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By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By R. A. Swalin, L. A. Neimark

The research work presented in this paper had initially a two-fold goal. First, further data concerning the low-temperature recovery of cold work was desired. Recovery phenomena have been extensively studied in face-centered-cubic metals but at the time of initiation of this research, no investigation concerning the low-temperature recovery in body-centered-cubic metals had been made. During the course of the investigation a paper by Martin on the recovery of point defects in molybdenum appeared.&apos; Comparison of our results on tungsten with Martin&apos;s results on molybdenum will be made. Secondly, knowledge concerning the influence of a particular type of impurity addition on the recovery kinetics was desired. It has been known for a long time that extremely small amounts of certain impurity additions exert a profound influence on the recrystallization behavior and the resulting microstructure of tungsten. Small amounts of potassium silicate and aluminum chloride added prior to the reduction of tungsten oxide to the metal have been found by Smithells to raise the recrystallization temperature markedly,2 and yield an ultimate microstructure in which grains several millimeters long are produced in fine wires of say 10 mil diam. If the impurities are added singly, ordinary secondary recrystallization results with none of the spectacular properties of the wire to which special additions were made. Swalin and Geisler3 and Rieck4 have studied the recrystallization behavior of such doped wire in some detail. The former workers found that small amounts of these impurities raised the recrystallization temperature over 400°C and electron microscopic examination revealed no obvious inclusions in the microstructures. In fact. chemical analysis showed that there was <0.001 pct K, <0.002 pct Al, trace of Si, and <0.0003 pct 0 in the wire studied. The possibility that the role of the special impurities is to keep the structure open by void formation and that submicroscopic porosity acts as the inhibiting agent has been discussed.2&apos;3 Meijering and Rieck5 have suggested that the impurities are strung out as second-phase particles in a direction parallel to the drawing direction. It was thought that a kinetic study of recovery could perhaps elucidate the role of the impurities to some extent. When a metal is deformed by cold work three basic types of defects are thought to be introduced into the crystal lattice, namely, interstitials, vacancies, and dislocations. Van Bueren6 has proposed that recovery of cold-worked metal is a four-stage process, each step being the result of the annealing of a primary defect or a combination of defects and having a unique activation energy. The steps in order of increasing activation energy are attributed to a) the diffusion of interstitials recombining with vacancies, b) diffusion of vacancy pairs, c) the diffusion of single vacancies, and d) climb of dislocations. In metals with relatively low- or medium-range melting points the temperatures for recovery are low enough so that the first three steps may occur during room-temperature deformation. For tungsten, because of the high melting point and subsequently high recovery temperature, it was calculated, using Nowick&apos;s approach7 that this recovery would occur in the temperature range 200" to 600°C. It is also known that recovery of X-ray line broadening, presumably due to dislocation climb, occurs at about 600°C.8 EXPERIMENTAL METHOD Two types of cold-rolled 10-mil-diam tungsten wire were used in the investigation; a) pure tungsten, (called undoped) and b) G. E. No. 218 wire (called

Jan 1, 1961

By J. Phillip Neal, Kefton H. Teague, Carroll P. Rogers

Feldspars, the most abundant minerals of the igneous rocks, occur in numerous forms and mixtures. The feldspars of commercial significance are found in widely distributed pegmatites as large crystals usually free of iron-bearing impurities and thus suitable for hand-cobbing, and also in larger bodies where the ore contains various types of feldspar intermingled with quartz and relatively free of iron-bearing impurities, or at least readily unlocked from impurities present at relatively coarse mesh. The latter type of ore includes some pegmatites, and the "alaskite" bodies so common in the Spruce Pine district of North Carolina. On the west coast of the US and in Oklahoma there is-or has been-commercial recovery of natural feldspathic sand as a source of alumina in glass and ceramics. "Aplite" in commercial terminology is a light-colored igneous rock with a granitic composition and a fine sugary texture, often banded with readily removable iron impurities. Only one area in Virginia produces aplite for the glass industry; it is located near Montpelier in Hanover County. According to Deer et al. (1966) the word feldspar derives from the Swedish feldt or jolt (field) and "spath:" chunks of rock appearing in tilled ground overlying granite. Castle and Gillson (1960) indicate a Germanic origin, citing "spat," which is said to refer to any transparent or translucent material which is readily cleavable. The term "spar" has in the past been applied to minerals other than feldspar, such as barite, calcite, and fluorite. It is correct to call the latter "fluorspar." There is a true barium feldspar, but it is rare and of no present economic importance. What is recognized as feldspar or "spar" by present producers and consumers consists of three silicate minerals which, if pure, would have the formulas KA1Si3O8 (microcline or orthoclase), NaAlSi3O8 (albite), and CaAl2Si2O8 (anorthite). These are almost never found in pure form in nature, but occur together in great abundance in a three-component system. A considerable number of different combined ratios of these three exists, with the exception that isomorphism between potassium spar and calcium spar is very limited. User specifications for feldspar products are largely built around the prevalent naturally occurring ratios. Passages following will refer to "K-spar," "Naspar," or "Ca-spar." Nomenclature and Descriptive Terms Relating to both the mineralogy and the economics of feldspar are certain terms whose coverage it is useful to specify. Commercially, aplite is a feldspathic rock mined and beneficiated in one location in Virginia, in which both titanium and feldspar minerals are present-the latter now being the major, if not the only, economic product. Technically, the term aplite when applied to this rock is of questionable accuracy. But, in light of accepted commercial usage, the term will be here used to designate it. Regarding the Virginia rock, Ross (1941) is cited. Alaskite is another term requiring understanding if not precise use. A distinctive rock type customarily called by this name is found near Spruce Pine, Mitchell County, North Carolina. An important major feldspar source, it contains somewhat higher levels of plagioclase feldspar and quartz than alaskite as defined in the Glossary of Geology and Related Sciences, which states that `orthoclase, microcline, and subordinate quartz are the principal

Jan 1, 1983

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday&apos;s constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By C. R. Criss, R. J. McCormick

ThiS paper .summarizes the development and perform. ance of the Coldwater Oil field, Isabella County, Mich. Production is obtained at a depth of 3750 ft from a dolomite reservoir, which is probably both Rogers City and Dundee. There appears to be no persistent barrier to vertical fluid movement between the Rogers City and Dundee, and both formations are believed to have a common original oil-water contact. No we1ls are open to production at the level of the Dundee. The discovery of the field in 1944 was followed by the drilling of 81 producing wells and nine dry holes. By the end of 1952, the field had produced 12,763,000 bbl of oil, at which time 69 active wells were producing 3600 B/D oil and 21,000 B/D water. The reservoir has an effective natural water drive, and bottom-hole pressure has declined 75 psi from an original pressure of 1453 psi. Oil is undersaturated at reservoir conditions with a solution GOR of 512 cu ft/bbl and a saturation pressure of 1190 psi. INTRODUCTION Although the Coldwater Field is now in its ninth year of production, it ranks seventh in cumulative recovery, and second in current daily oil production in the State. Following complete development of the field in 1946, it has consistently contributed approximately 11 per cent of Michigan&apos;s daily production. Coldwater appears to have a greater pay thickness than most fields producing from the Rogers City forma- tion in the west central part of the Michigan basin. Except as influenced by the extent of closure and the thickness of the oil column, reservoir performance is believed to be representative of Rogers City fields in this part of the basin. For this reason, it is felt that the following presentation of factual data for the field will be of general interest. HISTORY AND DEVELOPMENT Discovery of the Coldwater field during Aug., 1944, followed favorable subsurface geological correlations and core tests drilled to a shallow stratigraphic marker horizon. The field is located in the west central part of the Michigan Basin in Coldwater Township (T16N-R6W), Isabella County. It is 60 miles west-northwest of Bay City, and near the geographic center of the southern peninsula of Michigan. The discovery well flowed 200 bbl of oil the first 24 hours from the Rogers City dolomite at a depth of approximately 3750 ft. Field production is principally from the Rogers City with a minor amount assumed to come from the underlying Dundee dolomite, although none of the wells are open to production at the level of the Dundee. Both the Rogers City and Dundee formations belong to the Devonian system (See Geologic Column-Fig. I.) In addition to Rogers City-Dundee oil production, sweet gas is produced from the Michigan Stray sand of the Mississippian system at a depth of 1400 ft. The gas reservoir has approximately the same areal extent as the underlying oil reservoir. Although gas production is an important feature of the Coldwater field, this report is concerned only with the oil reservoir. The productive area is approximately 3200 acres. The pool is developed on a 40 acre spacing pattern with wells drilled in the center of the north half of 40 acre tracts, except for a few off-pattern wells drilled along

Jan 1, 1955

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring&apos;s predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,&apos; who applied Eyring&apos;sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann&apos;s constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers&apos; data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By Arthur Taggart

Recent jig practice has shown such marked departures from the pronouncements of the textbooks, particularly as to particle size recovered and size range of feed, as to make it desirable to reexamine the mechanism of jig action. This paper presents the results of such a study. The general conclusions of the Paper are: I. A jig bed is a bi-functioned as well as bi-parted body. The upper layer comprises a plastic stream moving slowly in a substantially horizontal direction from feed lip to tail board. It serves to rough out tailing and light middling and to pick up heavy middling and lift it out 01 the jig box. The lower layer acts as the ultimate separating means by absorbing concentrate and rejecting heavy middling. 2. The separating function of the lower layer is performed in three definitely diflerent ways, depending upon the relative sizes of the grains presented to it and those composing it. Experimental The experimental work consisted of close and long-continued visual observations of operating beds in a plunger jig, eccentric driven, and in determinations of the settling rates of various metal spheres through a quartz bed under various conditions of operation. Falling velocities were measured by an ingenious method devised by A. 6. Dorenfeld, a student in the Mining Department at Colum- bia. Spheres of different metallic alloys, 3/8-in. diameter, were cast with a short piece of fine copper wire frozen in to Serve for suspension-A short piece of black cotton thread was looped to the top of the wire to serve as an indicator. The set-up for a test is shown in Fig. I. The thread should be boiled, if necessary, to make it freely water absorbent. The piece of clean plate glass D is supported rigidly at the proper height in a vertical position. The white scale E is similarly supported behind the glass. At the beginning of a test, D is filmed with water by holding it (best with clean rubber finger cots) under running tap water. It is then clamped in approximate position and C, already wet, is laid across it and drawn straight and vertical with the upper end at or near the top of D, and the ball A slightly above the top of the expanded bed. The water film holds the string to the glass. For a test the string is released, its upper end position noted just after the top of the ball becomes submerged, when the corresponding time is read, and thereafter simultaneous readings of position and time are taken as desired. Results of the visual studies of the bed are given at the pertinent places in the following discussion. Results of the settling tests are summarized in Figs- 2 and 3. Definitions The name bed as used herein refers to the entire mixture of solids and water filling the jig box. A layer is a stratum of a bed composed of particles of substantially the same specific gravities. A granular product is long-range when it approximates a crushed or ground product limited as to upper size only; a short-rafzge product is one closely sized. A bed is loaded when operating with continuous feed and discharge of products; it is unloaded when pulsating norma11y but neither being fed nor

Jan 1, 1943

By S. J. Rothman, J. J. Hines, D. Rokop, R. Bastar

Self-diffusion has been measured along each principal axis of mosaic-structured and relatively perfect a uvaniuln single crystals. The anisotropy reported before,&apos; D[loo] = D[001] » D[010 , has been confirmed. and is shown to represent volume diffusion. Diffusion along the dislocations in the imperfect crystals increases the measured value of D significantly without changingr either the shapes of the penetvation plots or the anisotropy. SINCE a uranium is orthorhombic, the diffusion coefficients along the principal crystallographic axes need not be equal. A previous measurement of self-diffusion in three mosaic-structured a uranium single crystals1 showed that Dil00| =D[001 >>D[010 This result was deduced from penetration plots similar to those in Fig. 1. That is, the plots for diffusion along [loo] and [001] were the straight lines expected from the solution of the diffusion equation for the boundary and initial conditions of the experiment, while the plot for diffusion along [010] was curved so that the part near X = 0 had a much steeper slope than the straight lines did. The observed anisotropy could have been due either to volume diffusion or to diffusion along the very large number of dislocations in such crystals, according to the model proposed by aart.&apos; The authors of Ref. 1 argued that the latter possibility was unlikely, but did not exclude it. To settle the question, a simultaneous measurement of self-diffusion in mosaic-structured and mosaic-free crystals was carried out. This paper reports the results, as well as a measurement of the temperature dependence of self-diffusion in a uranium. EXPERIMENTAL The single crystals of a uranium used in this experiment are listed in Table I, together with other experimental details. &apos;(Mosaic structured" here means crystals grown by solid-state phase change.3 The Laue spots from such crystals spread over about 6 deg of arc, which indicates that the density of dislocations is very large. "Perfect" crystals are ones grown by Fisher&apos;s grain-coarsening tehnique; the Laue spots from these are quite sharp,4 which shows that the dislocation density in these crystals is much lower. All of the crystals were made from high-purity uranium; a typical analysis is given in Ref. 1. The actual diffusion directions were within a few degrees of the nominal. The thin layer-sectioning method was used. The experimental techniques were similar to those described in Ref. 1, except the sectioning. Crystals Za, 2b, 2c, 4a, 4b, and 4c were sectioned on a lathe. Crystals 3a, 3b, and 3c were sectioned by grinding on glass plates, with 1 p diamond powder in butyl alcohol as the abrasive. The use of glass plates eliminated the crowning noted in Ref. 1, and the use of butyl alcohol as a lubricant simplified the chemical processing of the sections. Material from the sides of these three crystals was removed by spark machining before sectioning. The sectioning of crystals 4a and 4c was botched. A small cylinder of metal was extruded from the center of crystal 4a while turning off material from the side of the sample. Crystal 4c was misaligned by 2.1 x 10"3 cm because the dial gage jammed during the alignment. Notwithstanding these errors, useful data were still obtained from these crystals. The points

Jan 1, 1967

By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By R. H. Frazier, F. W. Boulger

THE performance of welded structures is closely associated with the ductile-to-brittle transition temperature of the steel from which they are made. A low transition temperature is desirable because it indicates that the steel is less likely to fail suddenly at low ambient temperatures. Structures such as bridges, ships, storage tanks, and pipelines are usually made from hot rolled semikilled steel. Changes in rolling practice or chemical composition appear to be the most practical methods for improving the toughness of such materials. This results from the fact that production is likely to be seriously curtailed if improvements were obtained by recourse to heat treatment or complete deoxidation. This paper discusses the effect of variations in carbon and manganese contents on the properties of semikilled steels. The transition temperature, a property to which considerable importance is attached, varies with specimen configuration, testing method, and criterion of performance. Both the Navy tear test&apos; and the keyhole Charpy test were used in the investigation. According to the terms used by Vanderbeck and Gensamer,V he tear test was used to measure a fracture transition and the Charpy test to measure a ductility transition. In either case the specimens absorb considerably less breaking energy in tests below the transition temperature than in tests above the transition temperature. Decreasing the testing temperature of notched-bar specimens seems to be equivalent in its effect to increasing the severity of loading on fabricated structures. Therefore, structures built from steels exhibiting lower transition temperatures in laboratory tests are expected to be less susceptible to sudden brittle fractures in service. Consequently, changes in composition which lowered the transition temperature of the experimental steels were judged desirable. Materials and Methods The steels for this study were made in a laboratory induction furnace and rolled to 3/4 in. plate, using a finishing temperature of 1850°F. Precautions taken to insure reproducible melting and testing practices are discussed in detail elsewhere.&apos; All tests were made on hot rolled steels. The analyses of the experimental steels are given in Table I. The list includes steels with manganese contents ranging from 0.21 to 1.46 pct, at each of five carbon levels. The phosphorus, silicon, sulphur, and nitrogen contents of the steels are reasonably constant. The tensile and notched-bar properties of the experimental steels are presented in Table 11. Both upper and lower yield points are listed, and all values are averages for duplicate specimens. Transition temperatures based on three criteria are given. The keyhole Charpy transition temperatures are the temperatures at which the energy-temperature curves based on averages of four specimens cross the 20 and 12 ft-lb levels. Both definitions of Charpy transition temperatures have been used by other investigators. Charpy tests were made at intervals of 10°F, using a pendulum with an available striking energy of 220 ft-lb and a velocity of 18.1 ft per sec. The specimens were oriented parallel to the rolling direction and notched normal to the surface of the plates. The tear test transition temperatures are based on the usual&apos; criterion of the highest temperature at which at least one of four specimens exhibits brittle behavior. The dimensions of the tear test specimens are shown in Fig. 1. The specimen is loaded eccentrically in tension, with pin and shackle fixtures, through the large holes while submerged in a liquid bath at the proper temperature. A specimen developing a fracture area with less than 50 pct shear or ductile texture is classed as brittle. Tear tests were made at intervals of 10°F.

Jan 1, 1955

By N. K. Chen, C. H. Mathewson

Single crystals of high purity aluminum of various orientations were carefully documented after plastic extension. Special attention was given to the formation of slip lines, deformation bands, and asterism. An explanation for the geometry and mechanism of formation of deformation bands is considered. WHILE the general process of plastic extension of face-centered cubic metals is well understood,&apos; the accompanying structural changes due to slip and rotation are far more complex than ordinarily assumed. In the case of stretched single crystals of aluminum, the complicated behavior is especially marked by the formation of deformation bands, as first indicated by Collins and Mathewson." Such bands were believed by them and also by others,".&apos;7 who have discussed banded structure in general, to represent one of the important modes of lattice reorientation and to be intimately connected with the recrystallization process. Yet, despite their fundamental importance to the understanding of the mechanism df both plastic deformation and recrystallization, practically no study of the crystallographic features of these bands in their relationship to the conventional slip process has been attempted. This paper describes part of an extensive investigation on the structural behavior during plastic deformation of aluminum single crystals and is especially concerned with the characteristics of deformation bands. The investigation of the subsequent re-crystallization of deformed aluminum single crystals will be discussed in a later publication. Experimental Procedure Single crystal specimens of 99.996+ pct pure aluminum, Yz in. in diam and 5 to 6 in. in length were made both by the Bridgman method5 nd by a modified temperature gradient method.&apos;* Crystals were selected in which the lineage deviation did not exceed 2"; i.e., as determined from the back-reflection Laue X-ray photograms. These crystals were radiographed to insure that no internal porosity was present. The orientations showed good coverage of the whole area of the Taylor and Elam triangle.&apos; Orientations of the crystals were obtained by the back-reflection Laue technique described by Greninger." Crystals so selected were tapered very carefully in a lathe to obtain a linear decrease in diameter from 0.500 to 0.350 in. along a gage length of 3 in. This is considered desirable because it permits a strain gradient to be introduced in a single specimen at one initial orientation. The advantages of tapered crystals for studying the development of slip lines and recrystallized grains have been pointed out by previous investigators." The cold-worked layer resulting from the machining operation was removed by alternate etching in aqua regia and careful polishing with 2/0 emery paper until undistorted Laue back-reflection spots were obtained. A homogenization treatment at 600 °C for 24 hr was then introduced to insure the removal of residual stress. Two of the crystals so prepared were also checked by use of a glancing angle technique. Using a copper target, at 30 kv and 10 microamperes, a monochromatic beam was positioned at right angles to the axis of the crystal about which it rotated. The time of exposure was 24 hr. From these X-ray photograms, it was concluded that the present method of preparation of single crystals is satisfactory. Following this procedure, the crystals were elec-trolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. Intermittent

Jan 1, 1952

By Oscar Johnson

The industry has been canvassed for information on methods of handling grinding steel at milling plants, an important subject overlooked in most descriptive articles on milling plant arrangements. The data collected are offered in this paper as a guide to designers and planners who have loading and storage problems to solve. WITH capacities of milling plants expanding from a few hundred tons per day to many thousand, replenishment of grinding media is an important phase of mill operation. Information on this aspect of milling procedure, solicited from several mining companies, is summarized here. At International Nickel&apos;s Copper Cliff concentrator the normally strenuous job of changing rods is considerably simplified by the use of the Garrow rod charging machine, Fig. 1. The overhead crane, Fig. 2, brings a bundle of rods, weighing four to a ton, to the loading platform of the machine, positioned in front of the mill. The rods roll one by one down the slight incline of the platform onto a conveyor which sends them into the mill. A modified version of the Garrow machine, Fig. 3, is used at the Federal mill of St. Joseph Lead Co. An overhead crane places the portable steel structure in position in front of the discharge end of any one of the five 9x12-ft rod mills. It then raises a bundle of about twenty 3-in. rods to the discharge platform of the charging machine. The rods are 11 ft 7 in. long and weigh about 278 lb. By tripping a lever the operator allows one rod at a time to roll onto the inclined rollers. A slight push by the operator sends the rod smoothly into the mill. The Union Miniére du Haut Katanga rod charging machine, Fig. 4, is mounted on a pair of wheels at the forward end with swiveling castors at the back for steering it to position for use or storage. Wheels are equipped with locking brakes to maintain the machine in position while it delivers rods to the mill. The device is made in two parts. The first consists of the base, which carries the supporting wheels, grooved rollers, and drive. The other part serves as the rod deck, which can carry up to six 3-in. x 12-ft rods. A short boom built integral with the base reaches through the mill trunnion and delivers the rods into the mill barrel. Three grooved guide rollers ,are provided to receive the rods from the sloping charging deck. One rod at a time is fed to the rollers and thus delivered into the mill. Two of the rollers are driven by 11/2-hp motor through a V-belt drive. The third roller is driven off the first by a single V belt in a groove below the rod groove and on the same center line. Rods are delivered to the charger by an overhead crane in bundles of three to six as needed. The power is supplied by cables plugged into power outlets, suitably located near the rod mill discharge end. The Oliver Iron Mining Co. uses a rod charger, Fig. 5, suspended from a monorail by cables. It is constructed .of structural steel and has two decks, each capable of carrying five rods of 4-in. maximum diameter. The rods ride in grooved free-turning rollers. Legs extending down from the mill end of the mechanism act as supports when the unit is ex-

Jan 1, 1955

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline&apos; and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By F. W. Luersson

High carbon, low phosphorus steel can now be made from pig iron containing 0.7 pct P or more, in a commercial sized open hearth furnace. No external heat is required for refining, and steel produced is identical with basic open hearth steel. THE classical Thomas process, which requires liquid pig iron containing over 11/2 pct P, yields a product relatively high in phosphorzs and nitrogen. Unless large quantities of recarburizers are added to the refined steel, the product is low in carbon content. Thus, the Thomas process is not well suited to American raw materials, and its product is often not acceptable according to the standards set by American industry. The shortcomings of the Thomas process have long been recognized; with the advent of low cost oxygen, studies were initiated to develop pneumatic processes which would conceivably overcome the inherent objections to Thomas steelmaking. Several such modified basic pneumatic processes have been tested experimentally in commercial trials during the past decade. Probably the most widely publicized of these developments has been the oxygen converter process as practiced in Austrial,2 and in Canada.8 n this process, oxygen is substituted for air and introduced above the liquid bath in order to increase the heat available to the metallurgical system. This avoids the need for high phosphorus raw materials and gives a product low in nitrogen. In this process, the phosphorus content in the final product depends, to a considerable extent, on the total amount of that element in the burden. The rotary furnace4 which is now in commercial operation at Domnarvet Steelworks, Sweden, is producing low phosphorus steel from iron containing 1.8 to 2 pct P. One or more early slags are removed and by this means high carbon steels of open hearth quality can be produced. At this stage of development there is some question as to the applicability of the rotary process to large heats. Another development has been the use of oxygen in combination with either steam6 or carbon dioxide yn the basic bessemer, thus avoiding the introduction of nitrogen gas into the refining system and giving a product relatively low in nitrogen content. A double slag process has been used in Europe7 in conjunction with a regular Thomas converter, by means of which it is possible to obtain a phosphorus content in the product approaching that obtained in basic open hearth steels. The Turbo-Hearth process:&apos; which uses the side blowing principle so as to produce low nitrogen steel from normal American pig irons, has been developed experimentally in this country. A process fitted to U. S. raw materials All of the preceding processes, with the exception of the rotary furnace, suffer from the common shortcoming that they cannot be adapted to the production of high-carbon, low-phosphorus steels unless large proportions of recarburizers are added. In 1947, a program was initiated by the Inland Steel Company1&apos; to study an oxygen steelmaking process specifically designed to utilize the full range of phosphorus analyses encountered in American pig irons and to give finai products with phosphorus and nitrogen contents comparable to steel produced by the basic open hearth process. Some of the objectives of the proposed process are: 1) the process should be able to accommodate molten pig iron conta;rl;rrg up to 1 pct P., 2) sne process should be subject to close control of carbon analysis, 3) the process should be capable of producing high carbon

Jan 1, 1958

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.&apos; A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By N. K. Chen, R. Maddin

Single crystals of molybdenum were extended at temperatures from 1300° to 2500°C. It was found that with increasing temperatures, the yield becomes more pronounced and the number of slip bands for equal amounts of elongation decreases. Slip at high temperatures fragments the structure. OTHER than the investigations on sodium and potassium by Andrade and Tsien,&apos; the researches of Steijn and Brick&apos; on a iron single crystals at low temperatures are about the only studies of the influence of temperature on glide of body-centered cubic single crystals. The effect of test temperature on glide has been rather widely investigated with hexagonal crystals" and less widely with face-centered cubic crystals. ~~ a result of these studies it can be said that, in general, the onset of plastic flow as measured by the initial rate of strain hardening becomes more abrupt with increasing temperature, and the value of the yield decreases with increasing temperature. Strain hardening, however, is markedly affected by changes in temperature except at very low and very high temperatures where the strain hardening rate becames constant. In the present investigation it is shown that temperature affects the glide of molybdenum single crystals in much the same manner as crystals of other classes, it., for comparable strains the number of slip bands decreases with increasing temperature; shear along the slip bands increases with increasing temperature; the yield becomes more pronounced with increasing temperature of test; and the strain hardening approaches a constant at very high temperatures. In addition, it is shown that, in agreement with the work of Tsien and Chow, Qlip occurs on (110) planes in <Ill> directions. It is further shown that slip at high temperatures fragments the structure into either irregular sized cells or bent atomic planes which are roughly aligned in crystallographic directions. Experimental Procedure Single crystals 3 mm in diameter by about 25 mm long were prepared using the technique previously described.&apos; The furnace in which the crystals were grown served as the extension apparatus for the tension tests. It consisted of a 4 in. water-cooled brass tube 20 in. long which was continuously evacuated at the bottom. Two water-cooled copper electrodes held the specimen by means of spherical collets secured in place in the electrodes by set screws. These electrodes served also to transmit power and stress to the specimen. The lower electrode was clamped to a stand, while the upper electrode was fastened to one side of a lever arm flexibly supported at the top through a slightly offset pinion. A metal bellows operating elastically was attached to the upper electrode to affect a vacuum seal and allow freedom of motion. The level of the arm was adjusted by rotating a graduated nut. Rotation of the electrode was prevented by a key fitted into a groove. After the specimen was mounted and the vacuum secured, the lever arm was adjusted so that the bellows was at its relaxed position. This insured that the total weight of the specimen, the upper electrode, and the downpull of the vacuum were balanced by the horizontal beam. Since the specimen was heated by its own resistance, expansion of the specimen proceeded freely by this arrangement. During the time of heating the specimen, the beam was maintained in a horizontal position by turning the nut at the top. By graduating the lever arm and using a known dead weight on the lever arm to supply a tensile stress, the graduated nut could be read to 0.0001 in. extension. Since

Jan 1, 1955

By A. G. Jordan, W. Jeitschko, Paul A. Beck

The occurrence qf the V phase structure /Zr,Co,Ge, type) in ternary syste7ns (titanium, zivconium, niobium, lanta1urn) -(nickel, cobalt, iron)-(silicon, germanium) was incestigated. Nine V silicides and four V gertrlanides were found and their lattice constants are reporled. The lattice constants of twenty-one preri-ously identified E phases (TiNiSi type) are given. The average atomic volumes of these phases are discussed in relation to similar binary phases. ThE occurrence of a phase Ti4Ni4Si7 was first reported by Westbrook. DiCerbo, and peat&apos; who gave it the name "V phase". They also reported the existence of an E phase TiNiSi. Subsequently a systematic study was undertaken in this laboratory to explore the occurrence of E&apos; and V phases3 in related ternary systems. In the meantime the crystal structure of the E phase TiNiSi 4 and of the V phase Zr4CO4Ge 75,6 was determined. In the present paper the details of the V phase investigation and the lattice constants of the E and V phases are presented. V PHASES Alloy specimens of approximately 10 to 15 g were prepared by arc melting under argon (99.996 pct Ar) atmosphere. The starting materials were all of purity higher than 99.9 pct, with the exception of cobalt. which contained 0.14 pct Fe as the only major impurity. The weight losses were in all cases less than 2 pct, in most cases less than 1 pct. The samples were encapsulated in fused silica tubes with sufficient argon to yield about 1 atm pressure at the annealing temperature. After the homogenization anneal. Table I. the specimens were water-quenched. A representative portion of each specimen was then examined metallographically (etchant: 20 pct HNO,. 10 pct HF. 25 pct glycerine, 45 pct H20). Only minor amounts of second- and third-phase particles were observed in the specimens listed in Table I, with the exception of alloys Zr4Fe4Si7 and Ta,Fe,Si,. which contained an estimated 10 pct by volume of foreign phases. X-ray powder photographs were taken with a Seeman-Bohlin type focusing camera and Fe-KO radiation. Of the thirty possible combinations of elements in the ternary systems (titanium, zirconium. vanadium. niobium. tantalum)-(iron. cobalt, nickel)-(silicon. germanium) thirteen V phases could be identified. In the remaining seventeen ternary systems and also in the systems Cr-Ni-Si and (M0.W)-(Ni.Co)-Si no V phase was found at the composition 4:4:7 after annealing at temperatures between 900" and 1200&apos;C. For the determination of the lattice constants of the V phases Debye-Scherrer photographs were taken using the asymmetric film arrangement and CrKcr radiation (ka1, = 2.28962A). Using the positional parameters, as determined6 for Zr,Co,Ge,. Table 11. intensity calculations were carried out for each of the V phases with the aid of a computer program.: Thus unequivocal indexing of the diffraction patterns was greatly facilitated. The lattice constants. Table I. were then computed by a least-squares fit of the high-angle lines with f (0) = cos2 Q as extrapolation function. Only few. if any. very weak impurity lines were observed, with the exception of the three iron alloys Zr,Fe,Si7. Zr4Fe,Ge7. and Ta,Fe,Si7. The agreement

Jan 1, 1970