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By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.' These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,' a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever's4 work on iron. Barnett's7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965

By A. Yoshikawa, T. Sugeno

To detenmine the origin of the sharp fatigue limit in many ferrous metals, S-N curvces were determined in push-pull fatigue at 18.6 kc per sec at room temperature and - 67°C for various kinds of iron. These differed in carbon and nitrogen content and grain size (25 and 2500 grains per sq mm). Sharp knees appeared in the S-N curves of fine-grained specimens with high interstitial content at both temperatures. In coarse-gruined specimens, knees were not sharp .regardless of the interstitial content and the testing temperature. It is concluded from these results that the controlling factov for the appeavance of the sharp fatigue limit is not strain aging but grain size. It has already been mentioned that iron and some iron alloys show fatigue curves characterized by a more or less sharp knee and a fatigue limit.' Explanations of the origin of this characteristic behavior of fatigue in iron appear to fall into two broad classes. One is concerned with interstitial impurities through the aging or locking effect and the other is based on intrinsic plastic properties of iron. Levy and sinclair2 and Lipsit and Horne3 have suggested that the fatigue limit observed generally in iron and steel is due to interstitial solute aging during the course of fatigue. On the other hand, Thompson and wadsworthl have suggested that the fatigue limit may be analogous to the sharp yield point, in the sense that alternating stresses above the fatigue limit are necessary to break down the dislocation locking. However, there are some experimental results which cast doubt on the general validity of these suppositions.4-8 Ferro and Montalenti' have recently suggested that the typical form of the fatigue curve of iron seems to come from an intrinsic plastic characteristic of the iron structure. This suggestion is based on the experimental result that pure iron containing an insufficient amount of interstitial solute to alldw appreciable strain-aging effects still showed a fatigue limit at room temperature. Although systematic investigations on the effect of grain size are scarce, it is thought that this effect is important in relation to the sharp fatigue limit. In fact, sensible differences were observed by Oates and Wilson4 in fatigue behaviors of a low-carbon steel depending on grain size. Ideally, the fatigue limit will be defined as the upper limit of stress amplitudes at which the life is infinite. This ideal fatigue limit can never be determined because of the limited time available for experiments, and moreover scattered data points often leave the construction of S-N curves somewhat arbitrary. And, it is usually stated that a material has a fatigue limit when its statistical S-N curve becomes apparently parallel to the N axis with a more or less sharp knee. The meaning of the fatigue limit and the sharp knee will be discussed in detail in relation to the construction of S-N curves. The origin of this sharp knee was investigated by determining S-N curves of iron for various interstitial contents, testing temperatures, and grain sizes. EXPERTMENTAL PROCEDURE The material as received was a commercial-grade low-carbon steel in the form of 4-mm-diameter rods with the following composition in weight percent: C, 0.09; Si, 0.017; Mn, 0.43; P, 0.006; S, 0.012; Cu, 0.11. Five different groups of specimens were tested. The grain sizes and interstitial contents in each group are given in Table I. The specimens of group C-02 were decarburized by annealing for 100 hr at 700°C, followed by an additional 100 hr at 850°C in wet hydrogen. Specimens of groups N-2 and N-9 nitrided in a mixed atmosphere of ammonia and hydrogen after an initial treatment identical to group C-02. The specimens of group C-9 were prepared in a manner similar to those of group C-02, except heat treatment was carried out in a vacuum. After polishing their surface with emery paper, the specimens of all groups were given a final anneal for 30 min at 930°C and air-cooled in an evacuated quartz tube. For group C*-9 this

Jan 1, 1965

Edwin H. MessiteR, New Pork City (communication to the Secretary*):—Under the heading " Flues," Mr. Edwards refers to the Bee-hive construction, a cross-section of which is shown in Fig. 4 of his paper. A flue similar to this was designed by me about six years ago,' in which the walls though much thinner than those described by Mr. Edwards gave entire satisfaction. These walls, from 2.25 in. thick throughout in the smaller flues, to 3.25 in. in the larger, were built by plastering the cement mortar on expanded-metal lath without the use of any forms, or cribs, whatever, at a cost of labor generally less then $1 per sq. yd. of wall. Of course, where plasterers cannot be obtained on reasonable terms, the cement can be molded between wooden forms, though it is difficult to see how it can be done with an interior core only as stated by Mr. Edwards. In regard to the effect of sulphur dioxide and furnace-gases on the cement, I have found that, in certain cases, this is a matter which must be given very careful attention. Where there is sufficient heat to prevent the existence of condensed moisture inside of the flue, there is apparently no action whatever on the cement, but if the concrete is wet, it is rapidly affected by these gases. At points near the furnaces there is generally sufficient heat not only to prevent internal condensation of the aqueous vapor always present in the gases, but also to evaporate water from rain or snow falling on the outside of the flue. Further along, a point is reached where rain-water will percolate through minute cracks caused by expansion and contraction, and reach the interior, even though internal condensation does not occur there in dry weather. From this point to the end of the flue the roof must be coated on the outside with asphalt paint or other impervious material. In very long flues a point may be reached where moisture will condense on the inside of the malls in cold weather. From this point to

Jan 1, 1905

By John Chapman, J. C. Vaughan

Although a considerable amount of practical importance attaches to systems involving gases and molten metals, little is known regarding the effects of alloy elements upon the solubility of gases in liquid iron. The solubilities of hydrogen1 and nitrogen2,3 in pure liquid iron arc known and it has been shown that small amounts of silicon and aluminum3 exert only a small effect upon the solubility of nitrogen but greatly increase its rate of solution. This paper presents the results of a study of the solubility of nitrogen, at pressures approximately one atmosphere, in molten iron containing up to 15.8 per cent silicon. EXPEBIMENTAL METHOD There are two general methods by which the solubility of a gas in a molten metal may be determined. In the first, which Sievertsl employed, the gas is measured from a burette into the enclosure containing the metal and the amount absorbed is found by subtracting from the total volume that of the dead space in the container. The second method, which was used successfully for pure liquid iron, is to expose the molten metal to the gas until absorption ceases, then to solidify and analyze the metal. In either method the stirring produced by inductive heating prevents the development of a stagnant layer at the metal surface and ensures actual attainment of equilibrium. Obviously the second method is accurate only when the saturated metal is capable of solidifying without gas evolution. Since the rate of solution of nitrogen in iron is increased by the presence of silicon, it was to be expected that the rate of evolution would be correspondingly increased and for this reason the first method was selected. A sketch of the furnace is shown in Fig. 1. A small high-frequency coil having 17 turns fitted closely around a fused silica tube, 2 in. in diameter, in which was placed, on a bed of 60-mesh alumina sand, an

Jan 1, 1940

By Neil Johnson

IN the cyanidation of gold, silver and mixed ores, the solids suspended in the pulp after fine grinding, primary settling and series agitation are subjected to a washing step known, generally, as countercurrent decanta-tion, abbreviated C.C.D. The conventional C.C.D. plant consists of a series of separate thickeners-three to five in number-arranged in series on slightly different elevations. Solids settled in the first thickener are pumped at maximum density into the second thickener, where they are diluted with weak solution overflowing the third. After settling in the second thickener they are pumped to the third, where the process of repulping with still weaker solution is repeated, and so on throughout the system, until they reach the last thickener and are repulped with barren solution or water. Recently there has been developed a new type of thickener, known as the Dorr Washing Tray Thickener, consisting of up to five individual thickeners, which performs in a single unit all the functions of a conven-tional C.C.D. plant. Fig. 1 illustrates the essential features. It is a multicompartment tray thickener, in which the trays operate in series instead of in parallel for countercurrent washing. Feed enters the top compartment via a central, semisubmerged feed well. Strong solution overflows into a peripheral launder. Solids settle to the bottom, are raked to the center and flow into the top of the second compartment, directly below, via an inverted cup and seal. Solids pass downward, compartment by compartment, against a counter flow of wash solution and finally of fresh water. Thus, in accord-ance with the basic C.C.D. principle, the solids transfer the dissolved metal content to the wash solution and finally are removed by a dia-phragm pump from the bottom compartment virtually free of valuable material. Similarly, the wash water, as it flows through the system, becomes increasingly enriched in dissolved metal until it overflows from compartment two and returns to the process.

Jan 1, 1939

By J. C. Vaughan, John Chapman

Although a considerable amount of practical importance attaches to systems involving gases and molten metals, little is known regarding the effects of alloy elements upon the solubility of gases in liquid iron. The solubilities of hydrogen1 and nitrogen2,3 in pure liquid iron arc known and it has been shown that small amounts of silicon and aluminum3 exert only a small effect upon the solubility of nitrogen but greatly increase its rate of solution. This paper presents the results of a study of the solubility of nitrogen, at pressures approximately one atmosphere, in molten iron containing up to 15.8 per cent silicon. EXPEBIMENTAL METHOD There are two general methods by which the solubility of a gas in a molten metal may be determined. In the first, which Sievertsl employed, the gas is measured from a burette into the enclosure containing the metal and the amount absorbed is found by subtracting from the total volume that of the dead space in the container. The second method, which was used successfully for pure liquid iron, is to expose the molten metal to the gas until absorption ceases, then to solidify and analyze the metal. In either method the stirring produced by inductive heating prevents the development of a stagnant layer at the metal surface and ensures actual attainment of equilibrium. Obviously the second method is accurate only when the saturated metal is capable of solidifying without gas evolution. Since the rate of solution of nitrogen in iron is increased by the presence of silicon, it was to be expected that the rate of evolution would be correspondingly increased and for this reason the first method was selected. A sketch of the furnace is shown in Fig. 1. A small high-frequency coil having 17 turns fitted closely around a fused silica tube, 2 in. in diameter, in which was placed, on a bed of 60-mesh alumina sand, an

Jan 1, 1940

By J. H. Nead

The subject of this paper is one to which there are many references in the literature on the manufacture of steel in the open-hearth furnace, but few actual experimental data have been published. For that reason, the presentation of results obtained from two open-hearth heats where attempts were made to measure the sulfur absorption will be of considerable interest and value. The two heats on which the experiments were made were Armco ingot-iron heats and differ from the usual open-hearth heat of medium- or mild-carbon steel in that the refining is carried further; in this product the carbon and manganese are reduced practically to traces. In most other respects, and especially in respect to the absorption of sulfur from the producer gas, the two heats are typical of usual open-hearth practice. The object of the experiments made on the first Armco iron heat was to determine the fluctuation of the composition of the metal bath and the slag throughout the course of the heat, with especial reference to the variations in sulfur. It was hoped to determine whether there was an increase in sulfur in the bath from the producer gas and if so at what stage in the process the increase occurred. The experimental method consisted of charging analyzed scrap and pig iron, so that the sulfur in the charge could be calculated. Then, throughout the duration of the heat, metal and slag samples were takcn every half hour, beginning as soon as there was enough molten metal to take a sample. These samples were analyzed; the results are given in Table 1. All domestic scrap was used and the charge was made up as follows: Head End Finish Pounds Pound Pig iron........................ 36,300 Pig iron....................... 23,900 Sheet scrap bundles............. 36,200 Sheet bars..................... 23,900 Sheet bm..................... 40;200 The total charge, exclusive of the re-pig added near the end of the heat, was 160,500 Ib. The limestone charged was 21,400 Ib., or 13½ per cent.

Jan 1, 1924

By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By H. P. Greenwald

THE rapidly increasing use in coal mines of portable auxiliary fans, which are generally "blowers" employed in connection with canvas tubing, raises questions concerning the hazards of such equipment, especially where the practices are opposed to established methods of ventilating face workings. Half a dozen or more coal-mine explosions and some fires have been attributed to the use of auxiliary fans; moreover, competent mining engineers have found many dangerous installations and methods of use-for example, intermittent running of the fans in gassy mines with consequent accumulations of firedamp at the faces. These facts have led the U. S. Bureau of Mines to issue this recommendation: "In the interest of safety, the Bureau of Mines, Department of Commerce, recommends that auxiliary fans or blowers should not be used in coal mines as a substitute for methods of regular and continuous coursing of the air to every face in the mine." The comparatively recent introduction of new types of mining machines, mechanical loaders, face conveyors, and slabbing machines has encouraged the trial of new systems of face mining, all of which have for their object the rapid advance of the faces. Although the latter has certain economic advantages, in gassy mines the rate at which gas is given off is generally found to increase in proportion to the speed of advance into new territory, which in turn increases the difficulties of efficient ventilation of the face workings. Some of the systems of advance mining being tried in connection with new mechanizing methods practically compel the use of blower fans and tubing, as single narrow places are now driven, 300 ft. or more without crosscuts. In some instances a series of parallel headings are driven without crosscuts pre-

Jan 1, 1928

By W. J. Uren, Charles R. Kuzell

The industries engaged in winning minerals from the earth, because of their widespread dissemination, are faced with perhaps as wide a variety of labor-management problems as may be found in any other broad sphere of productive activity. Those problems are continually increasing in volume and complexity, and management has become aware of their growing importance. For the past quarter century at least, labor-management problems have largely been union-management problems. During this period tremendous assistance has been given labor unions through legislation and administrative and political action. In the United States, legislation favorable to unions has come about in the form of the now defunct National Industrial Recovery Act; the Wagner Act, most of which has been carried forward in the Taft-Hartley Act and the Landrum-Griffin Act; the Norris-La Guardia Act, the Wage and Hour Law, the Walsh-Healey Act, and others. The result has been to transfer from the hands of management to those who direct the affairs of the unions a large share of control over the industry and to hamper in many ways the remaining control left to management. In the United States there are many examples of the power of unions to injure whole industries seriously without regard to the interests of management, the employes, or the public. During 1958 and 1959 revelations of corruption and coercion in labor unions made before the McClellan Committee of the U. S. Senate generated considerable public sentiment in favor of legislation to protect the interests of employes and the public. However, the resulting legislation, the Labor-Management Reporting and Disclosure Act of 1959 (Landrum-Griffin Act), demonstrated quite clearly that the political power of the labor union leaders was adequate to prevent adoption of effective measures in this field.

Jan 1, 1964

By H. N. Kalia, J. B. Gresham

Several attempts have been made in the past 60 years to commercialize the vast oil shale deposits of the US. However, the industry has yet to become economically viable. To date, it has not been possible to produce oil from oil shales at a competitive price compared with oil produced by conventional methods. The development work, nevertheless, has been fruitful in furthering the art of thick bed mining and technology of in situ retorting. The in situ method has the potential of recovering oil from thick beds, and the resource recovery potential is much greater than that from underground mining and surface retorting. In situ methods require that the shales/marlstones be fragmented in place to induce adequate porosity and permeability to allow in situ heating of the fragmented shales. This can be accomplished by using explosives. However, it has been found that the existing blasting systems, though very efficient, have some drawbacks. The explosives become insensitive when shot in multiplevertical decks. They can also become insensitive when spaced horizontally at close proximity to other charges. Also, since the blasting is done in a very limited free face, the delay time that can be allowed between charges is also quite limited. Consequently, it is not always possible to routinely predict the performance of the blasting system. Furthermore, since it is not possible to undertake secondary blasting, it is imperative that the blast design function properly. Recent successful retorting by Occidental Petroleum Co. Of Retorts 7 and 8 suggests that some of these problems may have been overcome. This paper addresses some aspects of in situ retorting and problems that have impeded the development of a viable oil shale industry in the US.

Jan 1, 1986

By C. G. McLachlan

THIS paper outlines a series of tests carried out during the first six months of 1927, in the laboratory and mill of the Moctezuma Copper Co. The object of the tests was to determine whether the soluble salts present in the mill circuit water were having a detrimental effect on the recovery made by flotation. To accomplish this object a series of water analyses were made, followed by flotation experiments in which definite quantities of the salts found were added as addition agents. Before proceeding to describe the results obtained in the course of the investigation, reference will be made to five articles that have appeared during the last two years in which the action of such salts is discussed. Two of these are by A. T. Tye1,2 and describe flotation practice at Cananea and the way in which water high in ferrous and ferric salts is conditioned for differential flotation. Two, one by A. C. Munro and H. A. Pearse3 and the other by H. A. Pearse,4 outline Britannia milling methods, and the advantages that have been derived from ore washing; while in the fifth, A. W. Hahn5 summarizes the results of laboratory experiments in which ferrous, ferric and aluminum sulfates have been added in varying amounts. The mill of the Moctezuma Copper Co. has a daily capacity of 3000 tons, and is situated about 75 miles south of Douglas, Arizona, on the Rio de Nacozari, in the Mexican state of Sonora. The ore treated is mined from the company's mine at Pilares, about 5 miles southeast of the Concentrator. This ore contains about 2.5 per. cent. copper -- present almost entirely as chalcopyrite-and 10 per cent. iron, of which

Jan 1, 1928

By C. H. Li, J. Washburn, E. R. Parker

Yield stress in single crystals of zinc was shown to be dependent on prior annealing temperature and rate of cooling after annealing. Rate of strain hardening beyond the yield was not sensitive to annealing procedure. A tentative mechanism for the effect was discussed. COMPARATIVE mechanical tests of metal single crystals generally show a large scatter of results. Many factors may contribute to this variation. The present investigation was undertaken to evaluate the influence of two factors not ordinarily considered of major importance—annealing temperature and cooling rate after annealing. Since plastic properties of crystals are thought to depend on the presence of lattice imperfections, it follows that a variation in properties should result from differences in the distribution and density of these imperfections. Furthermore, in the light of current theories of interaction between edge dislocations and lattice vacancies,' it seems possible that annealing temperature and subsequent rate of cooling might play a part in this distribution. Analysis of the effect of these variables on plastic properties may lead to a better understanding of the annealed state. Single crystals of zinc which have been strained in simple shear undergo complete recovery of mechanical properties upon subsequent annealing. This behavior is useful because a single specimen can be used repeatedly, thus eliminating the uncontrollable variables introduced by the use of many crystals. The test section of the crystals used for these experiments was a cylinder 1/8 in. thick with a cross-sectional area of about 1/3 sq in. The specimens were acid-machined from spherical single crystals 1 in. in diameter in such a way that the slip plane (0001) was at right angles to the axis of the cylinder. In testing, a shear stress was applied along one of the slip directions, [2110] in the (0001) plane.' All crystals, unless otherwise noted, were grown in a helium atmosphere from molten 99.99 pct pure Horse Head Special Zinc. Fig. 1 is a family of curves obtained from one crystal. Each curve was obtained by deforming the crystal to 10 pct strain at a rate of 3 pct per min, following an anneal of 1 hr at 260°C. The strain direction was reversed every other time so that no progressive change in shape of the specimen took place during the series of tests. Since the stress-strain curve was reproducible within a fairly narrow range under the same conditions of annealing, it was then possible to determine the effect of changes in annealing conditions. A crystal was tested repeatedly as previously described but the annealing temperature and rate of cooling preceding each test were varied (Fig. 2). Two cooling rates were used, approximately 30°C per min and 3°C per min. Annealing was conducted at three temperatures, 200°, 300°, and 400°C. For a given annealing time and rate of cooling the room temperature flow stress was higher the higher the annealing temperature. The increase in flow stress was small as the annealing temperature was increased from 200° to 300°C but rose rapidly when the annealing temperature was raised from 300" to 400°C. Faster cooling from the high temperature produced an even greater strengthening of the crystal. The curves were obtained in the order indicated by the numbers. The stress level associated with a certain annealing treatment was, within the limits of scatter, always the same regardless of the

Jan 1, 1954

By P. Shahinian, R. L. Stegman, M. R. Achter

Creep strength has been determined as a function of oxygen pressure for nickel at 510" and 600°C. Creep-rupture life drops from its highest value at the ultimate vacuum of 10-7 torr to a high pressure plateau of nearly constant life which, at 600°C, commences at torr. This behavior is described in terms of a model that relates surface gas adsorption and the generation of fresh crack surfaces. In a calculation based a this model the predicted pressure beyond which the creep strength should not decrease further has been found to agree well with the observed value. The introduction of oxygen during creep in vacuum was found to cause a prompt rise of the creep rate. The magnitude of the environmental effect was much less than generally observed in fatigue and this is attributed to the diffarent crack morphologies in creep and fatigue. GASEOUS environments are known to affect creep resistance adversely1-5 but the effects have received less attention than the much larger ones in fatigue. At low temperatures it has been shown for nickel that the creep rates are faster and the rupture lives are shorter in air than in vacuum and that these environmental effects can be correlated with faster crack growth rates in the reactive environment.' In support of a mechanism of gas adsorption at the crack tip to explain the above effects, a calculation based on kinetic gas theory showed that surface coverage by gas was not as rapid as the exposure of fresh metal at the crack tip in the ultimate vacuum but was in air.7 In fatigue a number of investigations have demonstrated that the reduction of life with gas pressure usually follows a step curve with most of the reduction occurring in a transition range at intermediate pressures and little or no change at high and low pressure.8 There have been no studies, however, in which creep strength has been determined as a function of reactive gas pressure to see whether similar effects would be found. This investigation was undertaken to study the kinetics of the environmental effect in the creep of nickel. EXPERIMENTAL PROCEDURES The environmental creep apparatus was constructed to minimize many of the experimental conditions which can cause scatter in data. Dead weight loading is employed and weights are contained within the environmental chamber to eliminate bellows and the necessity for compensation for gas pressure changes. Elongation over the specimen gage length is recorded from a Riehle Model DV Controlled Environment Extensometer which provides readout to 2.5 x 10- in. Temperature is monitored and controlled from a thermocouple at- tached to the specimen gage length to +0.5oC or better. The freon trapped oil diffusion pump vacuum system included an auxiliary liquid nitrogen trap and, with a wide range variable conductance leak valve, pressures from the ultimate vacuum of 10"7 to l03 torr of any desired gas are obtainable. Pressure is measured by means of a hot filament ionization gage below 10"3 torr and a NRC Model 530 Alphatron Vacuum Gauge above 10-3 torr. The oxygen, which was leaked into the environmental chamber, was an Aviator's Grade of 99.5 pct purity with a dew point of -80°F. Analysis of the nominal 99.8 pct Ni showed the following percentages of major impurities: 0.02 C, 4.01 Mn, 0.005 Si, 0.01 Cu, 0.02 Fe, and 0.034 Mg. Cylindrical specimens were machined with a 0.180

Jan 1, 1970

By Erwin Pink

It has been pointed out in a previous publication' that, for a given strain rate, serrated yielding can be observed only at certain test temperatures. Fig. 1 shows the results obtained for polycrystalline and re-crystallized tantalum, Va group in the periodic table of elements, where serrations in the course of deformation match the decrease of total elongation. However, there was no evidence of repeated yielding when testing molybdenum or tungsten, VIa group, at similar conditions, i.e., annealed and air-cooled samples (serrations have been found in quenched tungsten2). The reason for the observed serrations in the stress-strain curve are dissolved impurities on interstitial sites of the lattice. Of importance is the concentration of oxygen, carbon, and nitrogen, which are in random solution. Two methods to calculate the limiting concentrations for serrated yielding have been evaluated and applied with more or less success in estimating the role of carbon and nitrogen in mild steel.3 J. Friedel4 has given two equations, which determine the upper and lower strain rates i for the appearance of serrations at a certain test temperature: W denotes the binding energy of the interstitial atom, -1 ev for refractory metals;5 e' the portion of continuous strain in the discontinuous stress-strain curve, measured as -3x10-3; b the Burgers vector, c the concentration, see Table 11, in atom fractions; p the dislocation density, -2 X l09 per cm2 at an average stress ?, -15 kp per mm2 at medium strain. k stands for the Boltzmann constant, T for the absolute temperature, and D for the diffusion coefficient. Table I. Eq. [1], for a given strain rate, determines the minimum temperature, and [2] the maximum temperature, below or above which no "dynamic strain-aging" can occur. According to the calculation, which uses the given quantities, serrations should only be observed within the cross-hatched temperature regions in Fig. 1, and this is in good agreement with the experiment. The effect of varying impurity concentrations is indicated schematically in Fig. 2: only Eq. [I] is affected. Setting Eq. [I] equal to [2], one can calculate the limiting concentration cmin which first causes serrations. The second method uses the aging condition by Cottrell and Bilby6,7 \£i/ \ n. a / where n(t) is the number of impurity atoms, which segregate at a dislocation line of 1 cm length after the time t (t in our case is the time between "repeated yield drops" in the serrated curve, or, the time until the above mentioned strain E' is obtained, i.e., -1 sec for medium intensity or serrations). no is the number of impurity atoms in 1 cm3 and A = Qb4ep[(1 + v)/(l - v)], derived from equations given in Ref. 7. p is the shear modulus, 18,800 kp per mm2 for tantalum, 12,200 for molybdenum, AE the tetragonal distortion caused by interstitial impurities in a bcc lattice (approximately 0.4 for both tantalum and molybdenum) and v Poisson's ratio (0.35 for tantalum, 0.30 for molybdenum). From Eq. [3], combined with the condition for a pronounced yield drop as formulated by cottrel16 (at least one impurity atom segregated at the unit length of a dislocation), again a no min, and hence the concentration Cmin can be calculated.

Jan 1, 1970

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By E. V. Manlapig, David J. Spottiswood

In recent years great advances in the automatic control of flotation plants have been made, mainly due to the development of reliable sensing instruments to monitor process performance and the development of an adequate understanding of system responses to process disturbances. Some of the control strategies used in flotation plants which apply computer control are presented here. These schemes, which involve the control of collector; depressant, frother, and air and pulp level, are analyzed with respect to their control objectives, control variables, and the instrumentation involved. The knowledge gained in understanding these strategies may be applied in the dew and implementation of control system in other concentrators.

Jan 1, 1981