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By Allan T. Gwathmey, J. Bruce Wagner, Kenneth R. Lawless

Between 250°and 550°C in oxygen pressures of 10 to 760 mm Hg, the relative oxide thicknesses formed per unit time on the (100), (111), (110), and (320), decreased in this order. The predominant oxide orientation was (001)Fe3O4 and [110] Fe304 A small amount of a-Fe2O3 which exhibited a fiber pattern was observed in all oxides except those formed at 250°c in low oxygen pressures. IN order to understand the properties and behavior of thin films, particularly their role in oxidation reactions, there is needed more experimental information on their structure, composition, and kinetics of formation on clean surfaces of known geometry. The present study was undertaken to obtain such information for thin oxide films formed on single crystals of a body centered cubic metal, iron. Crystals in the form of spheres were used in order to expose all possible crystal planes to the reactant gases simultaneously. Using this procedure the relative rates of oxidation of all planes could be estimated, and those exhibiting, maximum or minimum oxidation rates could be selected for a more intensive study of composition and expitaxy. Since the three types of information were obtained from the same experiment using a single crystal substrate, any differences between rate, composition, and expitaxy on the several planes may be attributed to the influence of the substrate structure. EXPERIMENTAL The starting material for this study was Armco iron rods, 6 in. long and 3/8 or 1/2 in. in diam. The analysis was reported to be 99.8 pct Fe, with major impurities listed as carbon 0.018 pct, manganese 0.027 pct, phosphorous 0.005 pct, sulfur 0.029 pct, silicon 0.005 pct, and copper 0.11 pct. These rods were cleaned with ether and heated in an atmosphere of moist hydrogen at 950°C for three days. The purpose of this treatment was to decarburize the iron and to provide a consistent, uniform grain size for the growth of single crystals. Crystals in the form of rods, up to 1/2 in. in diam and 2 in. long, were prepared by a method similar to that reported by Leidheiser and Buck.2 Spherical crystals, 3/8 and 1/2 in. in diam and having a handle about 1/4 in. in diam by 112 in. long, were machined from the single-crystal rods. After machining, each crystal was etched in aqueous nitric acid to remove the cold-worked metal at the surface. Before each experiment, the crystal was polished mechanically with metallographic papers through number 4/0, and electropolished in a perchloric acid-acetic anhydride mixture by the method of Jacquet and Rocquet.3 The crystal was washed in running distilled water for at least 5 min. The excess water was blotted with a soft paper tissue, and the crystal was placed in an all-glass reaction vessel (See Fig. 1). The crystal was heated at 550°C in hydrogen for at least 8 hr prior to the oxidation in order to reduce any surface oxides and to help relieve any stresses in the metal. For the structure and composition studies, flat faces were cut parallel to (loo), (111), and (110) planes on the iron crystal spheres. The orientation of these faces was checked by a back-reflection X-ray diffraction technique. The faces were within 2 deg of the desired orientation. The flat faces were treated as described above except that prior to electropolishing they were given an additional polish on metallographic felt saturated with twenty-minute levigated alumina. After the crystal was heated in hydrogen for at least 8 hr, the temperature was adjusted to the desired value, and the hydrogen was evacuated. Commercial oxygen which had been purified by successively passing through tubes containing magnesium perchlorate, Ascarite and magnesium perchlorate was admitted to the desired pressure as measured by a mercury manometer. A resistance-wound furnace surrounded the oxidation chamber, and a temperature controller maintained the temperature within ±3°C. The furnace was provided with a small window for observing the crystal. The changes in thickness of the oxide films were followed by observing the interference colors. The oxidation was allowed to proceed until the desired oxide thickness was attained on a given crystal plane. The experiment was terminated by evacuating the oxidation

Jan 1, 1962

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By H. Y. Bassett

THIS paper attempts to show the various major operations used in nonferrous tube mills and does not necessarily represent the current practices at the two plants of the Wolverine Tube Div., of Calumet and Hecla Consolidated Copper Co. Inc. The operations now utilized in the production of tubing are quite varied and show the continual interest and advance metallurgically and mechanically to produce the best quality at the lowest cost. Naturally, any advance or lowering of cost is dependent on large production runs, which mean longer machine running time with maximum worker productivity. Standardization of tube sizes and elimination of unnecessary alloys are therefore very necessary, otherwise the development of costly new production machines would be of little benefit to the consumer as a whole. It should be noted that in such a short presentation it is impossible to describe in any detail the major operations. The short descriptions, it is hoped, will enable all who are interested to obtain a general idea of present, day practices in the copper tube producing field. Fig. I is a flowchart or sequence of operations showing the steps usually employed in tube production. RAW MATERIALS Quality starts with the raw material, and it is absolutely necessary that raw material be controlled and held to rigid specifications. Little need be said, however, regarding the raw materials for the casting of bars or billets, as the material always is purchased and checked against the various governing A.S.T.M. specifications. CASTING Casting, as is indicated in Fig. I, is quite varied and for convenience can be classified into two groups: The casting of solid billets, and the casting of hollow tubes, each of which is the base for subsequent operations. In the melting of the raw materials various types of furnaces are used, and the selection of any one is dependent on many factors outside the scope of this paper. However, as of general interest, a short description will be made of each. Induction Furnace (Low Frequency) This is popular in the melting of copper-base alloys, Fig. 2. In the induction furnace the principle of an inefficient transformer is used for the production of the necessary melting heat. The primary coil is.arranged around a transformer core made of high permeability silicon steel sheet. The secondary circuit is through a melting channel around the primary coil and opens into a hearth which contains the main charge. The heat is generated only in the melting channel, but because of the stirring action there is a constant flow of metal around the channel, which when mixing with the charge causes very rapid melting. The volatilization losses are very low as the furnace atmosphere above the charge is heated only by the heat from the melting metal. The stirring action, however, makes the use of any slag cover difficult. Such furnaces- must be started with molten

Jan 1, 1951

By J. T. Ryan

POISONOUS, irritating, or explosive gases are found in almost every industry, and manufacturers of gas masks are called upon to provide gas mask protection for a great variety of conditions, such as operators in horseradish factories, fumigators of homes and ocean liners, and men engaged in the manufacture of tetra-ethyl-lead, the new motor fuel. The modern type of gas mask and respirator, to provide protection against all such industrial gases, is an outgrowth of the gas mask developed during the World War to protect the soldiers against the poisonous war gases. So far, it has been possible to develop ample mask protection from all known noxious gases and fumes present in atmospheres encountered in mines, metallurgical works, and chemical and other industries, so long as there is sufficient oxygen present to support the flame of an oil lamp. The most important development of the gas mask was in providing protection against carbon monoxide- which is the noxious gas that mining men are most concerned with and, in fact, is the noxious gas that man is most frequently exposed to. This paper will be con- fined largely to the discussion of masks for underground use in metal mines. Gases that contaminate the normal air in mines can be divided into two classes: those that are given off normally by the workings, and those that are produced in mine operation.

Jan 1, 1926

By Dozier Fircley

SOME nonmetallic minerals and their products, such as portland cement, common brick and hollow tile, sand, gravel, crushed rock, vitrified salt-glaze clay pipe, and the like, are a necessity in every community. They are mineral in nature but the establishment of plants for their production is usually a local and elementary problem. Yet it is probable that an economic study of the problem in every locality will show that such nonmetallic mineral commodities are not always obtained in the most economical way, or in the best quality. Other nonmetallic minerals are of such value that they may be shipped for long distances and sold in sufficient quantities to establish prosperous commercial ventures. Among these are phosphates, barium compounds, borates, nitrogen compounds, magnesium compounds, sulfur, asbestos, and potash. Success in marketing such products depends on quality, production cost, transportation, and similar conditions.

Jan 1, 1932

By Lewis Carroll

AS he contemplates the numerous good things the hard-working committees have evolved for the 140th Meeting of the Institute, the Editor knows just how the walrus felt when he uttered his memorable, if somewhat lugubrious lines. For there are the Annual Reception and Dinner at the Commodore, 'the Gold Supply Symposium, the luncheons, general and special, and the Annual Institute of Metals Lecture, a Round Table on Iron Ore and a wonderful Informal Dance at the Grand Central Art, Gallery, substantial general sessions, a Smoker-and many other things. -Old, friends and new, reminiscences and confidential chats, horizons pushed back by new information and adjusted perspectives, courage revived and ambitions stimulated-one with a flair for the modernistic might make something-or nothing-of the kaleidoscopic preview 'of the coming Annual Meeting.

Jan 1, 1931

By Edmund J. Pryor

DURING the war years restrictions on travel, pressure of work, and the irregular arrival of technical literature from abroad combined to severely isolate Great Britain in a period of intense war expansion of the art and practice of mineral dressing. Many British technicians were fully occupied with the day-to-day problems of improvising substitutes as regular sources of supply failed. and with mastering the strange demands and working conditions of wartime. After a long day spent between ones laboratory and production work, the rest of the waking hours were often filled with fire watching or home guard patrol activities, substituting for a night-shift manager, or "resting" in a dugout while the bombs came down. There was no time for serious study of such technical literature as survived the Atlantic crossing.

Jan 1, 1947

By Carel Robinson

MECHANIZATION of coal mine, is radically changing the requirements for under-ground transportation. It has increased materially the need for reliability and belt conveyors are the most dependable means of moving coal away from the place where it is mined. Their record of freedom from delays is almost 100 per cent. Why then are- not belt conveyors in more general use. Part of the answer lies in the pour records made at some of the earlier installations, and in the fact that belts have so long been identified as a type of equipment suitable, in the main, only to thin seams. Another reason is lack of knowledge of the full potentialities of belt transportation.

Jan 1, 1941

Jan 1, 1922

Jan 1, 1922

By Raymond M. Howe

Additional data have been secured on the disintegration of furnace linings and the spalling of stove brick. The first article on the disintegration of furnace linings appears to have been written by John Pattinson in 1876.l The furnace involved was 85 ft. (25.0 m.) higher and 27 ft. (8.2 m.) in diameter at the boshes; after being in blast five years, the top brick became contaminated with carbon and disintegrated. An examination of the lining showed that the discolored, disintegrated brick were in a zone found from 35 to 67 ft. (10.6 to 20.4 m.) above the hearth; immediately below, in a zone extending from 22 to 40 ft. (6.7 to 12.1 m.) above the hearth, the brick were hard and porcelain-like in appearance. Analyses of samples taken from the different sections are given in Table I. The water-soluble portion found in the sample taken 39 ft. (11.8 m.) above the hearth had a composition approximately as follows: silica, 0.50 per cent.; lime, 0.04 per cent.; potash, 0.78 per cent.; soda, 0.20 per cent.; potassium chloride, 6.19 per cent.; moisture, 1.03 per cent.; total, 8.74 per cent. The carbon Table 1.—-Analyses of Samples Taken from Diferent Sections of Furnace . I ii In Iv v Section 67 Section 45 Seotion 39 Section of Original ft Above ft above ft above vitrified Lining Hearth Hearth Hearth Portion Per Cent. per Cent per Cent per cent. per Cent Silica........................... 55.70 55.60 55.67 47.60 37.07, Alumina........................ 35.50 35.40 30.00 26.47 23.18 Ferric oxide..................... 3.00 1.32 0.96 Lime........................... 0.23 0.06 0.17 Magnesia....................... 1.22 0.95 0.86 0.00 Potash......................... 2.60 2.10 5.30 7.54 21.59 Soda.........,.................. 0.45 0.42 1.67 0-76 6.28 Ca1bon ......................... 2.05 3.24 5.97 Carbon dioxide.................................. 2.. 17 Water...................................... 7.70 Water-soluble........................... 8.74

Jan 1, 1920

By T. Kunitake, H. W. Paxton

The self-diffusion coefficient of chromium in various alloys in the iron-chromium system has been measured. A variation in Dofrom 10-4 for pure chromium to a maximum of 102 near 60 pct Cr appears with a range of activation energy from about 50 to 80 kcal per mol. The general pattern of behavior observed is not consistent with present theories of diffusion by a vacancy mechanism. Suggestions are made for further clarifying experiments. RECENT work on the self-diffusion of chromium,' ?-uranium2-4 and ß-zirconium,23, 26 has indicated that these elements have very low Do (10-3 to 10-4) compared to that conventionally expected for vacancy diffusion. Pound et al.5 have suggested that this may be due to ring diffusion being operative, and have proposed a model which gives Do of the correct order of magnitude. The essential difference between this model and Zener's earlier model6 is that whereas Zener assumes tight coupling between atoms in a ring to establish a vibrational frequency, Pound's model allows the atoms to vibrate essen- tially each in their own normal modes. The probability of each atom moving in the correct direction to cause a ring of n atoms to rotate by 2p/n must then be calculated as a "synchronal entropy" which may be -20 e.u. for a 4 atom ring. In iron, the latest determinations of self-diffusion yield Do in the range 18 to 522.7-9 The most accurate is probably that of Borg and Birchenall8 which is 118 ± 3. This value is not inconsistent with that expected for a vacancy mechanism. Since iron and chromium are very closely similar in size, are both transition metals, and their solution is thermodynamically ideal at temperatures of interest in diffusion, it appeared that a determination of self-diffusion coefficients, Do and Q as a function of composition would be of substantial interest to diffusion theory. The following measurements were made with this purpose in mind.

Jan 1, 1961

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.' Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.'-' Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

By J. V. W. REYNDERS

NOT only is your toastmaster silver-tongued in his references 'to myself, but he is also quite in the habit of "saying it in silver." I have analyzed with some care his statistics of the world's silver production, which have been distributed here along with the menu, although frankly from the point of view of most of us, the distribution rather than the production of silver is of immediate concern. Unlike the performers by whom we have been entertained between courses, the rest of us on the program will have to do without costume or musical accompaniment, which as my friend Rains can testify puts an artist under severe strain. I am entitled by right of office and of precedent to receive your attention for ten minutes. The Governor, who appears on the program as a speaker; however, has asked me for five minutes of my time, and Senator Thomas has insinuated that he would appreciate one-half of the remainder, wherefore, I must ask your close attention to the very brief remarks that I am able to make under such restricted circumstances. To begin with, I want you to believe that I am approaching the task set by your toastmaster with misgivings. In looking over the Institute records relating to the Salt Lake City meeting of 1914 for some precedent as to what I ought to say, I found but one reference-and that of the following indefinite char¬acter-" and Friday night there was a hilarious banquet to 350 members and guests."

Jan 1, 1925

By William B. Plank

AGAIN the records show an unprecedented enrollment of students in the mineral technology schools of the United States and Canada. In the current year, 1938-'39, 9619 students were resident in the 53 schools of the United States arid 1014 in the six schools of Canada. These data are from my fifth study of the mineral technology schools of the United States and Canada. the last previous study having been made for the year 1936-'37. The undertaking as previously was made under the auspices of the Mineral Industry Education Division of the A. I. M. E. The data or, the various schools were collected in the same way as for former studies.

Jan 1, 1939

By A. H. Geisler

The correlation of property changes during precipitation with structure has progressed, sometimes rapidly but other times more slowly, since the fundamental discovery of Merica, waltenberg and Scott.1 The predominent factor that hampered the progress has been limitations imposed by the various detection methods. Refiments in x ray diffraction tech-niques and in metallographic methods, which have been extended by the electron microscope, have contributed new information within the last few years. These permit an extension of the theory as proposed by Mehl and Jetter in 1940'2 Now that a sufficient number of alloys has been investigated to establish a general mechanism of the precipitation process, a correlation of the facts into a generally applicable theory of age-hardening is both warranted and desirable. The purpose of the paper is to provide an orderly correlation of the phenomenological facts of precipitation hardening. Speculation 011 mechanism of hardening will be confined to that consistent with existing theories of hardening, Age-hardening accompanies the formation of a new structure, the precipitate, as provided by a11 alloy system ill which solid solubility decreases with decreasing temperature. Upon this premise alone all such systems would be expected to include age-hardenable alloys. Alas, this is not always the case. Few attempts have been made to explain the variable degree of age-hardening among different alloys or to explain the influence of small alloying additions upon the hardening. Dispersion hardening as originally postulated3 is not adequate.* Coherency hardening—the term that will be used to distinguish the properties of a two-phase mixture in the unique and unstable transition state at which the phases are strained into precise atomic registry (continuity or coherency) in planes

Jan 1, 1949