (hcp with nearly ideal close packing) forms initially at temperatures below the eutectoid temperature, after which the k transforms to the a and y phases. Hof-mann et al.4 have proposed a metastable version of the phase diagram, showing the approximate boundaries for k formation below the eutectoid temperature. In view of the close-packed nature of both the a and k phases, it is essential to consider the role assumed by stacking faults in the transformation. Streaking effects have been reported by Barrett 1 in the rotating crystal X-ray patterns of strained Cu-Si alloys and were attributed to stacking faults rather than particle size effects. This deduction was based on the observation that streaks in the diffraction patterns did not occur tangent to the 220fee Debye ring. It is known that the atom movements involved in faulting leave some X-ray reflections unaffected while others are broadened,' and, in particular, it has been shown that faulting will not cause streaking of 220fee reflections tangent to the 220fee Debye ring as would be expected if all the reflections were broadened.' The formation

Jan 1, 1967