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By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Ursula E. Wolff

Il.lechanica1 twins have been observed in brigsten single crystals of a variety of axial orientations defornzed at room temperature in tension or bending. The twins formed near the final fracture and were up to 3 p thick. The twinning plane was always of the type (113). Twinning at room ternperature occurred only after considerable prior slip. Twins usually preceded fracture and nucleated cracks. The crack surfaces often alternated between a (001) plane and the twin interfaces. Secondary twins could also nucleate from cracks. In the absence of twinning tensile samples failed by shear; twinned samples failed by cleavage. On the assumption that observed sudden load drops in the stress-strain curves are associated with twinning, a critical resolved stress for twinning of 60, 000 to 65, 000 psi was calculated. MeCHANICAL twinning has been observed in iron and iron alloys at low temperature by a number of investigators.'-7 Similarly, for high-purity tungsten, twinning has been reported for deformation temperatures below 211°K.8-10 In W-Re and Mo-Re alloys, 20 pct Re was determined as the lower limit for twin formation at room temperature." Since the twins are generally very narrow, they are usually identified only by etching techniques. The expected (112) habit plane has always been confirmed by angular analysis of the surface traces. Recently, however, a complete identification by X-ray analysis has been performed on twins in a Mo-35 pct Re alloy.12 During an investigation of the deformation charac- teristics of tungsten single crystals, twins were revealed in tensile and bend samples deformed at room temperature. This paper deals with the conditions for such twinning and the relation of twinning to fracture. EXPERIMENTAL PROCEDURE Tungsten single crystals, 1/8 in. in diam, of a variety of axial orientations were grown from un-doped material by four-pass electron-beam zone melting. A representative analysis is given in the following table: From these crqstals, tensile samples with 1 in. gage lengths were made by surface grinding, leaving shoulders for gripping. The diameter after grinding was 0.082 in. The distorted surface layer was then removed by ele1:trolytic polishing which reduced the diameter of the gage length to 0.080 in. Tensile tests were carried out at room temperature in an Instron machine under two different sets of conditions: a) Rigid mounting; strain rate 0.02 in. per in. per min. b) Gimbal mounting; strain rate 0.002 in. per in. per min up to a total strain of approximately 0.2 pct, then 0.01 in. per in. per min to fracture. Stress axis and growth direction coincided in all samples and are subsequently called orientation.

Jan 1, 1962

By L. S. Richardson, N. J. Grant

Iodide-grade titanium, two oxygen alloys, and two aluminum alloys were studied by means of creep-rupture tests from 1000° to 2000°F. From the test information an evaluation was made of, 1) the relative creep-rupture strengths of the u (hexagonal-close-packed) and 0 (body-centered-cubic) forms of titanium and some of its alloys; 2) the effects of solid-solution strengthening by oxygen and aluminum on the u and 0 structures; and 3) the extent and effect of atmospheric oxygen alloying on rupture life in tests above about 1000°F. THE use of titanium alloys at temperatures above 1000° F has been considered unlikely by most investigators because of low creep strength (based on a requirement for room-temperature ductility, formability, and weldability) and low oxidation resistance. The results of this testing program do not entirely uphold this pessimism in terms of strength and oxidation resistance. The observations described below are based entirely on stress-rupture results, although some creep tests were also carried out on these alloys. Three items of primary importance are covered: 1) Stress-rupture data in the form of the Larson-Miller parameter curves for several titanium alloys at temperatures up to 2000°F; 2) The relative strengths of the hexagonal-close-packed a structure and the body-centered-cubic 0 structure; 3) The effects of solid-solution alloying on the creep-rupture properties of titaniu'm at elevated temperatures. Only two investigatons have reported the creep- rupture properties of titanium at temperatures above 1000° F. Lunsford and rant' tested iodide titanium; their values are also utilized in the paper. EXPERIMENTAL PROCEDURE After a few tests had been made in a conventional creep-rupture test machine, it became clear that some sort of atmospheric protection would be necessary for short-time tests conducted at temperatures above 1600°F, or for times greater than 100 hr at 1200°F or above. Several furnace units and test machines were constructed, the most successful of which is shown in Fig. 1. Certain experimental difficulties peculiar to titanium were encountered; for example, the use of molybdenum holders was dictated because titanium forms low melting-point eutectics with conventional high-temperature alloys containing appreciable amounts of iron, nickel, or cobalt. This same difficulty made the use of chrome l-alumel thermocouples in direct contact with a test specimen impossible, above about 1500" F. The high-temperature high-vacuum furnace shown in Fig. 1 was capable of maintaining a vacuum of better than 10"5 mm of mercury at 2000°F (pressure measured in cold part of system) and 5 X lo-' mm at room temperature. Most of the tests eonducted in vacuum were at temperatures

Jan 1, 1960

By W. L. Fink, L. A. Willey

DURING the war there was introduced a new higher strength aircraft alloy designated 75S.1,2.3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75S alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75S alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. PROCEDURE Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75S "as rolled" sheet (0.064 in. thick). The composition° was as follows: Weight Percentage Cu Mn Mg Zn Cr Al with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16 in. i.d. by ¼ -in. o.d. by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064 in. thickness over the junction and adjacent lead wires for a distance of 1 ½ in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3 in. by 9 in. by 0.064 in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75S extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of ¾ in., 2 in., 3 in. and 4 in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 ½ in. Thermocouples were peened into the bottoms of 1/8 in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1947

By B. H. Caudle, R. E. Watson, I. H. Silberberg

The production history of an inverted nine-spot injection pattern was studied with a porous plate model similar to Habermann's. Colored fluids were used so the boundary movements could be photographed. By varying the production rates of the side and corner producing wells, the optimum pattern sweep efficiency can be obtained. Results of the laboratory tests indicate that interpolation of the pattern sweep and conductivity ratio data will permit application of the data to predicting fluid injection operations with mobility ratios between 0.1 and 10 and production rate ratios between I and the optimum values. INTRODUCTION The inverted nine-spot injection pattern in Fig. 1 has some unique advantages over other regular injection patterns (five spot, line drive, etc.) used in secondary recovery operations. It has three producing wells for each injection well, while the five-spot and line-drive patterns require an equal number of injectors and producers. Futher-more, of the eight producing wells surrounding each injection well, four are of the "side well" type which lie nearer the injection well than the remaining four "corner wells". This allows the production rates of these two types of wells to be adjusted independently of each other to obtain better pattern sweep efficiency. This latter advantage may well be the reason why the nine-spot patterns have not been studied as extensively as the patterns containing only one type of injection or producing well. The pattern sweep efficiency of the inverted nine spot is affected almost as much by operating with different producing rates of the comer and side wells as by differing mobility ratios. Possibly because of this added operating parameter, published studies of nine-spot systems have been limited in their coverage of the pertinent variables.'-' The model studies reported here covered the mobility-ratio range normally found in waterflood operations, as well as the variation in well production rates necessary to achieve optimum pattern sweep efficiency. Conductivity ratios — a measure of the change in total flow at constant pressure difference — were obtained during each model run. A porous-plate model with miscible fluids representing the in-place and injected fluids was used in this study. This model technique is the same as that used in both X-ray shadowgraph" and visual techniques4 described in the literature. Using miscible fluids eliminates residual oil in the model, and the permeability to the injected fluid is the same as to the in-place fluid. Thus the mobility ratio in the model is given by the ratio of the viscosity of the displaced fluid to the viscosity of the injected fluid. Because of the non-linear nature of the viscosity vs composition curve for two miscible liquids, the mobility change across the boundary between the two fluids is reasonably sharp. This technique thus represents the displacement of a region of one fluid mobility by a region of possibly different mobility in an isotropic system under steady-state flow conditions. Table 1 shows the dimensionless similarity groups used to scale the model conditions and results to

Jan 1, 1965

By R. J. Sherman, M. R. Achter

IT has often been reported that coatings may strengthen single crystals and polycrystalline specimens of coarse grain size. This note reports the effect of a surface layer of fine grains on the creep-rupture properties of coarse grained nickel 99.8 pct pure. Sheet specimens were machined from cold-rolled material, finished by surface grinding and annealed at 1230°C in vacuum for 4 hr. Half of them were re-ground on faces and sides and annealed at 925"C for 1 1/4 hr. The double grind-anneal treatment produced a structure consisting of a surface layer of fine grains of 0.02 mm diam on a coarse-grained substrate of grains of 0.40 mm diam. Comparison with specimens which received only the single grind showed that the second grind-anneal did not alter the structure of the substrate. Several modifications were made in specimen design to eliminate erratic rupture behavior outside of the gage length. In the final design the gage section, oriented parallel to the rolling direction, was 1.00 in. long, 0.4 in. wide, and 0.0625 in. thick. End tabs were pinned in place. Although other configurations (welded end tabs, transverse orientation, and wider gage section) showed similar effects of a layer of fine grains, because of the erratic rupture behavior, only the data from the final design are reported here. Creep tests were performed at 650°C in air and in a vacuum of 10~5 mm Hg. Creep rates were measured from the movements of the lever arm. Since the broken sheet specimens could not be fitted together, elongations at fracture measured by means of gage marks, do not include the necked portions adjacent to the fracture. Results of the creep tests with and without the fine grained surface are given in Table I. An explanation for the lower strength in air than in vacuum has been proposed previously in terms of the reduction of crack propagation energy by gas adsorption.l In both environments the fine-grained layer produced a small decrease in minimum creep rate and, except for the shortest test in air, a substantial increase in rupture life. The elongation values at rupture, as they are measured here, do not demonstrate an appreciable effect of the grain structure but do show much smaller ductilities in air than in vacuum. Greater elongations maybe associated with the finegrained layer, however, especially in vacuum, in creep curves such as those in Fig. 1. Duplicate tests were not run to determine the re-producibility of the data. It is felt, however, that, in view of the consistent behavior, the prolongation of rupture life may be attributed to the effect of the fine-grained surface. In the data not reported be-

Jan 1, 1962

By A. G. McGregor

In the Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 1/2 in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining CO.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally 1/4in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft, from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 1/4-in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar —water, sodium silicate, and finely ground silica—was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By H. B. Hunter, F. G. Stone, F. J. Dunkerley

Introduction and Literature Survey This is the second in a series of papers coming from this laboratory on the correlation of the low temperature tensile properties of tin-binary alloys with microstructure. These engineering data and those of the previous paper1 were obtained as the initial part of a long-range program to determine the changes in the fundamental mechanical properties accompanying the beta to alpha phase change in tin and its binary alloys below 13.2°C. Since it appears now that the more fundamental studies will be delayed,* and since no summary of the low temperature properties of these tin-base white bearing alloys was found in the literature, it was decided to publish all the engineering data thus far obtained. Accordingly, the tensile properties of thirteen binary alloys containing from 0.1 to 60 pet cadmium and 0.1 to 10.43 pet antimony measured at six temperatures from —196 to +23°C are presented here and their variations rationalized in terms of microstructure. A literature search showed that these systems had not been investigated at low temperatures, although both the tin-cadmium and tin-antimony2,3,4,5 and the tin-rich corner of the ternary system67 have been studied at room temperature. Hanson and Pell-Wal-pole5 and Homer and Plummer4 determined the tensile properties of alloys containing from 0 to 10 pet cadmium. The same authors3 determined the tensile strength and elongation in the tin-antimony system from 2 to 18 pet antimony at room temperature while Pell-Walpole et al.6,7 studied the properties of high tin and tin-antimony-cadmium alloys. Since there were many variables besides composition in these tests, it was difficult to make a valid comparison with the room temperature data of the present study, but in general the tensile strength and ductility values are in reasonable agreement. Pell-Walpole2 also determined the effect of grain size on the tensile strength of pure tin and 1 pet alloys of both antimony and cadmium. The true maximum stress was found to decrease exponentially as the number of grains in the cross-section increased. This effect of grain size was strikingly revealed in the present work, as indicated in a later section. Hanson and Pell-Walpole8 placed the solid solubility limit of antimony in tin at 3.5 pet at 20°C, increasing to 4 pet at 190°C, and then sharply increasing to 10.3 pet at 246°C (the latter being a peritectic point). Their results are in disagreement with those of previous investigators,9 and the discrepancy seems to lie in the micro-graphic observation of the second phase

Jan 1, 1950

By R. D. Fisher, A. G. Metcalfe, F. A. Crossley

AN investigation of the application of magnetic stirring to the consumable arc melting of aluminum and nickel demonstrated that grain refinement could be obtained when there was sufficient stirring force. Also, it was found that grain refinement could be obtained in aluminum by alternately reversing the polarity of the current through the magnetic stirring coil. The effect of the latter was to periodically reverse the direction of rotation of the molten metal.' Because of their promise, these findings were applied to conventionally cast aluminum. Shortly after this work was begun, Kondic2 reported experiments in which aluminum cast with 40° C (72° F) of superheat exhibited a grain size of 10 to 20 grains per cm2. When interrupted rotation was applied during solidification by mechanical means, a grain size of 800 to 1000 grains per cm2 was obtained. Magnetic Stirring Applied to Conventional Casting— The applicability of magnetic stirring to producing grain refinement in conventionally cast metal was evaluated in the following way. Three pounds of aluminum were cast into a clay-bonded graphite mold. The mold was surrounded by a magnetic stirring coil of 1000 turns. A direct current of 200 amp was passed through the casting by means of a graphite electrode which was immersed from the top. A current of 5 amp was passed through the stirring coil. The aluminum (1100 or 25) was superheated to 1600° F (871° C) and fluxed by passing chlorine gas through the melt for 2 min prior to casting. Two additional castings were made for comparison: 1) a conventional casting of metal superheated to 1600° F and 2) a similar casting through which 200-amp current was passed during solidification, but without current in the magnetic coil. Macrosections of these three ingots are shown in Fig. 1. Very remarkable grain refinement resulted in the magnetically stirred casting. It may be noted that the casting through which 200-amp current was passed has a coarser structure than the conventional casting. It would appear that this is due to the additional heat input generated by the current to the former casting. Mechanical Rotation Applied to Conventional Casting—A casting temperature of 1600° F was used throughout. Some 1 1/2 -lb castings rotated at 150 rpm were predominantly columnar with small areas of coarse, equiaxed grains close to the lower mold wall. Following these, a series of 3-lb castings was made. Macrosections of these ingots are shown in Fig. 2. The imposed rotational speed was 250 rpm. Turbulence or acceleration in the solidifying liquid was the significant factor. Fine grain size resulted in the material solidified during the period of acceleration of the liquid to the imposed rotational speed. When uniform rotational motion was achieved, the grain structure reverted to columnar. The final casting shown in the lower right-

Jan 1, 1962

By Harry M. Mikami, A. Gene Sidler

Chemistry of the evolution of materials in contact with copper converter tuyeres is delineated by means of analyses of periodic punch rod samples taken during a converter cycle. Lining samples from known peripheral and end locations from three converters were investigated chemically and petrographically. One set of eight specimens representative of all lining parts was removed for study before completion of the campaign. Purely surface removal by slag action is minor. Slag filling of interconnecting cracks extending to the hot face results in a "stoping'' action which shapes the hot face contour and is a significant factor. Major wear mechanism is believed to be copper metal slabbbing caused by metal first penetrating joins and invading fractures or impregnating brick structure laterally from the joints. Importance of lining design and joint fit are emphasized. New laboratory tests are indicated. In the copper converter, molten matte, which is essentially a solution of iron and copper sulfides, is blown with air to produce blister copper. During the first stage of the process the FeS component is oxidized to SOz and FeO, the latter combining with a siliceous flux to form a predominantly ferrous silicate slag. Successive increments of matte and flux are charged, blown, and skimmed of slag until sufficient CuzS ("white metal") has accumulated. This white metal is then blown to copper metal in the final or blister-forming stage by the oxidation of sulfur to SOz and the reduction of combined copper to metal. The reactions of both stages are exothermic so provide the required heat. Temperature is controlled by cold scrap copper, flue dusts, smelter reverts, and so forth. Considerable vari- ation in practices occur depending on the type of converter, grades of the matte and flu, and other factors. Lathe and Hodnett's' survey of world converter practices gives much information on these variations and their effects on the refractories. Principles of converting chemistry are presented by Newton and wilson,' Ruddle,' and schuhmann. Most copper converting occurs within the temperature range 2100" to 2370°F although individual smelters report1 ranges from as low as 1700" to 2240°F to a high of 2200" to 2400°F. Temperature intervals reported from beginning to end of blow varied from 45" to 540°F. Average temperature range was 2030" to 2260°F and the average interval 250°F During the matte-blowing stage varying amounts of magnetite (FeO.Fe,O,) are formed in the slag as suspended crystals and also the liquid portion of the slag will contain, in addition to ferrous silicate, some Fe20s which adds to the potential magnetite formation if the temperature falls. This is a component of the so-called "dissolved magnetite" often referred to in the literature. Although the slag may contain minor amounts of CaO, A1209, MgO, and alkalies, the principal components are Fe0-Fez03-SiO,. The phase equilibria relationships of this system have been elucidated by Muan~ and Schuhmann, et a1.' These data and estimates of converting atmospheres by schuhmann4 are useful tools in studying slag behavior. It would appear that in many cases reported magnetite contents of slags are apparently higher than actually is present at operating temperature. This is probably because much of it is formed during slag solidification. The quaternary systems which have Mg-0,1,0,' and addition to iron oxides and silica are also of interest in considering the reactions of the slags with basic refractories. The formation of magnetite has an important interrelationship throughout the pyrometallurgy of copper (Mossman,' Gronningsater and Drummond," Ruddle,' Elwood and Henderson") but its presence in the converter particularly relates to operating efficiency and lining life in certain instances. Archi-

Jan 1, 1963

By M. R. J. Wyllie, Walter D. Rose

The use of electrical well logs for the quantitative determination of such reservoir parameters as connate water saturation, formation permeability and connate water salinity has recently been attracting the attention of a number of workers1,2,3,4,5. While the theory of the determination of connate water salinity from the self potential S.P. log has received rather detailed treatment, relatively little attention has been paid to the theoretical aspects involved in the quantitative interpretation of resistivity data. It is clear that if electrical well logs can be used for the quantitative evaluation of physical characteristics of reservoir rock, they will provide a valuable tool to supplement cheaply information obtained by more laborious core analysis. In certain cases it is conceivable that the coring program could be considerably curtailed if the electric log could be relied upon to give reasonably accurate quantitative information. It is our object in this paper to examine the theoretical basis of quantitative log interpretation as expressed in such well-established logging concepts as formation factor and cementation factor. It is also our object to investigate the physical aspects of the rela- tionship which is presumed to exist between resistivity index and brine saturation in reservoir rock. In particular, we will endeavor to draw attention to the fact that it is possible to express these logging concepts in terms of capillary pressure-saturation relationships, permeability and tortuosity, parameters which we will consider in this paper to be fundamentally indicative of rock texture. The probability of being able to obtain from log recordings alone the data theoretically essential to permit quantitative log interpretatiou will be examined, and consideration will also be given to the problem of formulating simple semi-empirical relationships for use in the field. THEORETICAL CONSIDERATIONS The concept of formation resistivity factor, or as it is now commonly called, formation factor, appears to have been introduced by G. E. Archie",". Formation resistivity factor as defined by Archie is the resistivity of a rock 100 per cent brine-saturated divided by the resistivity of the brine. This relationship had previously been used by physical chemists and the concept is, for example, implicit in an early treatment by Fricke7 of the conductivity of aqueous slurries. Archie was able to establish the fact that although the relationship between formation factor and porosity did not change too greatly for different rock textures, the relationship between formation factor and permeability was markedly dependent on rock texture. The relationship found by Archie between formation factor and porosity was expanded by H. Guyod8. Archie had suggested that the formation factor, F, could be expressed in terms of the porosity, F, as follows: F =F-m .... (11 where, F = effective porosity fraction of the sand, and, m = an exponent greater than about 1.3. Guyod introduced the term cementation factor for the exponent, m, since it may be qualitatively shown that formation factor for any given porosity tends to increase as the sand becomes more cemented. It would appear that the concept of m as an exponent representing the cementation in a sand is strictly only of qualitative value, since the quantitative estimation of m by means other than the determination of F and F has not been possible. Guyod suggests that m can be estimated from a visual examination of a sample of rock, but this method appears to be both arbitrary and unreliable. It can be said, however, that in intergranular reservoirs of practical interest, the range of m is from about 1.4 to 3.0. A possible explanation for the fact that m is found to lie between these limits will be offered below. The determination of formation factor is an essential preliminary to the

Jan 1, 1950

By Euclid P. Worden

In 1977, an article in World Mining1 reported a total of 2726 rotary blasthole drills in service. This figure included only those machines produced by three of the manufacturers building drills of this type. The total, therefore, is much higher. Rotary drilling in the mining industry is big business to the manufacturers and suppliers involved, and a significant cost item to mine operators. The time has come to take a hard look at rotary drilling technology with an eye to reducing costs by increasing drilling efficiency. The efficiency of any rotary drilling operation is best measured in terms of the rate of penetration achieved by the bit. In blast hole drilling, there are five factors which affect the rate of penetration. They are: (1) bit selection, (2) weight on the bit, (3) rotary speed, (4) hole cleaning, and (5) formation properties. Of these factors, all but one may be controlled by the operator. Looking at any one in detail may reveal possible improvements in the system. One of these factors -- proper hole cleaning - will be discussed in this paper. In order for a bit to perform at its maximum capability, each tooth or insert should strike fresh clean rock as it falls into its drilling position. If the tooth or insert lands on previously drilled cuttings, a major portion of the energy delivered to the bit is absorbed in redrilling this broken material. A major portion of the interest, therefore, should be directed to the proper cleaning of the bottom of the hole. In an in-depth study of the cleaning of large diameter holes, Allen2 reports that horizontal air velocities of 38.10 m/s are necessary to prevent the saltation of drilled cuttings on the bottom of the hole. The exact flow pattern on the bottom of the hole, however, is not generally known. The air leaves the bit through the jet nozzles and the mouths of the cones, but where it goes from there is uncertain. This problem should be investigated by the bit manufacturers because they can best utilize the results of such an investigation to provide a more effective product. Some work has been initiated in this area and competition will probably increase its intensity. Bailing velocity is the best criteria to measure the cleaning of the hole, including the bottom, and is the factor on which efforts toward improvement must be concentrated. The first consideration is "What should the bailing velocity really be?" In drilling deep holes for oil and gas, 15.24 m/s is the generally accepted figure. In blasthole drilling, the figures of 25.40 m/s for average rock to 35.56 m/s for iron ore were first mentioned by Capp3 in 1962. The recommendations are the same to this day. A number of questions could be asked in regard to the apparent disparity between these two sets of figures. Various investigators have derived formulas which support one or another of these criteria. A thesis on the subject was written by Alexander4 who derived a formula based on research which resulted in velocities in the lower end of the ranges quoted previously. He set out to compare this figure to laboratory tests and his tests indicated that the velocities given by the derived formula appeared to be high.1 Perhaps the best reason that the 25.40 to 35.56 m/s range has been used, is that these velocities seem to work. Below the accepted figures, low bit life and slow penetration rates occur. Above these figures, increasing amounts of abrasive wear on the drill pipe and stabilizers seem to appear. There is a fallacy to this entire approach, however. The entire velocity calculation is made using nominal bit and pipe sizes and compressor deliveries with no compensation made for losses in the system. Perhaps an examination of some of the things that are not presently considered could lead to some practical improvements in the operation.

Jan 1, 1980

By H. Matlock

Beam-columns with continuous or discontinuous transverse and angular loads and elastic restraints are represented mathematically in a manner corresponding to finite-element mechanical models. Solutions for linearly elastic cases are accomplished by direct recursion-equation elimination of unknowns, and for cases involving nonlinear loads and supports, by repeated trial-and-adjustment of complete elastic-type solutions. Five practical applications are presented by which various capabilities of the general method are illustrated. The examples include simulation of a pipeline launching and the bending and collapse of a conductor pipe in deep-water drilling operations. INTRODUCTION The diversified and complex operations being conducted in support of the production of offshore oil have produced a wide variety of new problems in structural mechanics. Many of these problems cannot be solved by conventional analytical or experimental approaches and have therefore stimulated inquiry into new methods of solution. It is the purpose of this paper to give a brief description of an analytical method for solving nonlinear beam-column problems and to illustrate the generality of the method by applying it to several problems related to offshore operations. Although the data for all of the examples are artificial, the cases discussed will be recognized as being based on actual situations. DESCRIPTION OF METHOD The analytical approach which is to be described stems from research on offshore foundations, in particular, the study of lateral-load behavior of foundation piles. The method represents a generalization of a technique which was suggested by Gleser' and extended by Focht and McClelland2 and Reese and Matlock." To maintain generality and therefore versatility in the method, a considerable variety of input data is considered. Fig. 1 illustrates the various types of loads and restraints which might be applied to a short segment of a beam. Each of the terms illustrated in the figure is shown acting in a positive sense. Capital letters are used to designate concentrated quantities whereas the corresponding lower-case symbols indicate effects which are distributed in some way along the length of the beam. The transverse loads and the elastic restraints may be divided into two classes: (1) loads Q and q and springs S and s, which act normal to the axis of the beam, and (2) couples T and t and rotational springs R and r, which act in an angular sense. In addition, there is an axial force P which may be constant or may vary along the length of the beam. The bending stiffness of the beam (the product EI of the modulus of elasticity and the moment of inertia) is designated by the symbol F. The assumptions of conventional elementary beam theory provide the basis for the present method. Among these are the neglect of shearing and axial deformations and the limiting of consideration to straight beams of symmetrical cross-section. Lateral deflections are considered to be small compared to original dimensions. A deformed element of such a beam is shown in Fig. 2a. The curvature of the beam is approximated by the second derivative of the deflection y with respect to distance x along the beam. It is assumed that the material of the beam is linearly elastic and therefore the relation of Eq. 1 between curvature and bending moment M is the ordinary expression from elementary beam theory. A generalized beam element is shown in Fig. 2b. The element has been deflected in a positive direction by an amount y and tilted through a small positive angle dy/dx. The various loads and elastic restraint reactions are detailed in the figure. Temporarily, only distributed effects are considered; provision for concentrated loads and restraints will be made subsequently. Eq. 2 in Fig. 2b is obtained by summing the forces and moments acting on

By A. D. Wilkinson

A CROSS-SECTION of the converter aisle through one of the converters and reverberatories is shown in Fig. 5. The aisle is 280 ft. long by 60, ft. wide by 681 ft. to the roof trusse, which have a 63-ft. span and are us )ported by steel columns spaced at 2b-ft. centers. Two 80-ton electric trails, supplied by the Welman Smith .Owen Engineering Co., with 20-ton auxiliary lifts, serve this building. Matte shells and converter-slag shells are dumped into heavily con¬structed flat-bottom bins located on the south side of the converter aisle and 1.0 ft. above the floor. The material is broken by ball and by hand, shoveled off into ladles for unloading on to the reverberatory charge floor, and charged into the furnace as previously mentioned.

Jan 1, 1934

By Herbert Haas

ChEap power is essential to large-scale mining and metallurgical operations, particularly where fine grinding of large tonnages has to be resorted to, as is the case with an increasing number of mines treating disseminated copper ores, or low-grade gold ores, in the grinding of which considerable power is consumed. A comparison of the cost of generating power with Diesel engines and steam turbines and a brief discussion of the different factors governing the profitable use of either type of prime mover may be timely in view of the importance of a cheap supply of power to the mining industry, and the prominence that has lately been given to Diesel engines in America. As many of our most important mines and largest producers of metals are located in sections where neither cheap coal nor water power is available, and the price of oil fuel is increased by long hauls, the Diesel engine will become a prime mover of increasing importance. This applies particularly to the Southwestern States, where an ample supply of cold water for condensing purposes is unusual and local climatological conditions interfere in securing the high vacua essential to high turbine efficiency. About 12 times as much water will be required for condensing purposes with steam turbines under general conditions as is needed for jacket-cooling of two-stroke cycle Diesel engines; four-stroke cycle Diesel engines require only one-twentieth of the cooling water. Another condition favoring the use of Diesel engines is the high load factor at which most mine power plants operate. The influence of load factor on the cost of generating power is shown in Tables 1. and 2 and in Fig. 1. The higher the cost of fuel and the load factor, the greater will be the proportion of the fuel to the other costs making up the total cost of generating power. Capital charges (interest and redemption), maintenance, operating labor, and lubrication are practically constant amounts regardless of the load-output of the station; the fuel consumption and its cost are practically the only variables with the load. The costs here given are based on conditions as generally found in the Southwestern States, and on Diesel engine operating experience in European countries, where this type of prime mover has reached a high state of perfection, units upward of 4,000 hp. having proved entirely successful in operation.

Jan 1, 1917

By C. R. Ince

The term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalco-pyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggartl has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 Ib. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 Ib. per ton were added to the thickened pulp and the whole

Jan 1, 1930

By S. A. Falconer

Much attention and publicity has been given, during recent years, to grinding, classification, flotation, and thickening. The various technical papers, and symposiums held to discuss these important phases of milling, have contributed to a better understanding of the fundamental principles and operating variables involved. Another important part of milling— to the flotation operator—is a treatment step to which frequently too little attention is given—"conditioning," or the treatment the ground mineral pulp receives before it enters the flotation machines. "Conditioning" is a hackneyed and frequently misused term, commonly employed to describe the pretreatment of surfaces of minerals in ore pulps or mill products prior to froth flotation. In general, such pretreatment is for the purpose of changing the flotation characteristics of these mineral sur- faces to enable them to respond in some desired predetermined manner when subjected to flotation. Taggartl states that the function of conditioning is "either to insure selective collector coating of one mineral species while another species is not; or to take such steps as will compensate for departure therefrom." As 0. C. Ralston has stated? ... we are still faced with the fact that some mineral particles are water-avid, others air-avid, and that by properly modifying them they may be enhanced or diminished in desirable or undesirable avidity. Coatings on minerals must still be assumed to fall into three classes: (1) a coating of immiscible oil, (2) a layer of adsorbed substance, (3) a chemically produced coating. It is submitted that the process of preparing mineral surfaces for subsequent flotation treatment should take into consideration physical as well as chemical means for altering the normal flotation response of the mineral surfaces. A more descriptive word than "conditioning" is needed to designate broadly these procedures. The minerals in many ores cannot be made to respond in a normal manner to usual methods of "conditioning" with selectivity modifying reagents, until they have been cleansed, or interfering slimes and soluble salts have been removed from the ore. Therefore, it appears important to include under the general subject of "conditioning" a discussion of the purposes, methods used, and some of the advantages of these pretreatment steps. This is dealt with under the subject heading " Initial Treatment of Mineral Surfaces and Ore Pulps." Under this broader interpretation, the methods employed for treating mineral surfaces to alter their flotation characteristics may be divided into three general classes: 1. Physical methods.

Jan 1, 1950