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G. K. BURGESS, ? Washington, D. C.-At the Bureau of Standards it was decided, in order to study the high-aluminum end of these curves, that efforts should be made to prepare pure aluminum, and the promise of getting aluminum, practically free from the two elements that have such great effect in very small quantities, namely, silicon and iron, and which

Jan 12, 1919

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST' PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F..RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY K. KENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1914

By A. K. Bhasin

A. K. Bhasin, (Development Engineer, Marcona Corp., San Francisco, Calif)-The author suggests the use of the term "consistency" for apparent viscosity and accordingly calls his viscometer a "consistometer." However, he goes on to refer to "consistency" as a combination of plastic viscosity, yield stress, and stability (p. 104, col. 2, line 6). Unfortunately, such conflicting terminology is encountered too often in rheological

Jan 1, 1973

The following list of US companies, mines, and mills engaged in uranium production was compiled by the Health and Safety Analysis Center, Mine Safety and Health Administration, in Denver, Colo. The list includes those companies reporting to the Center in 1978. Thanks to D. K. Walker, Chief of the Health and Safety Analysis Center, for providing the information to MINING ENGINEERING.

Jan 10, 1978

By O. J. Kensok

THE literature contains three previous studies of the chemical activities of Cd-Mg alloys: Trumbore, Wallace, and craigl obtained chemical activities of magnesium at 543" by performing electromotive-force measurements; Borg and irchenall calculated activities at 590°K based on vapor-pressure measurements of cadmium over Mg-Cd alloys by the Knud-sen effusion method; and Terpilouski and arcka measured the chemical activities of magnesium in the liquid state by means of electromotive-force measurements. In this study the vapor pressure of cadmium was determined over nine solid Cd-Mg alloys in the temperature range 571" to 697°K by the Knudsen effusion method. This study was prompted by the lack of precision in the data reported by Borg and Birchenall. Knudsen cells used during this study were fabricated from 0.020-in.-thick tantalum tubing. The tops and bottoms of the cells were cut from 0.010-in.-thick tantalum sheet, press-fitted, and welded in place. The orifice was drilled in the cell top and subsequently reamed to a knife-edge thickness. The diameter of the orifice was measured with a traveling microscope capable of reading 0.0001 cm. The sample was heated by means of a resistance

Jan 1, 1967

By J. Menashi, D. A. Douglas, A. S. Rappas

Aqueous solutions of Na2Cr04 are reduced with CO to produce hydrous Cr2O3 and NaHCO3/Na2CO3. CH3OH, HCOO- and HCHO in the presence of CO2 also reduce Cr(VI) and yield similar products. It is shown that the rate of Cr(VI) reduction can be represented by the expression -d [Cr(VI) ]/dt = k[Cr(VI)]0.5[R], where [R] is the aqueous phase concentration of CH3OH, HCOO- or CO. With these three reductants, the activation energies for the reduction processes are comparable and are of the order of 100 kJ/mol (43,000 Btu per lb mol). Rapid reduction rates are attained at temperatures in excess of 220°C (428°F). With these three reductants, a green acid-insoluble readily filterable hydrous Cr203, is formed. With HCHO, significant reduction of Cr(VI) occurs at about 80° to 100° C (176° to 212° F). The product is an acid-soluble violet modification of hydrous Cr203. Solutions of Na2CrO4 contaminated with Mo(VI) and W(VI) can be reduced to yield a Cr2O3 product with significantly reduced contaminant levels.

Jan 1, 1986

By A. L. Mular

lnput energy-size modulus relation at small reduc-tion ratios is expressed by Et = (M, -Mt) k;. In some cases 13 is close to Schuhmann's distribution modulus a in value. Experimental results in conjunc-tion with the equation demonstrate the fact that energy input which produced fracture is not expended on unbroken starting material inside the mill at any time. Recently, schuhmann1 derived the Charles equation2 using the postulate that complex com-minution operations can be considered as a summa- tion of many comminution events. The fragments resulting from each event are assumed to follow the Gaudin-Schuhmamn distribution. In his derivation, Schuhmann implies that the size distribution of the total mass of a material is determined by the fraction of that mass actually subjected to comminution. Consider a feed to contain a volume, Vo, of uni- formly sized homogeneous material. After t seconds of grinding, let the volume of broken material be Vo - Vt where Vt is the volume of starting material not yet broken. The size distribution of the broken material is given by: where V is the cumulative volume less than size X, and k, is the size modulus of the broken material at time t. The distribution for the total volume at this

Jan 1, 1962

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By A. W. Fahrenwald

CELL depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence-i.e., the depth in the pulp at which the impeller is required to produce aeration. THE FLOTATION MACHINE A COMPRESSOR A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure[t] (14.7 lb. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 lb. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 lb. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 [-] 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 [=] 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the finer, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. THE FLOTATION MACHINE AS A PUMP Since, in impeller machines that rely upon their own operation to produce aeration, pulp passes through the im-

Jan 1, 1946

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By Benj. E. Shackelford

THE present paper is concerned with typical temperature values experienced in lamp-filament measurements as made on regular factory and engineering products. It deals with the relations existing between temperature, efficiency, lamp size, and life of incandescent lamps, insofar as they affect the rating of the product and its use by the individual consumer. The temperatures measured lie in that range covered only by the general method of radiation pyrometry, as opposed to direct methods used under contact conditions. The range of temperatures ordinarily experienced extends from about 2125° K., for the now almost extinct carbon-filament lamp, to 3200° K. for the comparatively new tungsten-filament motion-picture lamp. Most of the more common sizes of tungsten lamps have temperatures ranging from 2500 to 3000° K. Because of the high temperatures involved and the relatively small area of the sources used, we are practically restricted to two methods of measurement, both of which depend on the light radiated front the filament. The first and more usual method is that of the Morse pyrometer, dependent on the variation in temperature of the amount of light of a given color range yielded by the filament. In this case, the measured temperature is that of a small part of the incandescent body, that is, the part which is focused on the comparison filament. The second method, known usually in this country as that of "color match" and in England as "color-identity" is based on the color of the total light yielded by the filament, the comparison being facilitated by the use of an ordinary photometer- head. A more definite idea of the temperatures involved in the case of filaments of various vacuum and gas-filled lamps, is given by Fig. 1. The size of the lamp, in watts, is plotted along the horizontal axis and the temperature of the filament is plotted along the vertical axis. The lamps concerned are regular product, rated for 1000 hr. life. The temperature values for the old 16-candlepower carbon lamp and the new motion-picture lamp are shown by the cross and circle respectively.

Jan 9, 1919

By R. W. Parsons

wben a displacement front encounters an isolated permeability heterogeneity, it will be perturbed. The details of this perturbation will depend on the beterogeneity size and shape, the Permeability contrast, and the mobility ratio. This paper deals with the displacement front behavior for one, simple, mathematically tractable model: a circular permeability discontinuity and unit mobility ratio. The progress of an initially planar front is shown for four permeability contrasts: k2/k1 = 0, 5/2, 2, m. The front distortion is more pronounced than streamline and isopotential distortion and it approaches a constant shape downstream from the discontinuity. INTRODUCTION The impact of reservoir heterogeneities on oil displacing processes depends upon the variation of the heterogeneous property (frequency distribution), its disposition (spatial distribution), and the inherent stability of the displacement mechanism.l The interplay of these factors plus the impracticability, if not impossibility, of describing a natural rock system in any detail makes exact displacement front movements difficult to determine. It is useful, however, to be able to qualitatively visualize what heterogeneities will do to a displacement front. In this respect certain simple models that can be treated analytically are of value. The following analysis will show the displacement front behavior for one such model. MODEL DESCRIPTION The flow field is two-dimensional and infinite in extent. The fluid flow is single phase, steady state and unidirectional at x, y = 2 m, or before insertion of the discontinuity. A circular permea- bility discontinuity is placed at the origin. Porosity and thickness are the same within and exterior to the heterogeneity. This is exactly the same model that was used by Greenkorn et al. to check analytically Streamlines as determined by Heie-Shaw flow models and finite difference computer techniques.2 FRONT POSITION CALCULATIONS The results of displacement front calculations are presented in Figs. 1 through 4 for four different permeability contrasts: k2/kl = O, %, 2, m. The times corresponding to the front locations are the Same for the 0 and cases! and for the 1/2 and 2 cases. The determination of front positions at various times is based on known analytical expressions for velocity potentials ().2 and stream functions ().2 These expressions are in terms of the x and y

Jan 1, 1969

By S. Atak, M. C. Fuerstenau

Clean quartz cannot be floated with a high molecular weight sulfonate as collector at any pH. Good flotation is achieved from pH 6 to 12 when Pb is added at low additions of sulfonate. The active species of lead responsible for flotation is shown to be Pb(OH), which in the presence of sulfonate forms precipitated lead-hydroxy-sulfonate, the apparent collector in these systems. The ratio of collector to metal ion addition is critical for flotation to be effected at a given value of pH. At low Pb++ additions, the constant, k, k = (hydroxyl activity)/(sulfonate addition)', must be equalled or exceeded for flotation to result. Similarly, at high additions of Pb ++, k1 = (hydroxyl activity)/(sulfonate addition) " must be exceeded. Previous work has shown that clean quartz cannot be floated at any pH with a high molecular weight sulfonate as collector.'" Flotation can be effected, however, when a polyvalent metal ion is added to the system in a pH region in which the metal ion is hydrolyzing to its first hydroxide complex. Although the basic phenomenon responsible for activation is apparently metal ion hydrolysis, the amount of collector added in relation to the amount of metal ion is critical. In fact, Schuhmann and Prakash,3 and Gaudin and Rizo-Patron4 have demonstrated that this ratio of collector addition to metal ion addition determines whether any flotation is possible at a particular value of pH. The object of this paper is to explain and quantify the relationship between collector and activator additions as a function of pH. For this work, Pb++ was selected as activator, and a high molecular weight sulfonate was chosen as collector. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate (mol wt 450) was used as collector. Reagent grade n-amyl alcohol was added as frother, and pH adjustments were made with KOH. Lead was added to the systems as the chloride salt. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample

Jan 1, 1965

By W. Rostoker

IN the course of the development of the phase equilibrium diagram for the system Zr-Cr,' the structure of an as-cast allov having the composition ZrCr2 was analyzed and established to be isomorphous with MgZn2 (C14, hexagonal lattice, 12 atoms per unit cell). In a recent paper on the same system, Hayes, Roberson, and Davies' report for the ZrCr2 phase an isomorphy with MgCu2 (C15, cubic lattice, 24 atoms per unit cell). It appeared that this conflict might be resolved by assuming a high and low temperature modification for ZrCr2. That this was the case with the phase TiCr2 has recently been demonstrated by Levinger." Specimens of ZrCr2 annealed at 1200°, 1100°, 994", 900°, 834", 800°, and 700°C, respectively, and subsequently quenched were examined by X-ray diffraction analysis. It was successfully demonstrated that a transition from the MgZn, structure at lower temperatures to the MgCu, structure did occur at some temperature between 900" and 994°C. Table I lists the observed structures at the various annealing temperatures. In Table II, a summary of line spacings and intensities is given for each of the allotropic modifications. The first six lines of the MgCu2 structures have been located in the table to illustrate the close similarity between the patterns. Lattice parameters of the two modifications were calculated by a least squares solution of equations for interplanar spacings for a series of high angle lines. The results are as follows: MgZn2 type - c = 8.262 kX, A = 5.079 kX. MgCu2 type — a = 7.195 kX. It is interesting to note that TiCr2 behaves in reverse fashion yn that the MgCu, structure is the low temperature modification and the MgZn2 structure is the high temperature modification. References lR. F. Domagala, D. J. McPherson, and M. Hansen: This issue p. 279. 'E. T. Hayes, A. H. Roberson, M. H. Davies: Trans. AIME (1952) 194, p. 304; Journal of Metals (March 1952). 3B. W. Levinger: Trans. AIME (1953) 197, pp. 195-196; Journal of Metals (February 1953).

Jan 1, 1954

By M. H. Richman, W. D. Sproul

THE indexing of a field-ion micrograph is in many cases similar to the indexing of the poles of a stereo-graphic projection.* If one has a standard projection as a guide, the task of indexing is relatively simple. In this way, field-ion micrographs of bcc and fcc wires have been oriented from projections available in most any text on X-ray diffraction. These books always illustrate the projections for the bcc and fcc structures and even for a particular hcp structure. There is no "standard" hcp projection because the angles between planes depend on the c/o ratio of the unit cell. In order to index field-ion micrographs of hcp metals, one must compute the angles between various planes—a rather laborious task. In recent work,, we have had to identify the structure and index the orientation of field-ion micrographs of the compounds WC and W,C. To overcome the problem of computing angles by hand or calculator, a program was written in Fortran lV for use on the IBM 360, Model 50 which will compute all angles between planeswith indices (hlklll) and (17,k,l2) in the range from (447) to (444) for any given c/o ratio. The program, which is more specific than that of Camp and clum, was so written as to take advantage of the multiplicity of the hexagonal system, and, for the limits defined above, only 26,649 values out of a possible 265,721 values had to be computed. This is a 90 pct saving in time (and cost) and was accomplished in the following way. Because the lattice parameters of the hexagonal crystal system are defined such that: a = b * c [1] the I index does not enter into the multiplicity (i.e., it cannot be transposed with the h or k indices), and all possible values of h and I, from 4 to 4 must be used—a total of eighty-one combinations. The index h2 varies the most—it must assume values from - Ill,: to 3Ihl. The indices kl and k2 are always equal and vary

Jan 1, 1969

By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

ALABAMA Altoona -Cain, J Anniston -Cowie, L K Heimrod, A A White, H E Bessemer-Abbott, C C Ball, E M Mitchell, F R Thompson, N E Birmingham -Adler, T E Aldrich T H Aldrich, T H, Jr Blackburn, A R Bush, 117 W Clark, G H Cowin, P G Crane, W R Crawford, G G Crockard, F H Darnelspn, G E Davis, C B

Jan 1, 1923