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By D. A. Rice, M. C. Fuerstenau

Flotation data indicate that sulfonate and amine adsorb physically on manganese oxide; oleate also adsorbs physically if the zero point of charge is sufficiently high. Chemisorption of oleate occurs on pyrolusite between pH 8 and 9, and possible mechan- isms of collector adsorption involving metal ion hydrolysis are discussed. The flotation characteristics of most metal oxides1-15 have been examined with standard collectors such as fatty acids and sulfonates. From these studies it would appear as though electrical phenomena are important when shorte r-chained collectors are involved. For example, Iwasaki, Cooke, and Choi9 have shown that dodecyl amine and dodecyl sulfate float iron oxide above and below the zero point of charge, respectively. In another system, D.W. Fuerstenau and Modi10 have shown that dodecyl sulfate, dodecyl

Jan 1, 1969

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By Harry A. Wahl

Precent fracture design procedures are bared on the total fracture area created. A method to distinguish beI,,.ecn total area and [he propped or effective fracture area has not been available. This paper presents a solution to this problem, applicable to horizontal fractures. The difierences between effective fracture area and torn] area are demonstrared in example calculations. This work is hayed on experimentally determined transport efficiencier of solids in sand-liquid slurries. Newtonian and non-Ne~vtoninn systems are considered. INTRODUCTION Fifteen years after commercial introduction, hydraulic fracturing remains the most successful stimulation technique in the oil field. This success is primarily due to ability of induced fractures to penetrate and alter permeabilities deep within formations. Many fields producing today could not have been developed without the hydraulic fracturing process. Because of wide usage, fracture-treatment design has received a great deal of engineering and research effort. This work, resulting in improved equipment and materials, has increased the benefits from fracture treatments as well as the applicability of the process. A major contribution was the development of fluid-loss additives. Necessarily, the number of parameters to be considered in treatment design has steadily increased, resulting in more complicated design techniques. Almost all present design procedures are based on the precepts set forth by Howard and Fast. Relating the fluid volume lost into the formation, the volume required in extending the fracture, and the total slurry volume injected, they developed an expression for the total fracture area created in terms of pertinent treatment parameters. Fluid loss during treatment was expressed as a function of time for three flow mechanisms. Although modifications of fluid loss equations have been made, the total fracture area concept has remained unaltered. A vast amount of field data indicate that induced fractures must be propped and held open to be effective. A notable exception is the Mesa Verde formation in the San Juan basin. However, analysis of these treatments shows that improved well productivities are obtained when propping agents are incorporated in the treating fluid. Although propped fracture area has been recognized as an important design parameter, a method to distinguish between total area and effective fracture area has not been available. The necessary information on slurry-sand transport in fractures has been lacking. Interest in the propped region of induced fractures is not restricted to areal extent alone. The distribution of sand within fractures is important from the standpoint of fracture flow capacities. Flow capacity affects the increase in well productivity after stimulation. The work of Huitt and Darin4 hows that partial monolayers of sand have large flow capacities compared to thick* dense sand packs. It has been postulated that gelled fluids have the ability to transport sand within the fractures at the deired low concentrations. An early contribution in the area of sand placement in fractures was made by Kern et al.' They studied sand movement in a transparent vertical fracture model. It was observed that the sand tended to settle out in the bottom of the model before moving very far. When the fluid velocity exceeded a certain critical value, all of the sand injected began moving through the crack even though it settled to the bottom. This critical velocity was determined under several flow conditions. Some work on sand movement in horizontal fractures has been reported in Russian publications. Sand movement was studied by Izyumova and Shan'gin' using a transparent "pie-shaped" flow model to simulate a horizontal radial flow system. However, the data were limited, especially in a quantitative sense. Dorozhkin, Zheltov and Zheltow studied the behavior of sand-liquid slurries in a horizontal linear flow model. The quantitative data were restricted primarily to the thickness of sand deposits formed at the bottom of the fracture. An earlier paper provided basic data on the flow of sand in horizontal fractures. This study was designed to yield specific quantitative information on rate of advance of sand particles and pressure behavior under various flow conditions. A comprehensive photographic study was undertaken in a 10-ft windowed flow cell to provide the necessary qualitative and quantitative data. Since the number of potential variables far exceeded the capacity of the initial study, emphasis was placed on the effects of sand concentration, oil viscosity and oil flow rate. A detailed description of these experiments and the results are described in Ref. 9. However. the implications of this work on the fracture design calculations were not discussed. An analysis of these data as well as new data is provided in the following sections. EXPERIMENTAL RESULTS The primary objective of the experimental investigation was to provide information on the rate of advance of the solids in sand-liquid sturries. A 10%-ft long transparent

Jan 1, 1966

By Arvid E. Nissen, Knox Taylor, John H. Hall

Some months ago one of the authors was asked to write a paper on the heat treatment of steel castings that would be more comprehensive than other matter he had published; this is an attempt to present in condensed form the results of experimental work and actual practice carried out for the most part in 1907, 1908, and 1909. It is not a laboratory research and the work done was carried out for the express purpose of putting in practice the processes discovered as fast as possible. Most of the tests are the result of commercial practice and not of bars annealed in our laboratory; most of the micrographs were made for our own records and not for publication. Certain of the micrographs, therefore, are not as clear as we may wish but they were good enough for our purpose at the time they were made. The tests and micrographs are selected from several thousands in our files. All of these micrographs are magnified 60 diameters. These experiments were conducted almost entirely on steel made in a 3-ton bottom-blown converter, and most of the steel illustrated analyzes about 0.05 in phosphorus and sulfur. Unfortunately, a certain number of specimens are shown of which we do not have the complete analysis, but in most cases in which the phosphorus and sulfur vary much from the figure just given that fact is noted. For purposes of comparison, we have included a certain number of micrographs and tests of steel made in the electric furnace, some of which were from specimens made in other shops and some in our own shop, and some tests of acid open-hearth and tropenas steel. A brief examination of the tests in Table 1 shows that certain treatments of, for instance, 0.30 per cent, carbon steel are not represented by any test data. Had this been a laboratory research, this information would undoubtedly have been furnished, but as this work was done for commercial purposes the omissions are due to the fact that, at the time the work was done, we saw no advantage in trying every composition of steel with each treatment discussed in the paper.

Jan 1, 1920

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By AIME AIME

NATURE was in a smiling mood on December 18, 1883. On that day, Chester Alan Fulton, the sixty-first President of the American Institute of Mining and Metallurgical Engineers, was born, and she endowed him with every good quality within her reach - looks, physique, intelligence, and character. Brought up in the valley of the Hudson River, with the mighty Palisades which make it the "Rhine of America," he has lived up to his early promise - as a man, as an engineer and as a friend.

Jan 1, 1943

By W. D. Forgeng, R. E. Grace

The rate of copper corrosion in liquid lead was studied as a function of flow rate and temperature in a closed isothermal loop system between 350" and 500°C. Kinetic data were interpreted with the Nernst-Brunner equation and the Chilton-Colbum mass transfer analogy to heat transfer. Over the range of temperatures and flow rates employed the solution rate constant varied from 2 x 10-3 to 20 x 10-3 cm per sec. The rate constant was found to vary with the 0.76 power of the Reynolds number in the range 7500 < Re < 40,000. The results of this investigation indicate that the Cu-Pb corrosion process is controlled largely by diffusion across a boundary layer. particularly at the higher temperatures. The effective boundary layer for diffusion is found to be approximately three to four times smaller than the momentum boundary layer. CORROSION by liquid metals has long been a problem during melting, static containment, and casting. Recently, considerable emphasis has been placed on the understanding of liquid metal corrosion mechanisms in an effort to prevent mass transfer and eventual failure in liquid metal heat exchangers and in liquid-metal-fueled nuclear reactors. The present investigation was conducted to determine the relationships which exist between corrosion kinetics and hydrodynamic conditions in an isothermal loop containing a simple liquid metal-solid metal corrosion system. The Cu-Pb system was chosen for its simplicity and ease in handling. Previous isothermal Cu-Pb corrosion studies1-3 have been conducted in both static and dynamic systems but not under conditions which allow easy "scale-up" to engineering systems, such as liquid metal heat exchangers. On the other hand, most liquid metal loops which have been used to evaluate mass transfer rates4 have been driven with temperature gradients under conditions of natural convection and unknown flow rates. The primary contributions of this research are twofold: 1) to evaluate the design of a simple isothermal loop corrosion system and 2) to investigate liquid metal corrosion behavior under well-defined hydrodynamic conditions. MATERIALS AND EXPERIMENTAL WORK The apparatus used to measure the Cu-Pb corrosion rates is shown schematically in Fig. 1. The loop system consisted of 1) a reservoir made of Type 316 stainless steel containing a centrifugal pump and 2) stainless-steel tubing containing a removable copper test section. The copper test section was OFHC hard-drawn tubing, 11.0 0.05 cm in length and 0.775 ±0.005 cm ID. A Type 316 stainless-steel venturi meter* was inserted in place of the copper test sec- tion in order to determine the lead velocity as a function of pump speed at each temperature. The Cu-Pb system was chosen for this study because the solubility of copper in liquid lead is large enough to measure accurately but small enough that the diameter of the copper tubing was not changed significantly by corrosion. There are no intermediate phases formed in the system, and the solid solubility of lead in copper is vanishingly small so that back-diffusion cannot occur. Molten lead (corroding grade; 99.94+ pct Pb, 0.0015 max pct Cu) was charged from an auxiliary melting furnace into the system under an argon cover to minimize oxidation. The lead was then maintained at constant temperature by a stirred molten salt bath in which the loop was immersed to a depth just above the lead level in the reservoir, Fig. 1. The total volume of lead in the system was 320 2 cu cm.

Jan 1, 1969

By G. L. Smit

The Buffelsfontein Gold Mining Company is situated in the Klerksdorp district of the Province of the Transvaal in the Republic of South Africa, approximately 100 miles west of Johannesburg. Gold production commenced in January 1957 and Uranium treatment of residue slimes as a by-product started in July 1957. The mining property is 5435 mining claims in extent, the equivalent of 7988 acres or 12.5 sq miles. The mine was initially exploited by the Pioneer Twin Shaft System, consisting of a 26-ft diam down-cast shaft and a 22 ft-diam up-cast shaft, sunk in the north-west area of the mine to cater for the hoisting and ventilation requirements for a milling rate of 150,000 tons per month. To exploit the Eastern zone of the property and assist in increasing production to 200,000 tons milled per month, it was decided to sink a further Twin Shaft System consisting of a 28-ft diam downcast shaft and a ventilation up-cast shaft -22-ft in diam, both monolithic concrete lined — 200 ft apart and 5300 ft deep. This paper deals with the sinking and commissioning of these Eastern Twin Shafts. This was achieved by one sinking crew within a period of 20 months. A) PLANNING 1) Siting: The Eastern Shaft System was sited in the north-east area of the property, 12,000 ft east on strike from the Pioneer System. (Fig. 1). Initially the system was sunk to the 5300 ft elevation to conform with the original Pioneer Shaft System. On completion a sub-vertical main shaft will be sunk to the 8000 ft elevation in the immediate vicinity, and subsequently the surface ventilation shaft will be deepened to this elevation by raising from level to level and sliping to full size. The exact positions of the shafts were chosen after: a) underground development had located certain known water bearing zones, and b) geophysical and topographical surveys had been carried out. The shafts passed through the following geological succession: Surface to 4430 ft - Dolomites of the Transvaal System 4430 to 4470 ft - Quartzites and conglomerates of the Black Reef Series of the Transvaal System. 4470 to 4470 ft - Diabasic Lava of the Venters-dorp System (Ventersdorp Contact Reef at base). 4470 to 5250 ft - Quartzites of the Elsburg Series of the Upper Witwaters-rand System. The shafts were sited to ensure that the least possible water would be encountered during sinking, and this contributed to the rapid rate of sinking. 2) Duties: a) The 22-ft diam ventilation shaft was designed to up-cast 1,400,000 cfm of air (0.060 density) against a resistance of 22 in. water gauge. b) The main shaft was designed to handle 160,000 tons hoisted per month as well as the men, material and down-cast ventilation to serve this tonnage. The 284 diam main shaft is equipped with streamlined buntons spaced at 15 ft centers set in pockets which were left during sinking. There are six compartments, four of which are sewed by two dual purpose hoists, hoisting either, twedeck man cages or 13-ton bottom discharge skips. The other two compartments are served by a single purpose winder hoisting double deck cages accommodating 60 men per deck. (Fig. 2). 3) Timing: Permanent equipment was ordered well in advance to insure continuity in the operation. Development underground reached the shaft positions before the start of sinking operations. From this development, boreholes were drilled into shaft positions to drain off water in the vicinity of the shafts. To ensure complete co-ordination of effort, all relevant data, as well as the allocation of responsibility, were made known to all persons and departments concerned. 4) Models: The extensive use of scale models during the preliminary planning stages proved most useful in deciding on design such as buntons, bunton pockets and guide cleats, and complex layouts concerning loading, spillage and pumping arrangements. (Fig. 3). These models also proved invaluable in determining the walling routine. Normal working conditions could

Jan 1, 1964

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer&apos; and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.&apos; Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner&apos;s treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1&apos;2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959

By William Buell

As used in connection with open-hearth or other high-temperature operations, "insulation" refers to a multitude of substances, natural or manufactured, that have the one principal property of preventing the flow of heat by conduction to a greater degree than refractories can prevent it, the principal properties of the latter being resistance to tem-perature and/or chemical action. The term "control" as commonly applied to the mechanization of management functions is inappropriate without qualification, for without some degree of control of every operation we could produce no steel worthy of the name. Although grouped together in this paper, insulation and control in open-hearth furnaces have little, if any, interrelationship, therefore the paper is made up of two distinct parts.

Jan 1, 1935

By G. J. Armstrong, K. S. Lynch, C. G. Thomas, L. A. Baker, R. J. Cornelius

The presence of geothite in a hematite ore has been shown to strongly affect the time of heating to the firing temperature. The investigation of spalling of single pellets and of packed beds has enabled free water and goethite spalling to be identified as separate phenomena. In addition, it has been shown that even for an 18-in. deep bed of green balls, the free water and goethite drying periods can be considered separately. Based on this observation, a method of predicting production rate and hood temperature profile is presented. The method required knowledge of the ore goethite content, ore grind, and the green pellet bulk density. Laboratory results were found to be in good agreement with actual plant practice and have led to improved process performance.

Jan 1, 1974

By Roman Šejnoha, Karel Mazanec

A pronounced tendency for delayed fracture zoas observed in the martensite structure of low-alloy steels in the as-quenched condition. Cracks of predominantly intercrystalline nature nucleated and propagated at stresses substantially lower than the short-titne tensile strength of- the steels, and were observed even in hydrogen-free speciunens. The occurrence of delayed fractures in the as-quenched condition is interpreted as a supevposition of the effect of free dislocations generated during the martensite transforlnation, and of a weakening of the prior austenite grain boundaries caused by dynamic shocks exerted on the boundaries by growing martensite plates. AN important metallurgical problem, connected with the production and use of high-strength steels, is delayed fracture in martensitic structures. Such fractures occur in quenched steels as a result of prolonged loading with external stresses far lower than the short-time tensile strength of the steel. The same effect can be produced by sufficiently high internal stresses: it is well-known that quenched structures will in some cases crack intergranularly at room temperature if not tempered quickly enough even in the absence of any externally applied stress. In Troiano&apos;s papers1,2 on delayed fractures in high-strength steels, the fundamental role of hydrogen migrating under the influence of multiaxial stress towards the nuclei of cracks was found. Fig. 1 shows the typical relationship between stress and the time to fracture found by Troiano in hydrogen-charged high-strength steels. On the other hand, Shurakov 3,4 explains the realization of delayed fractures in martensite as due to a "quasi-viscous" behavior of the austenite grain boundaries immediately after the martensitic transformation. 1) MATERIALS AND EXPERIMENTAL METHODS Two low-alloy steels of commercial purity were used for the experiments reported in this paper. Their chemical composition is shown in Table I. The heats were melted in a laboratory furnace, cast to ingots, forged to bars of 3/4 in. diameter, and annealed. Machined test pieces were heat-treated as follows: Ni-Cr-Mo steel held at 900°C for 30 min and quenched in oil; Mn-Si-Cr steel held at 900°C for 30 min and quenched in water. For the delayed-fracture tests, notched cylindrical test pieces, Fig. 2, stressed in torsion, and unnotched cylindrical tensile-test pieces, 1/4 in. diameter, were used. The specimens were normally loaded with a constant static load 45 min after quenching for the torsional tests and 10 min

Jan 1, 1965

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

US 4,192,852-Precipitation of iron values as a jarosite from a sulfate solution obtained as a byproduct in the hydrometallurgical processing of zinc sulfide ore The solution is cooled, partially neutralized, and clarified. The clarified solution is heated to a temperature of 80 to 100°C in the presence of sodium, potassium, or ammonium ions to precipitate substantially all of the ferric iron as jarosite The precipitate is thickened, filtered, and washed The residual solution may be processed for zinc or other nonferrous metal values R V. Pammenter and C J Haigh, assigned to Electrolytic Zinc Co of Australasia Ltd. Mar. 11, 1980. 16 pp. (423-42) Filed: 5-8-78 (903,524). Priority- Australia, 5-9-77 (PD0030) (Drawings below.)

Jan 1, 1982

By L. R. van Wert

CAREFUL research into the nature of the metallic state has yet to discover, with any certainty, its essential quality. We do riot yet know, for sure, what it is that makes the metallic elements different from, if not actually unique among, all created things. We do know, of course, that metals have certain more or less characteristic properties-they are hard, strong, and tough, and good conductors of heat and electricity, and these so-called metallic properties provide a definition of a sort. How- ever, it is the structure rather than the behavior of the metals which gives the really fundamental information necessary to the understanding of metallicity. But this information is not easily obtained. Nature has a way of keeping secrets. But happily we do possess some knowledge of how a metal is built up, and it is this matter, rather than the presentation of a formal definition, that will be discussed here.

Jan 1, 1937