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By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,' and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.' Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

The State School of Mines, University of Utah, is this year giving-a four weeks' course for prospectors-Jan. 8 to Feb. 3, 1917-covering the fundamentals of geology, mineralogy, mining and the metallurgical treatment of ores. There will be 36 lectures of 1 hr. each and about 20 laboratory periods, each 3 hr. in length. It is the purpose of the School of Mines to make the course entirely a practical one, and purely theoretical considerations will be omitted. The laboratory work is designed to supplement the lectures and-to give those taking the course a working knowledge of the principles involved. In order to bring the course within the reach of all, no laboratory fees will be charged, and the only fee will be a nominal one for registration in the University, of $1.00, but it is expected that those who attend will be genuinely interested in the work.

Jan 2, 1917

Vols. 52 and 53 have been shipped 60 all who have paid their dues for 1916. Members who do not receive them within a-reasonable time are asked to notify the Secretary.

Jan 10, 1916

Detailed Geology of Certain Areas in the Mineral Hill and Warm Springs Mining District. By A. L. Anderson. T. H. Kilsgaard and V. C. Fryklund. Jr. Idaho Bureau of Mines and Geology. University of Idaho. 73 P. Maps, Illus.-Divided into three parts, this pamphlet covers the geology and ore deposits of the Hailey-Bellevue Mineral Belt, the Triumph-Parker mine mineral belt, and the ore deposits of the Mayflower Area. Numerous maps and illustrations are included for each area. Government Administration of the Copper Industry, World War 11. By John W. Douglas. 1950.51 P. $1.-This pamphlet covers in detail all the steps relating to control and operation of copper and copper products, and is of particular interest to primary producers, brass mills, wire mills, and foundries. Of particular current interest is the booklet's coverage of the steps leading to the Controlled Material Plan, into which industry is now once again heading. Copies can be obtained for $1 from John W. Douglas, Republic Foil & Metal Mills Inc., 55 Triangle St., Danbury, Conn.

Jan 12, 1951

By C. W. Arnold, H. L. Stone, D. L. Luffel

The purpose of this research is to determine (I) the efficiency of small banks of enriched gar driven by methane in displacing oil from a porous medium and (2) the effects of variation in bank size and composition of that efficiency. Most of the experiments were conducted in a sand-packed tube 20-ft long and 1/2-in. in diameter. The hydrocarbon system generally used was methane, butane and decane at 2,500 psia and 160°F. The results of these experiments indicate that, in the regions contacted by the gas, a small bank of an oil-miscible gas driven by methane can displace all of the oil in a piston-like manner. If the enriched gas is of such composition as to remain immiscible with the oil, displacement of oil is less efficient than for the miscible case, and the gas bank travels through the sand with a velocity less than that of the driving gas. These data along with theories discussed imply that smaller banks and less total gas are required when the enriched gas and oil are miscible. INTRODUCTION Widespread application of enriched-gas drive to the recovery of oil rests upon a key factor — the use of limited quantities, or "banks", of enriched gas. At the present time, the value of liquefied petroleum gas or other enriching agents discourages their use in a continuous injection technique, or even in a large bank, except in a few isolated reservoirs. If small banks of enriched gas driven by methane were as effective in displacing oil as is continuous injection, the enriched-gas drive process might be applied to a larger number of reservoirs. Previous research on the mechanics of the enriched-gas drive process reported by Stone and Crurnpl and by Kehn, Pyndus and Gaskell has utilized continuous injection of enriched gas. This work has shown that two types of displacements occur. With gases containing sufficient intermediates. the oil is displaced misciblv and complete recovery is obtained from the regions swept. When gases are used which contain insufficient intermediate hydrocarbon for miscible displacement, oil is displaced immiscibly. In the latter type, selective solution of the intermediate hydrocarbons causes a swelling and reduction in viscosity of the oil and leads to an increased recovery over that obtained by dry-gas (methane) drive. The size of the enriched-gas bank necessary for efficient displacement of oil is determined by those factors which cause deterioration of the bank. A differentiation may be made between those factors which operate on a microscopic scale and those which act on a macroscopic scale. On the smaller scale, the enriched gas mixes in the direction of flow by diffusion and convection with the fluids immediately preceding and following it. On the larger scale, the gas may by-pass the oil by flowing through permeable streaks, by overriding the oil because of density difference, or by fingering because of unfavorable viscosity ratios. In such cases, the enriching material tends to mix with the oil both laterally and in the direction of flow. The increase in effective area available for diffusion and dispersion of the enriching components leads to a faster degradation of the bank and a need for a larger bank than is necessary for those cases in which no by-passing occurs. The effects of such macroscopic factors in the deterioration of enriched-gas banks have been reported in a separate paper by Blackwell, Terry and Rayne. The present study was confined to the factors which operate on the smaller scale, in particular to the behavior of banks of enriched gas in sands uniformly swept by the gas. Experiments were designed to answer the following questions. 1. Can small banks of enriched gas driven by methane be used to secure oil recoveries comparable to those obtained by continuous injection of enriched gas? 2. What is the optimum bank size (the minimum bank size necessary to obtain a recovery comparable to that obtained by continuous injection of the same enriched gas)? 3. How many total pore volumes of gas must be injected to obtain the maximum recovery when the optimum bank size is used? 4. What is the effect of varying the number of enriching components in a gas bank? This report describes the experimental investigations and discusses the results in terms of their significance to reservoir behavior.

By J. Philip Neal, Carroll P. Rogers

Feldspars, the most abundant minerals of the igneous rocks, occur in numerous forms and mixtures. The feldspars of commercial significance are found in widely distributed pegmatites as large crystals usually free of iron- bearing impurities and thus suitable for hand-cobbing, and also in larger bodies where the ore contains various types of feldspar inter- mingled with quartz and relatively free of iron- bearing impurities, or at least readily unlocked from impurities present at relatively coarse mesh. The latter type of ore includes some pegmatites, and the ''alaskite" bodies so common in the Spruce Pine district of North Carolina. On the west coast of the U.S. and in Oklahoma there is-r has been--commercial recovery of natural feldspathic sand as a source of alumina in glass and ceramics. "Aplite" in commercial terminology is a light-colored igneous rock with a granitic composition and a fine sugary texture, often banded with readily removable iron impurities. Two areas in Virginia produce aplite for the glass industry: one located in the vicinity of Piney River, Amherst County, and the other near Montpelier in Hanover County. According to Deer et al. (1966) the word feldspar derives from the Swedish feldt or falt (field) and "spath:" chunks of rock appearing in tilled ground overlying granite. Castle and Gillson (1960) indicate a Germanic origin, citing "spat," which is said to refer to any transparent or translucent material which is readily cleavable. The term "spar" has in the past been applied to minerals other than feld- spar, such as barite, calcite, and fluorite. It is correct to call the latter "fluorspar." There is a true barium feldspar, but it is rare and of no present economic importance. What is recognized as feldspar or "spar" by present producers and consumers consists of three silicate minerals which, if pure, would have the formu- las KAISi,O, (microcline or orthoclase), NaAlSi,O, (albite), and CaAl,Si,O, (anorthite). These are almost never found in pure form in nature, but occur together in great abundance in a three-component system. A considerable number of different combined ratios of these three exists, with the exception that isomorphism between potassium spar and calcium spar is very limited. User specifications for feldspar products are largely built around the prevalent naturally occurring ratios. Pas- sages following will refer to "K-spar," "Na- spar," or "Ca-spar." Nomenclature and Descriptive Terms Relating to both the mineralogy and the economics of feldspar are certain terms whose coverage it is useful to specify. Commercially, aplite is a feldspathic rock mined and beneficiated in two locations in Virginia, in which both titanium and feldspar minerals are present-the latter now being the major, if not the only, economic product. Technically, the term aplite when applied to this rock is of questionable accuracy. But, in light of accepted commercial usage, the term will be here used to designate it. Regarding the Virginia rock, Ross (1941) is cited.

Jan 1, 1975

By A. J. Strauss

The solubilily of lead in PbS as a funclion of lemperature has been investigated by means of Hall coej'icient (RH) measurentents OIL samples prepared by annealing and quenching Bridgman-grourz single crystals, which contain excess lead incorporated during /heir growth from the mell. For sufficiently long annealing times and sufficiently rapid quench rules, the samples obtained consist of n-lybe PbS snturated with In the semiconducting compounds PbS, PbSe, and PbTe, the point defects associated with the presence of lead in excess of the stoichio metric composition are shallow donors. The defects associated with the presence of excess nonmetal are shallow acceptors. lead at the annealing teuiperatiire, together luilh a dispersed second phase of lead microprecipitates. Due to the retrograde solubility of lead, the measured free carrier concentration (n = l/eR77) decreases with decreasing annealing tewperature (T) from- 2.4 X 10 em-3 for 1l85OK to 1.3 X 1018 cm-3 for 623°K. The dala are well-represented by the equation n =(1.08 x 102) exp[ - (0.37 ev.)/kT] cm-3 For most undoped samples of these compounds, the carrier concentration at room temperature and below is determined primarily by the stoichiometry, since the concentration of either excess lead or excess non-metal is large compared to the concentrations of intrinsic carriers and electrically active impurities. Therefore the dependence of composition in temperature and partial pressure can be investigated by means of Hall coefficient measurements, even though the deviations from stoichiometry do not exceed 0.03 at. Pct

Jan 1, 1968

By T. B. Massalski, Horace Pops

The occurrence and the temperature dependence of the athermal martensitic transformation in bcc Cu-Zn ß-phase alloys have been studied by cold-state microscopy, differential thermal analysis, and electrical -resistivity measurements. CinenzatograpJzic studies have shown that in the majority of alloys the transformation occurs in two stages. A thermoelastic phase, having a 'needlelike" uppearance, forms initially at the MS temperature and grows relatively slowly, chiefly in the edge (lengthwise) direction. With further cooling, an additional martensitic phase forms in rapid bursts at a lower temperature, MB, Both martensitic phases appear to have the same cry stallographic habit hut their modes of formation and growth are different. For the composition range studied, between 38.55 and 41.49 wt pct Zn, the habit planes determined are close to the (2.17 ,12) plane of the matrix, in general agreement with the prediction of the phenomenological theory of martensite formation. Thermal cycling through the MB temperature produces permanent plastic deformation in the 0 matrix and gradutally eliminates the typical burst phenomena. Thermal cycling only through the MS temperature produces no noticeable deformation effects. THE bcc Cu-Zn ß-phase alloys tend to become unstable at low temperatures and undergo a martensitic transformation,'-3 but the details of the transformation have not been completely determined. Following earlier metal log raphic and X-ray work1 Tichener and ever' determined by means of electrical-resistivity measurements the temperature range of the martensite transformation during continuous cooling. The transformation temperature was found to decrease with increasing zinc content, becoming about -130°C for an alloy containing 40.04 wt pct Zn. Hull and Garwood3 made a metallo-graphic study of Cu-Zn 0 brasses at temperatures down to -160°C, and determined the habit plane of the transformation product for an alloy containing 38.88 wt pct Zn. No metallographic studies below liquid-nitrogen temperatures have been reported. The martensitic transformation in ß-brass alloys can also be induced by deformation.1,4 The MD temperature corresponding to the appearance of the strain-induced martensite is some 300°C higher than that observed without strain, and hence the transformation can be strain-induced in alloys containing a higher percentage of zinc. Massalski and Barrett4 found that alloys containing as much as 51.89 wt pct Zn could be transformed into a faulted hcp structure by cold working at liquid-helium temperature. Because the details of the MS temperature and morphology reported in the literature are somewhat incomplete, a further study has been made of some of the above features. A design of a cryogenic stage for optical metallography5 has permitted the examination of specimens at temperatures down to 4.2oK, and the use of a cinecamera has permitted a study of the morphology on cooling and heating. The particular aim of the present work was to examine the transformation temperatures, the habit planes, and the growth morphology over a wide composition range in the ß-phase field. The effect of thermal cycling upon the subsequent transformation was also examined.

Jan 1, 1964

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

Vol. 51 has been sent to all members who have paid their 1916 dues. Vols. 52 and 53, the last two volumes for 1916, will be shipped about the middle of-August to all except those owing current dues. Members who do not receive them within a reasonable time are asked to notify the Secretary. Back volumes to complete sets may be purchased from the Institute at reduced rates.

Jan 8, 1916

By J. R. Long, E. T. Hayes, R. S. Dean, F. S. Wartman

THE production of titanium in 15-1b. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,1 has provided adequate material for a study of the : physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the properties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. [ ] CONSOLIDATION OF THE POWDER The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at so tons per

Jan 1, 1946

By B. B. Gottsberger

HAVE given considerable thought during the past year to the subject of licensing of engineers and par-ticularly to the position which the mining engineer should take on this question. I have found, however, that it is not a subject which yields much result for the thought expended on it. So far as any published record will show, mining engineers have been either ignorant of the extent to which the movement for the licensing of engineers has progressed or else indifferent to it. It is true that the Mining and Metallurgical Society of America, by a questionnaire sent out to its member-ship, did a great deal in calling this matter to the atten-tion of the mining profession, and so far as I know, the report of its committee, which analyzed the replies received, is the only published statement of the feelings and opinions of our branch of the engineering profes-sion. It is to be hoped that the conclusions shown by that report, namely, that mining engineers are almost unanimously opposed to the principle of licensing and consequently any legislation dealing with it, has received serious thought and that we are ready for an even more thorough consideration of the subject.

Jan 3, 1922

By T. F. Mueller, P. A. Witherspoon

For the case of an infinite radial system operating at constant terminal rate, the reservoir engineer often uses the "point source" solution of the diffiusivity equation to study pressure interference effects. At early times and at short distances from the inner boundary these solutions are invalid. The amount of error is often not precisely defined because of mathematical difficulties. Work presented here shows that, if dimensionless time is defined appropriately, previous solutions of the pressure equation can be displayed .as a family of curves on one chart. These solutions include the point source solution (referred to in the field of hydrology as the Theis solution) and other solutions obtained with digital computer methods. With these curves, an exact evaluation of the pressure drop within a reservoir or an aquifer can be made by the engineer. Examples of field problem solutions are presented. In most reservoirs the error involved when the Theis solution is employed is often negligible; whereas, in the calculation of interference effects in an aquifer, a substantial error can occur through such an approach. INTRODUCTION Flow equations are used in petroleum engineering to study the behavior of individual wells and reservoirs. In the case of wells, the pressure response at the wellbore face is the major point of interest; whereas, in the case of reservoirs, the pressure response at the interface of the aquifer boundary is sought. To aid in such studies, the flow equations have been solved in terms of the behavior at these two inner boundaries. Only limited work has been published in regard to the pressure conditions away from these points, i.e., within the reservoir or aquifer. Theis and Mortada are among the few who have reported on this problem. The Theis approach employs the exponential integral and is valid for pressure conditions that occur some distance away from the flow disturbance. It is derived from the concept of a point source, as opposed to a flow across some finite area. The Mortada results, on the other hand, are valid at all points within the reservoir or aquifer. They are presented in terms of dimension less ratios of the radius where the pressure is desired to the radius where the flow rate is measured. Their main use, in the past, has been in aquifer studies. The published results are presented in the form of graphs that are limited to a maximum radius ratio of 64. These graphical results are cumbersome to interpolate at non-integral radius ratios, so that one may be forced to utilize a rather involved analytical expression presented by Mortada. BASIC EQUATIONS The solutions of Mortada and Theis are both based on the diffusivity equation as applied to the case of an infinite radial system subject to a constant terminal rate. The equation is obtained by combining the material balance equation with Darcy's flow equation. The assumptions implicit in the use of this equation are as follows: (1) a single fluid is present that occupies the entire pore volume; (2) the reservoir is horizontal, homogeneous, uniform in thickness, and of infinite radial extent; (3) compressibility and viscosity of the fluid remain constant at all pressures; and (4) fluid density obeys the equation Using the diffusivity equation in situations where the above conditions do not hold will result in errors. These errors (not discussed here) but only the errors which arise in the solution of the equation itself. The diffusivity equation for the homogeneous reservoir conditions cited above can be written in cylindrical coordinates, as To obtain a dimensionless equation, so a single solution can be used for applications of different porosity, permeability and fluid properties, the following transformations are usually made: After these transformations are made, Eq. 3 .can be written in dimensionless form, as MORTADA SOLUTION One solution of Eq. 6 has been given by Mortada.

Jan 1, 1966

By C. R. Garr, A. R. Troiano

FLAKING or hair-line crack formation has been a major problem confronting the producer of large alloy steel forgings.' Today it is generally conceded that hydrogen in one or more forms in alloy steel sections is a requisite for flaking. Hence an obvious remedy is a thermal cycle that reduces the hydrogen content to some low level. In practice, this generally means holding the material at some subcritical temperature for a period of time depending on the size of the ingot or forging. Another method that will suffice in some cases is to cool large forgings slowly, i.e., bury in ashes. In practice, this hydrogen bake is sometimes accemplished inadvertently by a series

Jan 1, 1958

By C. D. Demond

IN reverberatory smelting, fuel is the chief item of expense, as it commonly is in processes using large percentages of it. Hence the most suitable supply is eagerly sought; that is, the supply which, in the end, yields the greatest net profit. The better grades are not infrequently bought, even at an advanced price, because they are apt to be decidedly more economical. High price, of itself, however, is no merit, for freight is generally the largest part of the cost of fuel, and the nearby supply may yield as high efficiency as that from a greater distance. If a poorer grade is reasonably good, and if its cost is low enough to more than offset the decreased technical efficiency, it is of course the more suitable. Any smelting, operation depends for both efficiency and economy on raising the furnace atmosphere considerably above the "critical" temperature; that is, above the temperature at which smelting is completed. If this temperature is not exceeded, smelting stops, no matter how much coal is burned; and the real value of a fuel depends on the number of degrees that the temperature is continuously kept above this point. For example, if one fuel maintains 2,500° F. and another only 2,100° F., while the "critical" temperature is 2,000° F., the first is worth at least five times as much as the second, although the increase above atmospheric temperature is only one-fifth more in one case than in the other. This "margin of temperature" above the smelting point is much more significant than the total number of heat units developed from the fuel. The case is parallel to that of water flowing from a pipe. The reservoir may contain a billion gallons of water; but, even though the fluid has come to the nozzle, not a drop will run out, where it can be of practical use, unless the level in the reservoir is higher than the nozzle; and the speed and volume of flow depend on how much higher the level is in the reservoir than at this point. If the temperature inn a furnace is not above the critical level there will be no slag to flow over the skimming plate, even though there are enough heat units to bring an unlimited quantity of charge up to the point of slag formation; and just as the value of a water supply for the purpose of putting out a fire depends largely on the effective head, so the difficulties of furnace management

Jan 8, 1914

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By L. S. Austin

I. Introduction............ 431 II. Organization............ 432 III. Production............ 434 IV. Transportation............ 435 V. Sampling..........436 VI. Concentration............ 440 VII. Blast-Furnace Plant........... 442 1. Construction........... 442 2. Operation............ 450 VIII. Advantages of Large Furnaces........ 455 1. Saving in Fuel........... 455 2. Saving in Jacket.Water..... 455 3. Quick and Large Discharge of Matte and Slag... 455 4. Decrease of Incrustation... 456 5. Elasticity of Operation..457 6. Large Flow Through Fore.Hearths...4. 57 7. Alterations Without Interruption..458 8. Variations in the Composition of Slag....458 9. Less Labor-Cost.......... 458 10. Less Initial Cost.......... 460 IX. Briquetting.Plant........... 460 X. Roasting-Plant............ 462 1. Kilns............ 462 2. Reverberatory Furnaces...468 XI. Converter-Plant........... 474 1. Construction ..........474 2. Operation.......... 476 XII. Flues and Stacks........... 478 XIII. Arsenic-Plant............ 480 XIV. Coke-Washing Plant.... 452 XV. Slime.Ponds ........... 483 XVI. Brick-Plant............ 484 I. Introduction. The Washoe plant; in Anaconda. Mont., together with the local street-railroad, ranches. a foundry and machine-shop. A

Jan 1, 1907

By Rossiter W. Raymond

In the case of The Eureka Consolidated Mining Company v. The Richmond Mining Company of Nevada, recently tried at San Francisco, California, the real defendant was the Richmond Consolidated Mining Company, of London; but this being a foreign corporation, holds its mining property in Nevada through the Nevada corporation of similar name, in which the London Company owns all the stock, except the few shares necessary to " qualify" the American directors. The trial would naturally have taken place in the Circuit Court at Carson City, Nevada, and before a jury. But by stipulation of the parties, the case was tried in San Francisco, before Hon. Stephen J. Field, Justice of the Supreme Court of the United States, Hon. Lorenzo Sawyer, United States Circuit Judge of the Ninth Circuit, and Hon. E. W. Hillyer, United States District Judge, for the District of Nevada. The hearing began July 23d, 1877. The witnesses occupied two weeks, and the argument of counsel three days. Very eminent lawyers were engaged on both sides; for the plaintiff, Messrs. Solomon Heydenfeldt, R. S. Mesick, John Garber, and H. J. Thornton; for the defendant, Messrs. S. M. Wilson, Thomas Wren, and J. J. Williams. The court held the case under advisement until August 22d, when Mr. Justice Field delivered its unanimous opinion in favor of the plaintiff. The action was a complaint in ejectment, and an appeal was taken to the United States Supreme Court. The questions at issue between the Eureka and the Richmond Company in this suit, comprised several points in the construction of the mining law of the United States, and its relation to the customs and regulations of the mining districts, which possess an importance and an applicability far beyond the limits of the case in which they arose. It is my purpose to state these points, the arguments

Jan 1, 1879

By R. D. Groves, G. M. Potter, T. H. Jeffers

Experiments on ammonium carbonate leaching of native copper ores crushed to 1-inch size showed that in 30 days 55 percent of the copper was extracted from 0.7 percent copper conglomerate-type ore, and 85 percent was extracted from 2.1 percent copper amygdaloid-type ore. Cupric ions were not necessary to initiate leaching, and dilute solution containing only 2.2 grams per liter NH3 and 1.9 grams CO, was a suitable solvent. Copper was recovered from the leach liquor by solvent extraction and electrolysis of the strip solution. Cyclic testing of the leach-solvent extraction-electrolytic procedure is in progress on a 6-ton charge of minus 12-inch conglomerate-type ore assaying 2.2 percent copper. Oxygen is metered to the closed leach vessel as required by the leaching reaction. Initial copper dissolution was much slower than from minus 1-inch ore, but the leaching rate then markedly improved.

Jan 1, 1974