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By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By Eli T. Conner

My connection, under a commission from the Councils and Board of School Control of the city of Scranton, Pa., with a recent investigation of mine-caves and the resultant damages to surface-improvements, has led to the preparation, at the invitation of our Secretary, of the present paper. It is notorious that there are, in the anthracite-fields, frequent subsidences of the surface, due to the removal of the coal beneath. No particular attention is paid to such occurrences, unless they happen to injure surface-improvements. Many caves have happened in Scranton and its viciuity, which hare excited but little remark, since they have generally caused no serious damage. In August, 1909, a cave occurred in the Hyde Park section of the city, generally known as the West Side, which nearly destroyed school-house No. 16 and considerable adjacent property. Fortunately, there were no pupils in the building at the time; but the thought of the possible result, had the usual number of pupils and teachers been present, aroused the public to the gravity of the situation; and the School Board employed engineers to investigate the case. Two reports were made by separate sets of engineers, which differed in some particulars. These differences were pointed out in the public press and magnified, and the consequent agitation of the subject was taken up and greatly exaggerated by some of the metropolitan newspapers, giving to uninformed people the very erroneous impression that the whole city of Scranton was in danger of sinking into the bowels of the earth. All this tended to affect the credit of the city and to depress real-estate values. The matter was considered at a joint meeting of the Board of Trade, the Councils, and the School Board. The Hon. J. Ben. Dimmick, a former Mayor, suggested that it

Jan 1, 1912

By Smith Bracewell

First evidence of bauxite in Jamaica resulted from an analysis of a soil sample collected at Bull Savannah in 1938 during a systematic local investigation of the island's soil types. Results of subsequent work indicated the possibility of the occurrence of deposits of commercial grade and dimensions, and in 1942, with a view to emergency development of the deposits as a war measure, the Jamaican Government declared all bauxite in the colony to be Crown property.

Jan 10, 1958

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By Eugene A. Mizikar

A mathetnatical model of heal transfer in continuously cast steel slabs is described. The model, consisting of a unidimensional transient conduction equation and boundary condition equations, has been pvogrammed for computer solution. Temperatuve and solidification profiles calculated for a 6-in. slab, being cast under several conditions of secondary cooling, are presented and compared. Calculated solidification profiles are in agreement with reported expevinle~ztal values. For the mold zone, the predicted slab shell thickness can be described by: Resuilts of the study indicate that multibank spray cooling followed by radiant cooling should be employed when solidifying thick slabs with minimum surface temperature of 1600°F. Under these conditions, a 6-in. slab can be expected to solidify in about 8.3 min. Computer results also indicate that radiant cooling can replace spray cooling during solidification of the final 30 pct of slab with little increase in overall solidification time. CONTINUOUS casting has come to the forefront of the steel industry in recent years because of economic advantages resulting from increased yields and elimination of several processing steps. Considerable work, however, remains to be done regarding modifications to the process and operating procedures. Both a lack of operating plants in this country and the experimental difficulties associated with direct measurements on moving castings have made determination of solidification rates and temperature distributions difficult. An alternate approach is to mathematically simulate heat transfer in a continuously cast section, and then calculate the temperature distributions as a function of the controllable variables of the process. Simulation of heat transfer during solidification requires that a nonlinear mathematical problem be solved. As pointed out by Ruddle,' there are two mathematical approaches to the problem- the analytical approach and the numerical approach. While the analytical approach is certainly the more elegant of the two, it does require a number of inexact assumptions because of the complexity of the problem. For example, noteworthy analytical treatments of heat transfer in continuous casting have been developed by Savage Hills,3 and pehlke4 only by making one or more simplifying assumptions such as invariant thermophysical properties, constant heat-transfer coefficients in the mold, and linear temperature profiles in the shell. Simplifying assumptions such as these can introduce considerable uncertainty in the validity of results calculated with analytical solutions. Numerical solutions, which are considerably more versatile, appear to be better suited for solving solidification problems. Complex variations in the boundary conditions and variable thermophysical properties can be handled readily with this technique. Whereas numerical computations can be long and tedious when done by hand, results can now be obtained quite rapidly with the use of either the digital or analog computer. Several numerical models of heat transfer in continuous casting have been published. In 1963, Adenis, Coats, and Ragones published a numerical model used to calculate temperature distributions in direct-chill-cast magnesium billets. More recently, Donaldson and Hess 6 presented results obtained with a numerical computer model of heat transfer in continuously cast steel billets. In the present study, a model of unidimensional heat transfer in continuously cast slabs is presented. The method of solution on a digital computer is also included. Calculated temperature distributions and solidification profiles for various schemes of secondary cooling along with attempts to verify the model are also discussed. MATHEMATICAL MODEL The schematic representation of the slab continuous casting process in Fig. 1 illustrates that the slab passes through three distinct zones of cooling. Accordingly, the mathematical model consists of three parts: 1) solidification in the mold; 2) solidification in the spray cooling zone ; 3) solidification in the radiant cooling zone. Heat-Transfer Equations. The model was developed bymaking a heat balance on a horizontal slice of slab over the time period required for the slice to proceed from the liquid metal meniscus in the mold to the cutoff station. As shown in Fig. 2, the imaginary slice extends from the center line to the surface of the slab. As the slice moves downward, heat is conducted from the center line to the surface of the slab at a rate governed by the surface boundary condition and thermophysical properties of the metal in the slice. The following partial differential equation describes the conduction of heat in a medium moving at velocity U in direction Z:

Jan 1, 1968

By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969

By E. C. Pechin

THE Lucy furnace, owned by Messrs. Carnegie, Kloman & Co., and located on the Alleghany River, on the outskirts of Pittsburgh, is a splendid modern furnace, 75 feet high, and 20 feet bosh. She had been working well on low grade ores of about 50 per cent., producing daily 68 to 75 tons. There was on stock 500 tons of Republic ore, one of the purest and best of the Lake Superior ores, averaging over 68 per cent. of iron, which had been procured for the purpose of making a trial for Bessemer iron. This was charged by itself, and Mr. Skelding, the founder, reports that he did not succeed in getting a single cast when it came down, before the furnace chilled from the hearth to the top of the boshes, some 25 feet. Every effort was made to save her, without avail, and the disagree-

Jan 1, 1874

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 64 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Postgraduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical

Jan 1, 1943

By HENRY FA

HENRY FAY (communication to the Secretary*).-In reply to the discussion of my paper, I wish to take this opportunity to express my appreciation to the Chairman and the various gentlemen who have taken part. I regret that others have not offered criticism, for honest differences of opinion often lead to the truth, and suggest new lines of work. An experiment has been made which bears on Prof. Sauveur's discussion and which helps to emphasize the conclusion that cementation is not a factor in the hardening of: the surface. Dr. Langenberg, of the Watertown Arsenal, has heated for me, in vacuo at 1,000° C., a piece of the metal containing a hard surface. The microstructure shows uniform distribution of carbon throughout the metal, showing that no carbon has been added to .the surface and heating in vacuo has prevented any oxidation of the surface.

Jan 6, 1917

By W. J. Taylor, H. J. Mutz, A. F. Brock

THE International Kickel Co. of Canada Ltd. operates five underground mines and an open pit. Four of the mines, the Frood-Stobie, Creighton, Murray, and Garson, are on the south range of the Sudbury Basin, map above, within a radius of 10 miles of the city of Sudbury, Ontario. The fifth mine, the Levack, is on the north range of the Sudbury Basin, 30 miles to the northwest of the city. The open pit is operating on surface ores of the Frood-Stobie orebody. Two pits were opened at the Frood-Stobie mine; the Frood section was started in 1938 and the Stobie section in 1942. To meet the heavy demand for nickel during World War 11, open-pit production was accelerated until it constituted over 40 pct of Inco's total tonnage. As a consequence open-pit ore was depleted considerably alhead of schedule; the Stobie pit was completed in the summer of 1951, and it is expected that mining at the Frood pit will be completed in 1953. The major program launched 10 years ago to develop additional underground production as a replacement of open-pit tonnage thus had to be greatly speeded up. This conversion to all-underground mining will be completed within the next two years, and the underground mines will then have an annual hoisting capacity of 13,000,000 tons. One of the new mines in the underground expansion program, the Murray, was brought into production in 1950. Ore production from the new Stobie section of the Frood-Stobie mine was commenced on a limited scale in 1951 and will be increased as the program progresses. Delivery of ore to the new Creighton mill was started in the summer of 1951 from the caving project launched at Creighton mine. When mining was started in the Sudbury district 65 years ago the ore deposits were opened on a small scale and mining methods conformed to a general pattern of small open cast pits, followed by open stopes as mining was extended below the pits. The open stoping methods used were heading-and-bench and shrinkage. In certain cases a type of cut-and-fill mining was used with drywall tramways and dry-wall chutes in the fill. As the mines were deepened,

Jan 1, 1954

By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

By W Lindlief, Cyril Stanley Smith

Several investigators, mainly concerned with the mechanical properties of the alloys, have studied the so-called aluminum bronzes after various quenching and reheating treatments. Of these works, perhaps the most complete is that of Bouldoires, who studied changes of length, electrical conductivity, thermoelectric force, hardness and micro-structure on tempering quenched alloys containing 5 to 20 per cent of aluminum, although the work of Carpenter and Edwards,² Curry13 Greenwood,4 Braesco,5 Matsuda,67 Grard8 and others has added much to our knowledge of the changes occurring during tempering. The so-called acicular ß decomposes on tempering at temperatures between 350" C. and the eutectoid, giving rise to a Widmanstätten structure of a needles in a matrix of 6 or fine a + 6, associated with an increase in hardness and almost complete loss of ductility. Matsuda studied the eutectoid transformation by means of dilatation and electrical conductivity measurements during cooling at different rates. He found that on cooling at the rate of 10" C. per minute there was a decrease in electrical resistance and in length instead of the usual increase which occurred with slow rates of cooling. On tempering the rapidly cooled samples, the increase commenced at about 400" C. and at 520" C. the resistance and length had reached the equilibrium values. These peculiarities he accounted for as being due to a transitional phase ß' being formed, ß' having an electrical resistance and volume less than either ß or a + 6. Obinata9 published some electrical conductivity curves for copper-aluminum alloys showing a double break at the eutectoid temperature,

Jan 1, 1933

By Edmund C. Pechin

The Lucy furnace, owned by Messrs. Carnegie, Kloman & Co., and located on the Alleghany River, on the outskirts of Pittsburgh, is a splendid modern furnace, 75 feet high, and 20 feet bosh. She had been working well on low grade ores of about 50 per cent., producing daily 68 to 75 tons. There was on stock 500 tons of Republic ore, one of the purest and best of the Lake Superior ores, averaging over 68 per cent. of iron, which had been procured for the purpose of making a trial for Bessemer iron. This was charged by itself, and Mr. Skelding, the founder, reports that he did not succeed in getting a single cast when it came down, before the furnace chilled from the hearth to the top of the boshes, some 25 feet. Every effort was made to save her, without avail, and the disagree-

Jan 1, 1955

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By S. Gstalder, J. Raynal

Consideration was given to simple tests which could be performed on rocks to give a measure of rock drillability. Various methods of breaking rocks were considered and the hardness test developed by Schreiner was selected for this study. The test involves application of an increasing load on the rock face through a flat-faced cylindrical punch until rupture occurs. Test results show that hardness is a good measure of the breaking strength of rocks. Useful relationships are shown to exist between hardness and other physical quantities such as specific disintegration, Young&apos;s modulus and sonic velocity. Specific disintegration (volume of rock broken per unit of work input) provides a possible means of comparing the effectiveness of other methods of rock breakage. The relationship between hardness and sonic velocity may be very significant for it may be possible to deduce rock drillability from sonic log data. provided that a mineralogical factor is taken into account. TO test further the results of the work, laboratory drilling tests were performed which closely simulated down-hole pressure conditions. Correlations of drilling results with rock hardness measurements were quite good. It was concluded that rock hardness, as measured in the laboratory or as deduced from sonic logs, could be used in relations for predicting rock drilling performance. INTRODUCTION Drillability of rocks cannot be defined in an absolute manner by a single quantity or measured by a single test. Resistance of rock to drilling depends to a large extent upon the means used for rock destruction. This complicates drillability classification of rocks for there may be as many classifications as there are methods of rock breakage without known functional relations between them. The objective of this work was to develop. in terms of rock destruction behavior, means of selecting the best drilling method for a given rock or the conditions for optimum output from a given drilling method. ANALYSIS OF ROCK DESTRUCTION TESTS Gauthier and Baron&apos; have reviewed the many test methods which have been developed for determining the resistance of rocks to breakage. These include drilling tests, punch tests, scratch tests, resistance to shock, wear tests, etc. A standard drilling test might be to determine the time required to drill a standard depth (1/16 in.) in a rock using a bi-cone microbit (1 1/4-in. diameter) when a standard load (417 Ib) is applied at a standard speed of bit rotation (110 rpm). From the standpoint of similarity, the results of microbit drilling tests would seem to be most representative of the several methods suggested above. However, evaluation of drilling performance by this method is only qualitative and cannot be applied directly to actual drilling conditions. Punch tests basically measure rock hardness. Punches of various shapes and sizes, including small cones for Vickers&apos; and Knoop&apos;s tests, the wedge for Epstein&apos;s test and the right circular cylinder for Schreiner&apos;s test, have been used. Results of these tests lead to a quantitative hardness classification which would seem to be related to the resistance of rock to bit-tooth penetration. Scratch tests are related to the resistance of rocks to abrasion such as would be encountered in drilling with diamonds. Either the width of the scratch obtained at a fixed load or the load required to give a scratch of a fixed width may be used to evaluate surface hardness of the rock. This should be related to the resistance of the rock to wear. The above tests, and probably many others. give relative measurements of the breakage or destruction characteristics of rocks. There is no direct relation between results of these tests and the drillability of rocks. Also, the tests each measure different quantities which have different dimensions and they do not permit direct comparison of numerical values. As one step in rectifying the above difficulties. it is proposed that the results of all test methods be expressed in terms of volume of rock destroyed per unit of work required; this is referred to as "specific disintegration". Test results may then be reported in a form which shows both a classification of rocks in regard to each method and a comparison of methods with regard to each rock. The disadvantage in using specific disintegration is the difficulty of measuring this quantity with accuracy. The volume of rock damage is difficult to measure. as is the true value of work input. Rock heterogeneity adds to the

Jan 1, 1967

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of&apos; slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By J. P. Myers, A. H. Flagg, E. S. Mardock, J. L. P. Campbell, J. M. Terry

The development process for the use of radioactive tracers as a means of locating zones of permeability is discussed. The general techniques for the safe handling of radioactive materials is given as developed by the Lane-Wells Co. and Well Surveys, Inc. The prob1em and. successes with tracers in waterflood systetns, oil and gas injection profiles, fracture sand tracing, squeeze (ement tracing. lost circulution, and cement top localion are discussed and illustrated. INTRODUCTION The exact location of the permeable zones lying within the productive horizon has been a major problem faced by the petroleum engineer for decades, and it has been a problem which has seldom been solved with certainty. Reservoir engineers usually have to incorporate a question mark in their estimates of future reservoir performance because of blanks in the core data. Although the use of radioactivity or electrical logs for the estimation of porosity has been of great assistance in furnishing a record for the reservoir engineer, this application of logging data has not completely solved the problem. In short, the industry needs an in-situ well surveying method which can locate and estimate the permeability of the zones existing within a given pay section. The initial development work with radioactive tracers has been towards filling the need for permeability information. Progress to date permits the location of permeable zones with a qualitative estimate of their relative importance with respect to permeability. The calibration of the method is still incomplete. but present development work on tracer preparations, borehole effect correction factors, and instrument limitations give a promise of quantitative "permeability profiles" in the near future. The development work on the radioactive tracer method discussed here began several years ago in the laboratories of Well Surveys, Inc., in Tulsa. At the outset of this work, three approaches to the problem were visualized as follows: 1. A fluid carrying a soluble, chemically inert, gamma ray emitting isotope is pumped down the borehole and out into the permeable zones of the formation. The greater gamma activity of the permeable zones thus permits them to be differentiated from the impermeable zones which contain no active tracer. It was found difficult to obtain a tracer material which was chemically inert. Absorption to some degree was noted in all experiments. Also, it proved impossible to hold the tracer near the horehole where it could be logged. 2. A fluid carrying a soluble, gamma ray emitting isotope is pumped down the borehole into the permeable formations. In contrast with proposal 1, above. the tracer is chemically active with the fluids and materials in the pore spaces of the permeable zones. The permeable zones are thus indicated by their higher radioactivity level. The main difficulty in this proposal was finding a tracer material which would not be absorbed by shale as well as in the permeable porosity. Very little field work was done with this system. 3. Radioactive particles suspended within the injection fluid are pumped down the well. As the fluid enters the permeable formations, the radioactive particles are filtered out on borehole wall. The permeable zones are differentiated from the impermeable by the gamma ray activity deposited on the formation wall.

Jan 1, 1956

By C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem&apos;ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam&apos;ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961

GWILLIAM H. CLAMER (Philadelphia, Pa.).-About 16,000 tons of tin is used annually in the production of white metals. The real reason for using the so-called genuine babbitt, which is a high-tin base babbitt, perhaps in the majority of cases, is that tin has always been. a high-priced metal and people naturally believe that what they pay a high price for must be good. Mr. Jones has shown that the common metal, lead, is a superior base for most purposes for Which babbitt metal is used. The addition of lead is often looked upon as adulterant to genuine babbitt, and specifications for this reason rigidly restrict the lead content. A sub-committee of the Society for Testing Materials, at the meeting in June, presented tentative specifications on babbitt metal, in which were included twelve formulas, containing from zero to: 20, per cent. of tin, and several containing from 65 and 92 per cent. Babbitts. containing

Jan 1, 1919