Search Documents

By E. J. Lintner

CLAY mining in the 'United States is by no means a small industry for approximately ten million tons of shale and clay are recovered yearly. The bulk of this tonnage enters into the manufacture of paving, building and refractory brick, draintile, pots, sewer pipe, stoneware, and wall and floor tile. This group of manufactures is commonly known as the heavy clay products industry. The winning of the raw materials for this industry constitutes merely a step in the manufacturing process because the manufacturer usually owns and operates his own source of supply. The mining of kaolin and the whiteware and chinaware claps, however, is usually a separate industry.

Jan 1, 1936

By Heihachi Kamura

The reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe2O3 + 3CO = 2Fe 4- 3CO2 2Fe2O3 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of earbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing equation, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also on the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium. Chemical Equilibrium of Iron, Oxygen, and Carbon Investigations concerning the equilibrium between iron, oxygen, and carbon have been carried out by E. Baur and A. Glaessner,1 who deter-

Jan 1, 1925

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By A. Blake Caldwell

The Anaconda Company, an organization of mining people, enters a new world of copper production as it brings on stream its recently constructed Twin Buttes operation some 25 miles south of Tucson, Ariz. Twin Buttes comprises the largest earth-moving task performed in the history of mining. Some people liken this job to moving enough earth and rock to complete the famed Aswan High Dam in Egypt. In all, some 236 million tons of overburden and rock were removed from over the ore deposit.

Jan 1, 1970

By R. T. Keyes, R. B. Clay, L. L. Udy, V. O. Cook, M. A. Cook

Based on compressibility and stress wave velocity in rock, initial explosive loading conditions, the thermochemistry of the explosive and reasonable description of the pressure-distance relations behind the shock front, the distribution of energy between the products of detonation and the burden are estimated as a function of time for various loading conditions. These include 'powder factor', loading density A (fraction of borehole occupied by explosive), and the explosive itself. Factors responsible for rock fragmentation are discussed in terms of: 1) 'release wave fracturing', 2) 'shear wave fracturing', and 3) 'release of loading fracturing' or 'rock bursting'. Release wave fracturing appears to occur only in the immediate vicinity of free faces, and shear wave fracturing only adjacent to the borehole under normal blasting conditions. Rock bursting is thus considered to be the most important means of rock fracturing in blasting. Means for maximizing it are considered. The most important factors to consider include maximum available energy A, explosive density p1, loading density A and 'powder factor'. Maximum efficiency is attained in general by maximizing the A . p1 product. This is achieved by using high density explosives at a loading density of unity (A = 1.0). Ways for achieving this condition are discussed. The bulk-handled aluminized slurry blasting agents have the desired properties for achieving optimum conditions for high blasting efficiency based on the theory outlined herein. Factors considered most important in the blasting of rock are: 1) The maximum available energy A, determined by the heat of explosion Q and the mechanical efficiency ?, a factor intimately associated with the mode of application (A = Q at highest gas concentrations). 2) The 'borehole pressure', pb, or the maximum pressure developed in the borehole after passage of the detonation wave and before the burden has had time to move or become compressed appreciably. (Owing to the short duration of the detonation wave at any particular point in the borehole, the fact that the explosive may not always fill the borehole completely and the further fact that the burden may not actually see the detonation pressure, the borehole pressure is considered more significant than the detonation pressure p2 as a performance factor in borehole blasting.) The borehole pressure is determined by the explosion or adiabatic pressure, p3 , and the loading density, A, or the fraction of the borehole filled by explosive. 3) The physical conditions important in the application of the explosive are: a) The 'powder factor,' (We/Wr), or the ratio of the wt of the explosive to that of the rock being blasted expressed as lb per ton or more generally in lb/cu yd. b) The bulk density, p1 ?. c) The 'burden' or 'line of least resistance,' the spacing between boreholes, the geometry of the borehole pattern and sequence of firing. d) The physical and chemical properties of the rock, most significant of which are possible heterogeneties, such as faulting, prefracture, and greater than micro-scale chemical heterogeneities. (This factor is not considered here but deserves a great deal of careful consideration.) All of these factors need to be carefully considered in the most economical engineering of a blast. Here is considered firstly an outline of the present status of dynamic rock mechanics, particularly as it pertains to blasting. The factors pertaining to the most efficient application of blasting agents are also considered, followed by a discussion of methods of application to achieve optimum explosives performance. ROCK MECHANICS Dynamic rock mechanics is currently a rapidly developing science contributing greatly to a better understanding and consequently the more effective application of explosives in blasting of rock.1-22 Basic to the development of the science of dynamic rock mechanics were the advances of Goransen23 and the Los Alamos and NOL groups24-28 concerning rock and stress wave phenomena and the transmission and reflection characteristics of stress waves at interfaces between different media. Basing considerations on this new knowledge as well as new experimental methods of study (ultra-high speed streak and framing cameras and electronic timers) the theory of fracture and failure of solids under impulsive loading by stress waves developed rapidly.14,16,27-29 Also the

Jan 1, 1967

F. E. BACHMAN, Port Henry, N. Y. (written discussion*).-Experi-ments with titaniferous ores found in Essex County, New York, made by the MacIntyre Iron Co. in 1914, showed' that titaniferous concentrates are reduced in the furnace with no greater, and probably with less, expenditure of heat, and consequently of fuel, than non-titaniferous mag-netites; and as a greater proportion of their oxygen is removed by carbon monoxide than is the case with non-titaniferous magnetites, a lower fuel consumption for the reduction of iron may be expected. After the furnace was blown out at the end of the experiment, the formation in the hearth was found to be abnormal. The brickwork was replaced, entirely around the furnace, by a layer which at -the tuyere circle was made up of cinder, fine carbon, and coke; the coke, however, gradually disappeared toward the bottom, being replaced by cinder and graphite. The usual salamander of graphite and iron was missing. The material left in the hearth seemed to be cinder that had not drained from the last cast; its composition, though, would indicate that it was in the furnace previous to the taking off of the titaniferous ore. At first, this material was thought to be blast-furnace cinder mixed with less iron and graphite than is normal; but an examination showed it to be made up of cinder with small masses of iron and graphite. There were also patches of a steel-gray material having a metallic luster; a microscope showed these patches to be made up of black metallic crystals interlacing white crystals.

Jan 11, 1919

By H. W. Camp

Research is defined, scientifically, as a "systematic investigation of some phenomenon, and also a search for hidden treasures." Chemists tell us that the hidden treasures of petroleum are far richer than the products which have been best known to us. However, these secrets will be discovered only through intensive and systematic, as well as scientific, industrial research. Indeed, the scope of the subject is so great that such an intensive research program should be assumed by a centralized organization supported by the petroleum industry as a whole. Such organization should assume the responsibilities for investigation of new products and development of markets for such products. Gasoline, the chief product of the petroleum industry has become a cheap commodity. The continual uncontrolled overproduction of crude petroleum, the intensive competitive condition in the marketing of petroleum products and the increase of refining efficiency and installing of cracking facilities, have all combined to lower the market value of gasoline. The purchaser has profited from the lower cost of gasoline by way of lower prices so that today the most important product can scarcely be manufactured at a profit. In other fields, manufacturing industries have diversified their products when faced by a similar situation. Thus, they have been able to widen their marketing outlook. Why cannot the petroleum industry employ the same tactics? Right now we are hearing much discussion concerning the development of a wider market for existing petroleum products and new products for existing or prospective markets. For instance, we can cite recent developments for use of propane, butane and ethylene. Butane has been found to be an efficient and inexpensive refrigerant, especially adapted to home refrigerating systems. Propane and butane fractions of natural gasoline may be shipped under pressure and may be used as a substitute for, acetylene in cutting torches in connection with oxygen. There is a possibility of substituting butane for gas oil in the carburation of coal gas, as we know that butane contains practically the gas enrichment as the same volume of gas oil and should prove to be a superior product for

Jan 1, 1928

By R. E. Reed, R. D. Leggett, Paxton, H. W.

TECHNIQUES have been developed for growing monocrystals and bicrystals of Fe-20 Cr, Fe-20 Cr-20 Ni, and Fe-18 Cr-8 Ni alloys by both the strain-anneal and the Bridgeman techniques. None of the techniques are new but since they are simple and many people have expressed interest, they are described here quantitatively as they could be modified for other single-phase "commercial" materials of high melting point. CRYSTAL GROWTH BY STRAIN ANNEAL Flat tensile specimens with a tapered gage length were initially studied to deduce the approximate critical strain. Normal flat tensile specimens were then used. The optimum procedure for the austenitic steels (Fe-Cr-Ni) deduced from a variety of cold reductions, recrystallization treatments, tensile strain, and growth anneals was as follows: cold reduce 70 pct, recrystallize (after machining tensile specimens) at 1000°C for 1 hr, strain in tension 2.5 pct, and then heat to 1350°C as rapidly as possible. A time of 100 hr at 1350°C is usually sufficient to pro-

Jan 1, 1960

By L. G. Graper, E. L. Ramsey

THE present program of increased production of armament and lend-lease material for mechanized war has created a problem for the shops that must do the machining. They have naturally turned to the steel producers to provide them with a steel that can be accurately machined with the greatest possible speed. The adding of sulphur to steel as an aid to machinability has long been practiced; however, it may cause red shortness in rolling and may result in billets with seams and cracks, which must be removed before rolling can be continued. This conditioning of billets slows down production and' adds to the cost of making steel. Experience with various grades of sulphur steel made to different specifications has shown that Bessemer sulphur steels roll better than similar grades made in the open hearth, and also that low-carbon steels that are open or semikilled .as tapped roll better than completely deoxidized or killed steels. This has led to the belief that oxygen plays an important part in the rolling qualities of sulphur-bearing steels. It is generally held that the red shortness of sulphur steels is due to the low melting point of the sulphide compounds that separate out at the grain boundaries when the steel solidifies. At the rolling temperature of steel these sulphide compounds melt and cause cracking. ADDING SULPHUR AS A SULPHITE These difficulties can be avoided if sulphur is introduced into the steel by means of an anhydrous sulphite, such as sodium sulphite or sodium bisulphite, which-upon decomposition-forms sulphur dioxide. It is assumed that, in this case, the oxygen of the sulphur dioxide forms part of the sulphide inclusions in the steel, and raises their solidification temperature enough so that the formation in the steel of a low-melting eutectic is prevented. The result is the prevention of hot shortness and a more uniform distribution of inclusions. Fig. I shows photomicrographs of steels made with sulphur, while Fig. 2 illustrates the structure of steels made with sodium . bisulphite. These samples were cut from the steels as cast-that is, before rollingand were polished and lightly etched to bring out the grain boundaries. Fig. I shows that sulphide -inclusions segregate more or less at the grain boundaries, and it can be seen how the continuity of these low-melting inclusions would cause red shortness. Fig. z shows that the sulphide inclusions are more or less uniformly distributed throughout the matrix. This arrangement of inclusions has no apparent effect on the rolling qualities of a steel. This statement has been substantiated by the observation of the rolling of over 6000 tons of steel made with a sulphite addition. RESULTS As stated before, the sulphur dioxide-is added to steel by means of the decomposi-

Jan 1, 1942

By P. A. Beck, W. D. Manly

In a recent note Sully and Head1 showed that the Cr-Fe sigma phase is isomorplious with the Cr-Co gamma phase, and that the lattice constants are also nearly identical. In a preliminary investigation of the ternary Cr-Co-Fe system at 800°C at this laboratory the above findings were confirmed, and it was found by microscopic techniques, using various etching reagents, that the two binary phases form an urinterrupted series of solid solutions with each other. These solid solutions occupy a straight narrow band which cuts across the 800°C isothermal section of the ternary system, connecting the two binary phases. A detailed investigation of the Cr-Co-Ni ternary system at 1200°C disclosed that here, too, the Cr-Co gamma phase extends deep into the ternary system in the form of a long narrow lip. The fact that this sigma type lattice is sustained even when well over half of the Co atoms in it are replaced by Ni atoms, with relatively little change in the Cr content, clearly indicates that Ni itself has a certain tendency to form the sigma phase with chromium. This tendency is hidden in the binary Cr-Ni alloys, where the sigma phase is not known to occur, but it becomes operative in the presence of a suficient amount of Co. The interpretation of these facts in terms of electron concentrations is rendered difficult by the uncertainty of our present knowledge of the valency electron structure of the transition elements in their alloys. However, Sully and Heal's results and the present work suggest that intermetallic phases with signla type lattice may occur more frequently in these little investigated alloys than heretofore suspected. In particular, it is expected that a similar phase may exist in the V-Co and perhaps in the V-Ni system, in analogy to the known sigma type phase in the V-Fe system, and that all these sigma type phases may form extensive solid solutions with one another.

Jan 1, 1950

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By L. H. de Wald, J. Walter Scott

It is usual practice in the copper industry to use open horizontal molds for casting tough-pitch copper wire bars.' A wire bar cast in this manner is partly characterized by heavy wrinkles and a comparatively deep skin of oxide on the top of the bar, corresponding to the open side of the mold. On the theory that the rough, high-oxide surface might have an adverse effect on the rolling and drawing properties of a wire bar and might account for some of the irregularities of mill behavior, several bars which had been planed to remove the wrinkled surface were processed into wire. These bars responded to mill treatment more satisfactorily than did the regular wire bars. Realizing that machining the surface of one face of each bar would not be commercially feasible, it was decided that casting the metal into a vertical mold and cropping off the pouring end would accomplish approximately the same result. Several wire bars of commercial size (250 Ib.) were so cast and processed into wire for comparative test with bars cast in the usual horizontal molds. It is the purpose of this paper to present the results obtained from this investigation, in which commercial bar sizes and processing technique were used throughout. The results show that in general copper wire bars cast vertically are superior to those cast horizontally. Experimental Procedure A horizontally cast bar and a vertically cast bar were obtained from each of several regular reverberatory furnace heats of copper which had been refined and poled to tough-pitch metal in accordance with usual methods.' Both bars were cast from the same part of the melt and within five minutes of each other, in order to produce as nearly as possible, in each case, wire bars of identical composition.

Jan 1, 1930

By A. L. Mowry, John T. Norton

Isothermal sections of the pseudo-ternary carbide systems TiC-VC-ZrC, TaC-VC-ZrC, and NbC-VC-ZrC have been examined. The sections contain an inverted U shaped two-phase field whose maximum extent is 77 molecular pct for Tic, 64 pct for TaC, and 51 pct for NbC. lsoparametric lines were determined which show the curvature of the single-phase field and the direction of tie lines in the two-phase field. It was not possible to show any relationship between atom size and the extent of the two-phase field. REVIOUS work' on the solubility relationship of several pairs of refractory cubic monocarbides from the group Tic, ZrC, VC, NbC, and TaC has shown that, with the exception of the system VC-ZrC, they all form continuous series of solid solutions. It was demonstrated that the limited solubility in the case of VC-ZrC system was primarily a question of the size factor, the size difference between vanadium and zirconium being greater than the limiting value of about 15 pet. It is interesting to consider the results of combining these isomorphous carbides in groups of three and to determine the isothermal section of the pseudo-ternary diagram at, for instance, 2000°C, a temperature that will assure an equilibrium structure in a reasonable length of time. In the ternary systems where the three pairs form complete solid solution series, it is probable that the isothermal ternary section would be a single- phase field, although this is not necessarily the case. However, if one pair of carbides has a very limited solubility, then there must be a two-phase field of some extent, and it is the purpose of the present work to examine the extension of this field and to determine if it can be related to the nature of the third carbide. This condition is fulfilled if the VC-ZrC pair, which has only limited solubility, is combined with Tic, TaC, or NbC. The relative sizes of the metal atoms undoubtedly play a role in the extent of the single-phase field, and the values obtained from the pure carbides, assuming close-packing between metal and carbon atoms and a carbon atom diameter of 1.54A, are

Jan 1, 1952

Organization Place Date International Mining Convention (Auspices, Van- 1919 couver Chamber of Mines) Vancouver, B. C. Jan. 8-10 American Institute of Consulting Engineers, Inc... New York, N. Y. Jan. 13 American Society of Civil Engineers New York, N. Y. Jan. 15-16 Institute of Chemical Engineers Chicago, 111. Jan. 15-18 American Wood Preservers Association St. Louis, Mo. Jan. 28-30 American Society of Heating and Ventilating Engineers New York, N. Y. Jan. 28-30 Automotive Engineers New York, N. Y. Feb. 4-6

Jan 1, 1919

By D. F. Lascelles

D. F. Lascelles (School of Earth Sciences, MacQuarie University, North Ryde, N. S. W., Australia)- The paper contains many misconceptions commonly held by both geologists and soil scientists with regard to soil processes. The analogy between supergene copper enrichment and "nickel laterite" deposits is quite apt and the use of nomenclature from the former in describing supergene nickel deposits is justified. However, care must be exercised with regard to the notable differences in

Jan 1, 1974

By C. H. Li, R. J. Stokes, S. H. Bendel, J. A. Sartell, T. L. Johnston

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained' For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above

Jan 1, 1960

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard' has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn' who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99' pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954

By Harry C. Gatos, Frank J. Bachner, Mario D. Banus

The portion of the Nb-Sn phase diagram between 75 and 79 at. pct Nb at temperatures near the liquidus has been investigated by melting alloys of known composition and examining the microstmc-tzlres resulting when these melts were quenched. The Nb-Sn samples were contained in magnesia sleeves, and were mounted in a high-pressure apparatus. It was shown that Nb3Sn me1ts by a peri-tectic decomposition and that the composition of the compound Nb3Sn at the peritectic horizontal lies between 77 and 78 at. pct Nb. Analysis of the phases present in the samples was accomplished by anodic staining techniques and an electron-microbeam analyzer. DURING the past several years a great deal of work has been devoted to the Nb-Sn system, and the bulk of this work has been primarily concerned with the intermetallic phase Nb3Sn. However, the melting characteristics of Nb3Sn have not been investigated because of the difficulty in maintaining known compositions due to tin losses by vaporization, and the added difficulty of containing Nb-Sn alloys without sample-container reaction at the high temperatures involved. This paper reports on the development of a technique for containing Nb-Sn alloys under pressure high enough to prevent tin losses at temperatures in excess of the liquidus. Using this technique, melts of known composition were made and a phase diagram near the liquidus is proposed based on the microstructures resulting when these melts were quenched. EXPERIMENTAL The Nb-Sn alloys weighing 0.7 g each were prepared in the form of cylinders. Niobium powder, -200, +325 mesh, and tin shavings with a minute amount of tin powder for a binder were mixed in the desired proportions and cold-pressed at 50,000 psi in a 0.150-in. die. This cylinder was then enclosed as shown in Fig. 1, and the entire arrangement mounted in a 2.6-in. pyrophyllite tetrahedron.' The desired temperatures (-2500°C) presented several problems in high-pressure container materials. Boron nitride, the usual sample holder, was found to react with niobium to form the nitride. However, MgO cans and plugs machined from refractory rods did not melt nor react with the sample. Thick tantalum contact disks were used to carry the large currents (~450 amps) to the graphite heater, since tantalum did not melt and had enough strength to prevent extrusion of the sample. It was further observed that the graphite heater and tantalum disks could not be in direct contact with the pyrophyllite because it melts and decomposes at these temperatures to kyanite and coesite (SiO2),2 the former reacting with graphite and the latter with tantalum to form the silicide. The use of a MgO outer sleeve

Jan 1, 1965

By J. S. Dodge, I. M. Krieger

The laminarturbulent transition was studied for monodisperse rigid polymer latices as functions of particle diameter and concentration at several tube diameters. Breaks in the graph of friction factor US Reynolds number were used to characterize the transition; rates of shear were sufficiently high so that Newtonian behavior at the high shear limiting viscosity could be assumed. No abnormal behavior was noted at concentrations below 30 volume percent. At higher concentrations, suppression of turbulence was observed with critical Reynolds numbers rising to as high as 5,500 at 50 volume percent. No definite effect on the transition was noted due to variation of particle size or tube diameter. The type of surfactant used to stabilize the latex was found to have an important influence on the critical Reynolds number. INTRODUCTION For some polymer solutions and solid-in-liquid suspensions, the transition from laminar behavior to turbulence in pipeline flow has been reported to take place at unusually low1-5 and in some cases at higher than normal6,7 critical Reynolds numbers. Extreme values of critical Reynolds numbers (NRe*) have been found to range from 1 to 6,000, as opposed to the values of 2,000 to 3,500 which are obtained for ordinary liquids. Observations have also been reported of drag reduction in fully developed turbulent flow, i.e., a decreased value of the friction factor in the Reynolds number-friction factor plot6*10-14 in colloidal and polymeric fluids. In some cases, turbulence suppression (unusually large values of Nre*) was noted to occur preceding the drag reduction,6 while a normal transition was noted in other cases of drag reduction.14 To relate the occurrence of turbulence suppression and drag reduction to the molecular or particulate structure of the fluid, it is desirable to characterize the structural variables with some precision. For most colloidal dispersions and polymeric fluids, this is very difficult; particle sizes, shapes and stiffnesses may vary over wide ranges in the same sample. Recently, however, a colloidal fluid has become available which consists of rigid spherical particles of highly uniform diameter dispersed in a simple Newtonian liquid. These are monodisperse polymer latices, prepared by carefully controlled emulsion polymerization reactions. The purpose of this research was to study the transition to turbulence in these well-characterized colloidal fluids as a function of concentration, particle diameter and tube diameter. Typical flow curves of latices of high solids content are shown in Fig. 1. While these curves were obtained with monodisperse latices, the general shape of the curve is also typical of a polydisperse latex. It is observed that a shear-thinning region occurs for low to moderate rates of shear. At sufficiently high shearing rates a limiting Newtonian viscosity is reached. The viscosity µ diminishes with decreasing volume fraction 4 at all shear rates. For 4 less than 0.25, latices are Newtonian at all rates of shear.15 An increase in average particle size (at a given extends the Newtonian viscosity region to lower rates of shear. A third factor which influences the