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By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By C. R. Sandberg, C. A. Connally, N. Stein

This paper describes the results of volumetric efficiency tests on oil well pumps handling gas oil mixtures. The work was performed in a large scale, above ground unit wherein test conditions could be accurately controlled and measured. The main variables studied were gas/oil ratio (including gas from solution and free gas mixed with oil), pump compression ratio, pump stroke length, pump speed, and clearance volume between the valves at their closest approach. Results are presented for two different pumps and for oils of two viscosities. Relatively small amounts of gas entering the pump resulted in large decreases in volumetric efficiency. Under conditions where the pump was operating at reduced efficiency because of the presence of gas, it was found that variation in the clearance volume between the standing and traveling valves had a considerable effect on pump efficiency level. This effect of the valve clearance volume was found to be significantly altered by the viscosity of the oil used in the tests. The effects on pump efficiency of the other variables studied were found to be relatively small over the range of conditions utilized. INTRODUCTION The production of oil by pumping is often hampered by low volumetric efficiency. A direct increase in lifting costs results from low volumetric efficiency. An indirect increase in lifting costs, probably greater than the direct increase, results from additional wear and tear on pumping equipment and from the down-time necessary for the repairs which can be traced to low-efficiency operation. Both increases in lifting costs tend to reduce economically recoverable oil. A number of different factors can contribute to low pump efficiency. A known basic cause of low efficiency is the presence of free gas in the pumped fluid. Pump volumetric efficiency is calculated only on the basis of liquid pumped and because any free gas pumped is discounted, this volume of free gas would represent a loss of pump efficiency. However, gas also causes a reduction in pump efficiency because it is a highly compressible fluid. It is known that pumps some- times "gas lock" because of excessive gas-to-liquid ratios in the pump barrel. Little is known of the role of gas compressibility in the intermediate case where the pump is operating at low efficiency. The opinion exists, however, that oil-well pumps tend to operate at higher efficiency with long stroke lengths at low speeds, but no quantitative studies of these pumping variables have been reported. It was believed that a much better understanding of the variables which control pump volumetric efficiency could be obtained and that possibly some suggestions as to the methods for increasing efficiency might be found from a study of the operation of pumps handling gas under closely controlled conditions. Previous investigators have studied the effects on pump efficiency of such factors as oil viscosity, oil temperature, slippage of oil. past pump plungers, pump submergence, valve size and spacing, pressure above pump plunger and fluid vapor pressure. However, none of these published investigations were conducted with pumps being subjected to large amounts of gas such as might be the case in a pumping well, nor did any of the investigations study the effect of variation in stroke length or pump speed. A large-scale teat unit was therefore constructed for studying the operation of pumps handling gas and for evaluating effects of such variables as pump stroke length and pump speed. PROCEDURE AND EQUIPMENT A schematic diagram of the pump testing equipment is given in Fig. 1. A 45-ft length of 6-in. casing is mounted vertically in a 65-ft tower. Sight ports are mounted in the casing at intervals near the location of the pump intake and the liquid level in the casing. These sight ports are fitted with Lucite windows sealed by neoprene "0" rings. The Lucite windows are machined to conform to the I.D. of the casing so that no obstruction to flow is present along the casing wall. The casing is fitted with a tubing head and 2-in. tubing is hung inside the casing. Pumps are seated in a shoe attached to the 2-in. tubing. A 1-in. polish rod is attacked directly to the pump without any intervening sucker rods. The top of the polish rod is attached to the weight carrier, which contains a number of weights to be used to force the polish rod in against tubing pressure on the down-stroke. This is necessary because a long string of sucker

Jan 1, 1953

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1'3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies', the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,' vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell' published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson' has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By D. W. Lillie

It has been demonstrated that considerable bend ductility exists in bulk specimens of polycrystalline high-purity silicon. The possibility of hot-forming at 1200°C is suggested. EXCELLENT corrosion resistance in many media and low cross section for absorption of thermal neutrons (0.13 barn) would make silicon of interest to nuclear engineers were it not for extreme brittle-ness and the difficulty of fabrication by any reasonable means. The use of silicon for structural purposes also has been considered in view of its light weight and oxidation resistance. Johnson and Han-sen' have investigated the properties of silicon-base alloys and concluded that there was no way of making pure silicon or silicon-rich alloys ductile at room temperature. In view of reports of appreciable ductility in germanium single crystals above 550°C'." and some plastic deformation in single-crystal silicon above 900oC,' the present investigation was undertaken to define more precisely the limits of high-temperature ductility in pure silicon. After this investigation was begun torsion ductility in both germanium and silicon was reported by Greiner." Through the courtesy of F. H. Horn, a small bar of cast extra high-purity silicon was obtained and small bend specimens were made from it by careful machining and grinding. All of the reported tests results were obtained from samples from this bar (bar No. 1) and one other of similar source (bar No. 2). No complete analysis was obtained but, based on analysis of similar semi-conductor grade material, metallic impurities were under 0.01 pct total. Vacuum-fusion analysis for oxygen showed a value of 0.0018 2 0.0003 pct for the first bar tested and metallographic analysis showed no evidence of a second phase. Bend tests were carried out on an Instron tensile machine using a bend fixture with a 1 -in. span loaded at the center. Supporting and loading bars were 0.250 in. round and the load was applied by downward motion of the pulling crosshead of the machine. Specimen thickness and width were approximately 0.10 in. and % in. respectively. Loading rate was controlled by holding crosshead motion constant at 0.02 ipm. In some cases a smaller specimen was used on a 5/8-in. span with a 0.129-in.-diam loading bar. The entire bend fixture was surrounded by a hinged furnace and all heating was done in air atmosphere. Temperature measurement was made with thermocouples fastened directly to the bend fixture within less than 1 in. from the specimen. Autographic stress-strain curves were recorded during each test, and breaking load, total deflection, and plastic strain could be obtained from these curves. Stress was calculated from the beam formula S = 3PL/2bh2, where P is the load in pounds, L the span in inches, b the specimen width in inches, and h the specimen thickness in inches. This formula is strictly correct only in the elastic range but has been used to calculate a nominal stress for convenience in the plastic range. The stress given is the maximum stress in the specimen. Results The results of the complete series of tests are shown in Table I. The first group of tests (specimens Nos. 1-6) showed the beginning of plastic flow at a test temperature of 900°C, so two additional tests (Nos. 8 and 9) were made at 950°C on small-size specimens from bar No. 2. Specimen No. 8 was tested in the as-machined condition, and No. 9 was heat-treated in hydrogen at 1300°C for 2 hr, cooled to 1200°C and held 1 hr, cooled to 1000°C and held 1 hr, cooled to 900°C and held 1 hr, and finally cooled to a low temperature before removal from the hydrogen. It is apparent that the heat-treatment had a significant effect on yield strength and ductility. In addition, the magnitude of the yield point was conslderably reduced in the heat-treated specimen as is shown m Fig. 1 by tracings of the stress-strain curves. After obtaining a furnace capable of reaching higher temperatures specimens Nos. 10 to 13 were tested at 1100 and 1200°C. Strain rate was increased by up to a factor of 10 to see whether the ductility observed was excessively strain sensitive. Specimen NO. 10, strained at 0.02 ipm and 1100oC, was still bending at a deflection of 0.322 in. when the load rate was increased to 0.2 ipm, resulting in immediate

Jan 1, 1959

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By W. O. Philbrook, K. Natesan

The oxidation kinetics of spherical pellets of zinc sulfide made from Santander concentrates were studied using a thermogravimetric technique. The experiments covered a temperature range-. of 740" to 102O°C, 0-N mixtures varying from 20 to LOO pct O2, and pellet diameters between 0.4 and 1.6 cm. Mathematical models were formulated to Predict the reaction rate on the assumption that a single transport or interface reaction step was rate -controlling. Analysis of the data indicated that the process of oxidation was predominantly controlled by transport through the zinc oxide reaction-Product layer. ROASTING processes, which are reactions between solids and gases, are very important because they are employed in the production of a number of basic metals. These processes are highly complicated, and one needs to consider the transport phenomena of heat and mass between the solids and gases in addition to the kinetics of various chemical reactions involved. Because of such complications there is a lack of knowledge concerning the rate-limiting factors, which may strongly depend on temperature, particle size, gas composition, and solid structure. The oxidation of zinc sulfide, which is of commercial importance in zinc production, falls into this class of reactions. The major goal of this work was to elucidate the roles played by different process variables, such as reaction temperature, gas composition, pellet size, and pellet porosity, on the kinetics of oxidation of single pellets of zinc sulfide. Roasting of zinc sulfide single particles has been a subject of both experimental and theoretical investigations.&apos;-&apos; The reaction is exothermic and may be considered to be irreversible. Such a reaction has been found to proceed in a topochemical manner. In other words, as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,1-9 that the particle retains its original dimensions and the process requires transport of gaseous oxygen across the porous product layer for continued reaction. The reaction may be represented by ZnS(s) + 3/2 O2(g) = ZnO(s) + SO2(g) [1] The solid product considered here is only zinc oxide, since the diffraction patterns of zinc sulfide pellets oxidized partially at &apos;798" and 960°C showed K. NATESAN, Junior Member AIME, formerly St. Joseph Lead Fellow, Department of Metallurgy and Materials Science, Carnegie-Mellon University, Pittsburgh, Pa., is now at Argonne National Laboratory, Argonne, Ill. W. 0. PHILBROOK, Member AIME, is Professor of Metallurgy and Materials Science, Carnegie-Mellon University. This paper is based on a them submitted by K. NATESAN in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science at Carnegie-Mellon University. Manuscript submitted December 2, 1968. EMD lines corresponding to original zinc sulfide and the newly formed zinc oxide. OXIDATION MODEL The generalized model for gaseous oxidation of zinc sulfide is illustrated in Fig. 1. This depicts a partially oxidized sphere of zinc sulfide in a gas stream surrounded by a laminar film of gas. The spherical sample of zinc sulfide of unchanging external radius r0 is suspended in a flowing gas stream of total pressure PT and composition specified by the partial pressures of the individual components. Partial pressures of the gaseous species in the bulk gas phase, at the exterior surface of the pellet, at the ZnS/ZnO interface, and at equilibrium for Reaction [I] are identified by the superscripts b, o, i, and eq, respectively. The overall reaction involves the following ~te~s:&apos;~&apos;~&apos; Step 1. Transfer of reactant gas (oxygen) from the bulk gas stream across the gas boundary layer to the exterior surface of the pellet and the reverse transfer of the product gas (sulfur dioxide). Step 2. Diffusion and bulk flow of oxygen from the pellet surface through the product shell (ZnO) onto the ZnS/ZnO interface and the reverse transfer of sulfur dioxide. Step 3. Chemical reaction at the interface, which results in consumption of oxygen gas and generation of sulfur dioxide gas and heat; at the same time the _________ PARTICLE SURFACE / x^^^^n^X / MOVING INTERFACE core-----/ sJSNxy " /T^T^02 \ V\V$\ ^NWX/ "*/— GAS BOUNDARY x. \\ZnO SHELLV/ / \^ . / &apos; ^ BULK GAS --------N_______ _____,------p£ w \ P« / (f> \ / a \ <i) / <----------------- _(o) ^^--------------(b) °- pso, pso2 ro ri 0 ri ro RADIAL POSITION Fig. 1—Generalized model for oxidation of a sphere of zinc sulfide.

Jan 1, 1970

By J. D. Mote, J. E. Dorn

This investigation was undertaken to study the effects of piledup arrays of dislocations on inducing slip, twinning, and fracturing in magnesium bicrystals. A series of variously oriented bicrystals of magnesium having a vertical grain boundary were prepared and tested in tension. It was found that piled-up arrays of dislocations at the grain boundary could, under appropriate conditions, induce slip, twinning- and cracking. The results that were obtained substantiate, at least qualitatively, the general dislocation mechanism for transmission of strain across grain boundaries and the Petch-Stroh concept of fracturing. WHEREAS single crystals of magnesium generally exhibit extensive deformation, coarse-grained poly-crystalline magnesium at subatmospheric temperatures fractures after a few percent elongation.&apos; Although a small amount of ductility is obtained, several features of this fracturing are characteristic of typical brittle behavior. Over a rather broad temperature range the fracture stress is insensitive to the test temperature and the fracture stress increases linearly with the reciprocal of the square root of the mean grain diameter. The course of fracturing is predominantly intergranular, but small fragments of adjacent grains frequently adhere to the fractured surface.2 The brittle behavior of polycrystalline magnesium is attributable to the limited number of facile deformation mechanisms it exhibits at low temperatures. For a general deformation of a randomly oriented polycrystalline aggregate, each grain must exhibit at least five independent mechanisms of deformation to permit accommodation of the imposed deformation from grain to grain.= Although minor amounts of prismatic slip occur in corners of grains where stress concentrations are known to be high, glide in polycrystalline magnesium at low temperatures takes place almost exclusively by basal slip.&apos; The common type of twinning, which takes place on the (1012) pyramidal planes, can under the most favorable orientations, lead to a. strain of only 6.9 pet; the contribution of twinning to the tensile strain would indeed be much less than this in a randomly oriented polycrystalline aggregate of magnesium. Since the three mechanisms of basal slip are coplanar, they are equivalent to only two independent mechanisms, a number insufficient for a general deformation. Consequently, once the permissible twinning has taken place in conjunction with basal slip, no further plastic deformation is possible because of interference to slip at the boundaries of dissimilarly oriented grains. At this stage brittle fracturing takes place due to high stress concentrations at the juncture of slip bands with the grain boundaries; the predominance of intergranular fracturing in magnesium, in preference to transcrystalline fracturing which is prevalent in zinc, has not yet been rationalized. A more atomistic description of the plastic behavior and fracture characteristics of magnesium follows from the analyses made by stroh4 on the stresses induced by piledup arrays of dislocations. Slip first takes place by dislocation motion in the most favorably oriented grains. As the dislocations approach the boundary of a dissimilarly oriented adjacent grain they begin to form an array of dislocations with its attendant stress field. Piledup arrays of screw and edge dislocations introduce high localized shear stresses at the spur of the array; piledup arrays of edge dislocations also induce high tensile stresses localized in the vicinity of the grain boundary. Whereas the shear stresses can induce slip to take place, the tensile stresses, if sufficiently high, can cause fracturing. The localized shear stress will be relieved if sufficient numbers of mechanisms of deformation become operative in the original and the adjacent grain to permit accommodation of the dislocations in the grain boundary. In this event a ductile behavior will be obtained. But if the number of deformation mechanisms is insufficient for complete migration of dislocation arrays into the grain boundary, the tensile stresses due to the edge components of piledup dislocation arrays will continue to increase with increasing applied stress until fracturing takes place. Whereas face-centered-cubic metals have a sufficient number of mechanisms of slip for accommodation of dislocations in their grain boundaries to exhibit ductile behavior, hexagonal-close-packed metals, in general, do not. Consequently, hexagonal-close-packed metals are usually brittle except when conditions such as alloying or temperature permit facile slip by a number of mechanisms. The arguments presented above suggest that the mechanical behavior of magnesium depends on whether or not dislocation arrays in adjacent grains can enter the grain boundary. When such accommodation is possible, ductile behavior is expected; but when such accommodation is impossible, fracturing will ensue. To further test the validity of these arguments it was considered advisable to study the

Jan 1, 1961

By David A. Thomas, David N. French

The lrnrdness of WC crystals has been measured with the Knoop indenter at loads of 100 and 500 g on the (0001) and (1070) planes. The hardness as tneasitred on the basal plane is 2400 kg per sq mm and shows little anisotropy. The hardness on the prism plane, however, shows a marked orientation dependence, with a low value of 1000 kg -per sq mm when the long axis of the Knoop indenter is oriented parallel to the c axis and a high value of 2400 kg per sq mm when the indenter is perpendicular to the c axis. Slip lines (Ire observed surrounding the microhardness indentations and they show slip on (1010) planes, probably in [0001] and (1120) directions. This slip behavior can be explained by the crystal structure of TVC, which is simple hexagonal with a c/a ralio of 0.976. The hardness anisotropy call be explained by [0001]{1010} and (1130) {10l0] slii) and the resolved shear-stress analysis of Daniels and Dunn. HARDNESS anisotropy is a well-known phenomenon and has been reported for many metals, with both cubic and hexagonal structure.1-6 For hexagonal tungsten carbide, WC, a wide range of hardness values is reported in the literature. For example, Schwarzkopf and Kieffer7 give a hardness of 2400 kg per sq mm and report a value of 2500 kg per sq mm by Hinnüber. Foster and coworkerss give the average Knoop microhardness as 1307 kg per sq mm with a maximum value of 2105 kg per sq mm. Although these values and the structure of WC suggest the likelihood of hardness anisotropy, no such measurements have been made. We first detected a large apparent hardness anisotropy in WC crystals about 75 p large, in over-sintered cemented tungsten carbide. Prominent slip lines also occurred around many indentations. This report presents further observations and interpretations of hardness anisotropy and slip in WC crystals obtained from Kennametal, Inc. Both Knoop and diamond pyramid indenters were used on a Wilson microhardness tester with loads of 100 and 500 g. EXPERIMENTAL RESULTS The carbide crystals tended to be triangular plates parallel to the (0001) basal plane of the hexagonal structure. The side faces were parallel to the ( 1010) prism planes. Specimens were mounted approximately parallel to these two types of faces and metallographically polished. Laue back-reflection X-ray patterns were used to orient the specimens, which werethen ground to within ±1 deg of the (0001) and (1010) planes. The Knoop hardness values measured on the basal plane are plotted in Fig. 1. There is only a small anisotropy, with a hardness range of 2240 to 2510 kg per sq mm. The additional points at angles from 52.5 to 67.5 deg confirm the sharp minimum hardness at 60-deg intervals, consistent with the sixfold hexagonal symmetry. The average hardness of all values obtained on the basal plane is 2400 kg per sq mm. While the basal plane shows only slight anisotropy, the (1010) plane exhibits marked hardness anisotropy, from 1000 to 2400 kg per sq mm. Fig. 2 shows the hardness as a function of the angle between the long axis of the indenter and the hexagonal c axis, the [0001] direction. The minimum and maximum occur when the indenter is oriented parallel and perpendicular to the [0001] direction, respectively. The anisotropy of the prism plane is contrary to that reported for hexagonal zinc and hard- However, the basal-plane anisotropy is similar to these two metals.1&apos;2 To check the accuracy and reproducibility of the measurements, a series of fifteen impressions was made at 100-g load in the same orientation in the same area of the specimen surface. The average for all was 2040 kg per sq mm, with a range of 1950 to 2130 kg per sq mm, giving an accuracy of about ± 5 pct. Thus the slight anisotropy on the basal plane is almost within experimental error. Fig. 3 shows slip lines around the Knoop indentations on the basal plane. The slip traces are in directions of the type (1130). The presence of slip steps on the basal plane indicates that the slip direction lies out of the (0001) plane. Because WC has a c/a ratio of 0.976,&apos; the shortest slip vector is [0001], which suggests slip systems of the type [0001] (1010). Fig. 4 shows slip lines around the Knoop intentations on the (1010) plane. These slip lines are inconsistent with [0001] slip but can be

Jan 1, 1965

By Luc Delaey, Horace Pops

The structure and morphology of thermoelastic and burst type martensitic phases that form upon cooling in Cu-Zn-Si p phase alloys have been studied by transmission electron microscopy. The martensitic phases are composed of a lamellar mixture of two close-packed structures with different stacking sequence, namely ABCBCACAB (orthorhombic) and ABC (fcc). Striations within thermoelastic martensite are most likely produced during interaction with impinging burst-type martensite and not as a consequence of secondary shears. In a study of the martensitic transformation in ternary Cu-Zn based 0 phase alloys1 the dependence of the martensitic transformation temperature, M,, with composition shows variations for elements within a constant valence subgroup and between different subgroups. Such variations are not reflected in a change in habit plane, which is approximately the same for each ternary alloy, namely in the vicinity of (2, 11, 12 Ip. The fact that the habit plane remained constant, despite large differences in M, temperature and electron concentration, suggested2 that the crystal structures of the martensitic phases could be nearly the same. Crystal structures of ternary Cu-Zn based martensites have been determined recently for alloys containing the three-valent elements gallium3, 4 and aluminm. The present studies have been made to examine the structures and morphology of the martensitic phase in ternary Cu-Zn based alloys containing a four-valent element, silicon. I) PROCEDURE Two alloys were prepared by melting and casting weighed quantities of the component high-purity metals in sealed quartz tubes under half an atmosphere of argon. They were subsequently remelted by levitation under a protective atmosphere of argon. After allowing for losses of zinc as determined by the difference in weight before and after casting, the compositions in atomic percent of both alloys were established to be Cu-33.5 Zn-1.8 Si and Cu-27 Zn-5.0 Si. These alloys were homogenized in the P-phase field for 2 days at 800" C. Bulk samples consisted of a martensite phase at room temperature, the M, temperature being approximately 30&apos; and 200" for the 1.8 and the 5 pct Si alloys, respectively. Thin disks were cut from the ingots using a spark machine, and they were heated for 5 min at 800&apos; and quenched into water in order to obtain martensite. These slices were thinned chemically at room temperature in a solution consisting of 40 parts HN03, 50 part H3PO4, and 10 parts HC1 and thinned further electrolytically by the Window technique, using a voltage of 15 to 25 v and a mixture of 1 part HN03 and 2 parts methanol, which was kept at a temperature near -30° c. Foils were examined by transmission electron microscopy using a Philips EM 200 electron microscope. 11) RESULTS AND DISCUSSION 1) Structure and Morphology. Fig. 1 shows the martensitic phase in the alloy containing 1.8 at. pct Si. This phase is composed of contiguous platelets, each containing striations. The direction of the striations changes at the boundary between individual platelets. These internal markings resemble the striations that are usually identified as stacking faults, as for example in Cu-A1 martensites6-a or the lamellar mixture of two close-packed phases in Cu-Zn-Ga marten-sites.3p &apos;9 lo In the present alloys, selected-area diffraction experiments have been obtained in order to determine the nature of the striations. Figs. 2(a), (61, and (c) are electron diffraction patterns of an area inside a single martensite plate. Fig. 2(a) contains diffraction spots which correspond to two close-packed structures with different stacking sequences, namely ABCBCACAB (orthorhombic) and ABC (fcc). Spots belonging only to the fcc structure are indicated by arrows. By tilting the foil either the orthorhombic structure, Fig. 2(b), or the cubic structure shown in Fig. 2(c) may be obtained. When the foil is oriented so that only the diffraction spots of the orthorhornbic structure are present, bright-field illumination shows small lamellae, as seen in Fig. 3. In this figure the lamellae that belong to the fcc structure are bright bands inside the dark extinction contours of the orthorhombic structure. The boundaries of the lamellae are parallel to the basal planes of the orthorhombic structure and to the {Ill} planes of the cubic structure, the close-packed directions of both structures being parallel. The 5 pct Si alloy shows similar features as those described for the 1.8 at. pct Si alloy.

Jan 1, 1969

By J. H. Moran, E. E. Finklea

The pressure build-up technique is a recognized method of determining permeability from conventional drillstem tests. In this paper an effort is made to extend such techniques to the interpretation of data obtained from the wireline formation tester. Such a study is necessary because of the differences, for this case, in the magnitude of the flow parameters (rate of flow, amount of recovered fluids) and in the flow geometry (flow through a perforation vs flow across the face of the wellbore, etc.) involved in the solution of the equations of flow for compressible fluids. The perforation is replaced by a spherical hole, and the effect of the borehole is neglected, so that the flow can be considered to be radial in a spherical co-ordinate system. Arguments are presented to justify this idealization. Assuming single-phase flow, general relations between pressure and flow rate are developed for a homogeneous medium. The study is then extended to permeable beds of finite thickness. It is shown that the early stages of pressure build-up tend towards spherical flow, while the later stages tend towards cylindrical flow. The thinner the bed, the more quickly flow approaches the cylindrical model. The prevalence of thin beds in practical work makes this analysis quite important. Cases involving permeability anisotropy are treated. INTRODUCTION From wireline formation tester operation, two types of data are obtained: (1) the nature and amount of recovered fluids, and (2) the pressure history recorded during the test. A number of papers have been written dealing with the interpretation of formation production on the basis of the recovered fluids.&apos;.&apos; In general, the methods described have been quite accurate for both high- and low-permeability formations. The present paper will deal with an analysis of the pressures observed. An analysis of the pressure build-up curves obtained in hard-rock country has already been attempted on the basis of the formula proposed by Hor-ner. Although this approach has met with success in many instances, some questions have been raised as to its validity. It is the aim of the present study to place the analysis of pressure build-up in the formation tester on a firmer basis, from which more detailed methods of interpretation can evolve. Because of the great differences between the operation of the wireline formation tester and the conventional drillstem test, modifications are necessary in the interpretation. The major difference relates to the flow geometry. Once the flow geometry has been established other features such as multiphase flow, skin effect, afterflow, etc., well described in the literature, can be introduced. It will be assumed that the mechanical operation of the formation tester is already known to the reader.6 t will suffice here merely to state that the tester provides the means for taking a relatively small sample of the fluid immediately adjacent to the borehole, and for recording the subsequent pressure response. In comparison with conventional drillstem tests, the time required for a satisfactory pressure build-up response is much shorter, because of the relatively small quantity of fluid withdrawn by the wireline tester. This feature is highly desirable in the case of low-permeability formations. For an analysis of the pressure response within the formation, three simple flow geometries are considered— linear, cylindrical and spherical. The spherical and cylindrical flow geometries are most pertinent to the formation tester; therefore, they will receive the major emphasis. Since the configuration of the borehole and the perforation made by the tester complicate the flow geometry, it is necessary to allow for them in the drawdown response. However, because of the volume of formations contributing to the pressure-response, the details of the perforation shape are unimportant in the build-up period. Since relatively small amounts of fluid are withdrawn from the formation, in contrast to a conventional drill-stem test, a study of the "depth of investigation" and the significance of drawdown as well as build-up data will be included. Because the "depth of investigation" will be shown to be rather large, the effect on the build-up curves of the finite thickness of the permeable bed is considered. It is this consideration that leads to the importance of cylindrical flow geometry. Also included is a discussion of permeability anisotropy and its effect on the interpretation of the tester results. The pressure curves recorded by the formation tester will follow two general patterns, depending upon whether the formation is of high or low permeability. Fig. I (a and b) schematically illustrates these two responses. In Fig. 1(a), the high pressure recorded during fill-up of the tool is essentially the pressure differential across the choke in the system. In Fig. l(b), the flow rate is

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By E. W. Stewart, G. P. Conard, J. F. Libsch

The effects of several additives upon the reduction characteristics of hydrogen-reduced ferrous formate are described. The various additives inhibit sintering of the reduced iron particles by apparently different mechanisms. The magnetic properties of the low density compacts produced from the resulting ultra-fine iron powders were improved markedly. THE permanent magnetic characteristics of ultra-fine iron powder prepared by various means have been a subject of considerable interest and experimentation in the past few years. When such particles are small enough to show single domain behavior, they possess&apos; 1—permanent saturation magnetization, and 2—high coercive force. In the absence of domain boundaries, the only magnetization changes in a particle occur through spin rotation which is opposed by relatively large anisotropy forces. With decreasing particle size, the coercive force tends to increase to a maximum and then decrease because of the instability in magnetization associated with thermal fluctuations. Kittel&apos; has calculated the critical diameter at which a spherical particle of iron can no longer sustain domain boundaries or walls to be approximately 1.5x10-&apos; cm. Stoner and Wohlfarthr in England and Neel4,6 in France have shown from purely theoretical calculations that the high coercive force expected from single domain particles is dependent upon crystal anisotropy, shape anisotropy, or strain anisotropy contributions. Further work by Weil, Bertaut,&apos; and many others has contributed much to the understanding of fine particle theory. Neel and Meikeljohn" have demonstrated that a decrease in particle size below a critical value of approximately 160A leads to a quite rapid decrease in coercive force because of the prevention of stable magnetization by thermal agitation. Lih1, working with powders prepared by the reduction of formate and oxalate salts of iron, has shown the marked influence of powder purity upon magnetic properties. Maximum coercive force was obtained in powders of approximately 65 pct metallic iron content while the maximum energy product, (BxH) occurred in powders of 85 pct metallic iron content. Careful consideration of the preceding theoretical considerations and experimental results has led to the manufacture of permanent magnets from ultra-fine ferromagnetic powders by powder metallurgy techniques. Such work has been done by Dean and Davis," the Ugine Co. of France, and Kopelman." The aforementioned work of Kopelman and the Ugine Co. was concerned somewhat with the effect of various additives upon the properties of hydrogen-reduced ferrous formate. Virtually no work, however, has been published on the effects of additives on the reduction rates of metal formates, although unpublished work by Ananthanarayanan16 howed promise of improved energy product in ultra-fine iron compacts prepared by the hydrogen reduction of a coprecipitated mixture of magnesium and ferrous formate. After consideration of the preceding information, it was hoped that a better balance between the metallic iron content and particle size of the reduced iron powder could be accomplished by a prevention of the attendant sintering of the partially reduced iron powder during the reduction reaction. It appeared possible that magnesium oxide might interpose a mechanical barrier between adjacent iron particles and prevent their sintering together, while metallic cadmium and metallic tin would interpose a liquid barrier which might accomplish the same purpose. The degree to which these materials were effective in accomplishing the foregoing objective and the experimental details associated with the work are reported in the following sections of this paper. Experimental Procedure Preparation of Formate and Oxide Mixtures: To obtain ferrous formate of reproducible reduction characteristics, a slight modification&apos; was made in the technique of Fraioli and Rhoda." A supersaturated solution of ferrous formate was mixed with an equal volume of 95 pct ethyl alcohol and the formate crystals precipitated by stirring and screened to —325 mesh. These crystals were in the shape of elongated hexagons, approximately 4x10 micron in dimension. Various preparations of such ferrous formate, designated as lot 111, were reduced for 2 hr, yielding ultra-fine iron particles of exceedingly reproducible size, metallic iron content, and magnetic properties. The magnesium and cadmium formates were prepared by the reaction of dilute formic acid with their respective carbonates, while the tin formate was prepared by the reaction of dilute formic acid with stannous hydroxide. To evaluate the effect of metallic formate additives in intimate mixture with the ferrous formate, varying amounts of magnesium, cadmium, and tin formates were coprecipitated with the latter. The designations of these materials and their chemical compositions are given in Table I. Due to the differing solubilities of the various formates in aqueous media,

Jan 1, 1956

By A. M. Johnson, M. M. Singh

The mechanism of failure under a drill bit is still improperly understood in spite of several investigations of the subject. Generally, the cratering process under static loading conditions is considered to be similar to that achieved dynamically by impact. This paper attempts to indicate that, although the sequence of fracturing in the two cases appear to be identical, at least some dissimilarities exist. For example, the width-to-depth ratios of the craters vary to some extent, and the amount of energy consumed per unit of volume of craters is unequal for the two different loading conditions. Prevalent rock penetration processes are dominated by methods utilizing mechanical attack on rock. It is, therefore, generally accepted that a better comprehension of the mechanism of rock failure under a wedge would prove beneficial towards improving present drilling techniques. Several attempts have been made in recent years to explain how craters are formed under a drill bit, but the mechanism of failure beneath a bit is still improperly understood. 1-11 Most investigators, to date, have inferred the sequence of events occurring during crater formation from analyses of force-time diagrams,1"6 from theoretical considerations,7 or from a study of the configurations of final craters.8-l0 These analyses have led to the presentation of widely divergent models for rock failure beneath a drill bit, ranging from brittle to viscoelastic. The cratering process under dynamic loading commonly is regarded as being similar to that obtained under gradually applied, or &apos;static&apos;, loads. But the effect of rate of loading on the action of a bit is still disputed. Some investigators11-12 maintain that there should be no such effects, whereas others have demonstrated experimentally that these exist.13-17&apos; The purpose of the investigation reported in this paper was to examine petrographically the damage done to rock under the action of a chisel-shaped wedge, both with &apos;static&apos; and dynamic loading, and to determine if rate-of-loading effects could be detected. Significant quantitative differences in crater volumes and depths were found to exist for a given consumption of energy. On the basis of this data, an attempt was made to indicate some of the rheological properties that a proposed model should possess. All the work reported herein was conducted at atmospheric pressures. EXPERIMENTAL APPARATUS AND PROCEDURE Two types of rocks were employed for most of the experiments reported in this paper, viz. Bedford (Indiana) limestone and Vermont marble. The mechanical properties of these rocks are given in Appendix A. Actually two types of Vermont marble were used, but since no marked difference could be discerned between the two varieties (as seen in Fig. 10) the data was used collectively for the analysis. Stronger rocks were not employed owing to difficulty in generation of observable craters without damage to the equipment. Six-in. diam cores were drilled from the rock samples and embedded in 8-in, diam steel pipe with 3/8-in. wall thickness, using hydrostone to fill the annulus between the core and the pipe. This procedure was adopted to confine the rock specimen so that fractures would not propagate to the edges of the cores. This goal was achieved satisfactorily for these tests because no cracks were observed to extend into the medium surrounding the rock, even when craters were formed only 1 in. from the rock core periphery. Three to four craters were formed on a core face, because the rock damage from any one crater generally did not appear to extend into the others. Whenever, interference between damaged areas around adjacent craters was suspected, the data was rejected for purposes of the analysis. The limestone and marble samples were tested with a 60-degree, wedge-shaped bit, 1 5/8-in. in length, made of tool steel. The bit shank had two SR-4 type electrical resistance strain gages, mounted axially, to record the force-time history during the loading operation. The static indentation tests were conducted using a 50-ton capacity press fitted with an adapter for drill bit attachment. See Fig. 1. The force exerted by the bit at any instant was measured with strain gages affixed to the bit shank. An aluminum cantilever, with two SR-4 strain gages mounted near its clamped end, was employed to measure bit displacement. Both sets of gages were included in Wheatstone bridge circuits,

Jan 1, 1968

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965