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By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By A. W. McReynolds

One characteristic of plastic deformation which distinguishes it from elastic strain is the essential inhomo-geneity of plastic strains. Elastic strain varies continuously through a material, and average relative displacements of initially adjacent atoms are only small fractions of their initial spacing, (strains of the order of 0.01 or less). On the other hand, plastic flow corresponds to the appearance of discontinuities in strain of the lattice, such as dislocations or slip bands, where local strain, on an atomic scale, is several orders of magnitude higher. These discontinuities are visible on a microscopic scale as the familiar slip lines (Fig 1). In spite of this obvious microscopic inhomogeneity, however, macroscopic measurements almost invariably show a smooth curve of stress vs. strain (Fig 2b) even if measurements of linear strains be made to an accuracy of one part in 107. This macroscopic homogeneity of strain indicates that the discontinuities in strain on slip planes occur in increments too small or too slow to be recorded individually, and further that they occur sufficiently independent of one another so that the small increments add at random to a smooth stress-strain curve. The present paper describes observations of plastic strain in aluminum of commercial purity and in high purity Al-Cu alloys, where there exists a strong coupling between slip in various regions of the specimen such that once initiated it spreads rapidly through a large volume. The total effect is that of relatively large, rapid, and regularly spaced steps of strain followed by periods of only elastic strain. Fig 2a illustrates the type of "stair-step" stress-strain curve which results. The properties of this cooperative slip phenomenon will be described further in the section on results: in par- ticular it will be shown that each step corresponds to the propagation of a wave of plastic deformation through the specimen. Some interpretations of the mechanism by which it occurs will be made in the following section. Although the type of plastic wave phenomena to be described has not previously been reported, there are numerous cases of related effects in the plastic yielding of metals: YIELD POINT PHENOMENA The most familiar of such effects is the "yield point" observed in low carbon steels, brass, duralurninum, and the like. It consists in the sudden termination of the elastic portion of the stress-strain curve by a large plastic strain. Since the usual tensile machine is such that yielding of the specimen relieves the load, the resulting curve is as shown in Fig 3. As the strain continues, deformation occurs at a lower stress for some time, then follows a rising curve, but with no further sudden yielding. This effect has been observed in brass by Sachs and Shojil and later by many others. Edwards, Phillips and Jones2 made extensive studies of the effect in steel, and of the role of various alloying elements. Although there seems to be fairly clear evidence that the yield point is caused by a hardening of the material by precipitation of impurities, no satisfactory explanation for the sudden yielding has been given. Winlock and Leiter3 have shown that the strain. level of the upper yield point depends strongly on the rate of loading, the yield point increasing by almost a fac- tor of two as the strain rate goes from 0.002 in. per in. per min. to 4.4 in. per in. per min. This effect would seem to imply an incubation period before yielding is initiated at a certain stress. On the other hand, by going to very slow loading rates, Edwards, Phillips and Jones2 showed that the yield point does not become lower and eventually disappear as might be expected, but, on the contrary, begins to rise at loading rates below about 25 Ib per in. per min. becoming much higher than at rapid loading rates. STRAIN AGING If, instead of continuing straining of a specimen after occurrence of a yield point, the load is removed and the specimen aged, resumption of the test results in occurrence of another yield point as shown by the dotted curve of Fig 3. The new yield stress is generally higher than the previous maximum applied stress. This hardening of the material by straining and subsequent aging is undoubtedly related to quench age-hardening resulting from the aging of a specimen quenched from high temperature. Since neither effect is observed in pure metals, it is generally accepted that quench-aging in all cases is the result of hardening by precipitation of a supersaturated alloying element, and that strain-aging is probably a similar precipitation, accelerated by disruptions of the lattice by previous strain. Pfeil4 has shown that strain-aging does not occur in iron from which all of the carbon has been removed, but that only a very small carbon content, around 0.003 pct, is necessary to cause strain-aging. In accord with this observation is recent work by Dijkstra5 in this laboratory showing that the solubility limit of carbon in iron is extremely low, less than 0.001 pct at 400°C. Edwards, Phillips and Jones2 have shown that the strain-aging effect is also removed by the addition of small quantities of elements such as Mo, Mn, Ti, and the like, which readily form carbides. Their results demonstrate the

Jan 1, 1950

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By I. R. Kramer, L. J. Demer

Aluminum single crystals were pulled in an electrolytic cell allowing surface removal during the deformation. The extent of Stages I and 11 of the stress-st-aitz curve was increased and the slope decreased as the rate of metal removed from the surface was increased. An increase of the strain rate caused a decrease in the effectiveness of the metal removal. The data indicate that the work-hardening coefficient in Stage I is determined primarily by the conditions which exist on the surface of the crystal. In Stages 11 and 111, both surface effects and internal barriers are important. ALTHOUGH numerous investigations have been conducted on the plastic flow characteristics of metals in an attempt to explain the mechanism of work-hardening, relatively few studies have taken into account the influence of the surface. In all current theories of work-hardening it is assumed that the impediments to the movement of dislocations are within the crystal. The barriers due to the surface and the existence of solid and liquid films have been neglected even though it has been demonstrated that the surface exerts a large effect. A number of investigators1-l8 have shown that solid films on the surface of single crystals markedly affect their mechanical behavior. In general, the presence of a solid film tends to increase the yield stress and increase the work-hardening rate. Often, on single crystals, Stage I and, at times, Stage II regions are completely suppressed. Various mechanisms have been offered for the effects of oxide and metal films as well as the influence of electrolytes. Of these, concepts concerned with the locking of surface dislocation sources and the blocking of dislocations at the surface resulting in pileups appear to be actively considered at present. Barrett,11 Takamura,6 Gilman,19 Lipsett and King,20 Shapiro and Read,10 and Weiner and Gensamer21 are among those who have interpreted their results in terms of piled-up dislocations at the surface, while Adams.22 and Chalmers and Davis23 have explained their experimental observations in terms of locking of surface dislocation sources. In general, the change in plastic flow properties due to electrolytes has been explained in terms of the unblocking or unlocking of dislocations by the removal of the oxide films. In considering the two proposed mechanisms, it appears that the locking of sources of surface dislocations by a solid film should exert a primary influence only on the critical resolved shear stress for flow and not on the slopes of Stages I and 11. However, the blocking at the surface of dislocations from internal sources may also affect the critical resolved stress and furthermore exert an influence throughout the whole plastic range. In certain cases it does not seem feasible to explain the results of experimental observations in terms of locking of surface dislocation sources. The abnormal aftereffects found by Barrettll,12 by removing the oxide by an acid treatment are excellent evidence of the blocking of dislocations at the surface. Additional evidence in favor of a blocking due to a pileup of dislocations at the surface may be found from the observations that the critical resolved shear strength continues to increase with the thickness of the oxide layer until very heavy oxide layers are formed. If the locking of surface dislocations sources were the dominant factor, the critical resolved shear stress would not be expected to increase after all of the surface sources were locked by the formation of the oxide. This may be expected to happen after a few atomic layers of the oxide are formed. In spite of the above evidence on the strong influence of the surface on the plastic flow characteristic, this has been ignored in current theories of work-hardening. Seeger24,25 suggested that most of the dislocations may slip out of the crystal only when the specimen axis is within certain areas of the orientation triangle. In other areas the resolved shear stress in other glide systems is large enough to generate dislocations which can form Lomer-Cottrell locks, thereby decreasing the average slip distance in some directions and causing a larger hardening rate. Friede126 assumed that at the beginning of Stage 11, a large number of Lomer-Cottrell dislocations are formed by a catastrophic process which used up all the Frank-Read sources on the secondary slip-planes. In this manner a fixed number of Lomer-Cottrell locks is formed which act as barriers against which the dislocations can pile up. In Stage 111, Seeger24 and Diehl, Mader, and Seeger25 proposed that Lomer-Cottrell barriers are circumvented by the cross slip of extended screw dislocations. Cottrell and Stokes,27 Friedel,26 Cottrell,26 and stroh29 suggest that the Lomer-Cottrell dislocations collapse under the stress field of the dislocation pileup. It is the purpose of this paper to report the changes in Stages I, II,and III of the deformation process in

Jan 1, 1962

By J. D. Livingston, H. E. Cline

Cu-Pb alloys in the vicinity of the monotectic composition have been directionally solidified under a high temperature gradient at rates up to 2 X l0-' cm per sec. Over a wide range of compositions, high growth rates yield a composite structure consisting of continuous rods of lead in a copper matrix. This range of compositions increases with increasing growth rate, in agreement with arguments based on the relative velocities of composite growth and the growth of copper dendrites or lead drops. The breakdown of the composite structure at slow growth rates is explained in terms of the relative interphase surface energies. The observed interrod spacings of the composite structure are large compared with the predictions of the Jackson-Hunt equations of eutectic growth. ThE directional solidification of many eutectic alloys produces fine composite structures of parallel lamellae or rods. There has been considerable interest not only in the fundamentals of this two-phase solidification process,'-3 but also in the interesting physical properties produced by such regular and aniso-tropic microstructures. Composite structures can be grown only over a limited range of composition, beyond which coarse primary dendrites of one phase appear. In organic eutec-tics, this composition range of composite structures has been shown to increase with increasing growth rate.7"10 These results were explained in terms of the relative velocities of composite (coupled) growth and dendritic growth. Although similar arguments should apply to metallic eutectics,11-13 suitable experimental results are lacking. In contrast to the work on eutectics, the directional solidification of monotectic alloys has received little attention. (The monotectic reaction is similar to the eutectic reaction, except that one of the resulting phases is a liquid, which subsequently solidifies in a separate reaction at a lower temperature.) Directional solidification of some monotectic alloys'4715 yields regular rodlike microstructures, whereas in other cases macroscopic separation of solid and liquid phases occurs.16 chadwick17 rationalized these results in terms of the probable relative magnitudes of the various interphase surface energies. A recent study of chill-cast Cu-Pb alloys18 revealed a fine rodlike microstructure in alloys near the monotectic composition. It was decided to investigate the directional solidification of such alloys, and to determine the range of composition and growth conditions yielding composite structures. The Cu-Pb system is convenient for such a study, both because it is simple metallurgically, with no compound formation and negligible solid solubilities, and because its basic properties are well-documented. Recent literature on the Cu-Pb system includes studies of bulk thermo-dynamic properties,'g surface energies,20"21 densi-ties,25 and diffusion constants.a6 A similar study of the directional solidification of Cu-Pb alloys was recently undertaken, independently, by Kamio and Oya." EXPERIMENTAL Alloys were prepared by melting 99.999 pct Cu and 99.999 pct Pb in a graphite crucible, stirring well, and pouring into a cold graphite mold. Rods 0.175 in. in diam were machined from the ingots. Alloy compositions studied ranged from 25 to 55 wt pct Pb. Samples were placed in graphite crucibles 5 in. long with 4 in. OD and 0.035-in. walls. They were melted under flowing argon in a vertical, two-zone. platinum -wound furnace. A voltage stabilizer was used to minimize fluctuations in input power. The narrow specimen diameter minimized convection. Directional solidification was achieved by driving the crucible downward into a +-in. hole in a water-cooled copper toroid. The toroid was located immediately below the narrow end zone of the furnace. The end zone was separately powered to maintain high local temperature. Therefore a high temperature gradient (approximately 300 deg per cm) was maintained in the specimen throughout the run. The crucible motion was screw-driven. and a wide range of drive speeds were available. The limited rate of heat removal caused a thermal lag in the specimens at high drive rates. However. temperature-time curves from thermocouples imbedded in a representative sample indicated that the average growth rate still approximately equaled the drive rate. Although the specimens were initially homogeneous, melting and re solidification redistributed the lead. producing composition variations of several percent along the specimen length. (During melting. lead melted first and ran down the sample surface. Rapid freezing tended to reproduce the resulting composition gr~dient, but slow freezing did not because a slow-moving interface tended to reject lead. as discussed later.) To determine local composition. ;-g samples were cut from regions exhibiting various microstructures and were chemically analyzed for lead content. Micrographs were taken on as-polished or lightly etched surfaces. Three-dimensional structure of the lead network was viewed with a scanning electron microscope after removal of some of the copper matrix with nitric acid. RESULTS Several different microstructures are observed, depending on composition and drive rate. Because melting and resolidification produced composition gradients, results are best presented in t&ms of final local composition, rather than initial or average composition. The ranges of local compositions and drive

Jan 1, 1970

By L. C. Brown, C. St. John, C. C. Sanderson

The diffusion rate in Cu-Te couples is very sensitive to compressive stress, with a load of 20 psi making a significant difference to the width of the diffusion zone. At zero stress, two phases appear in the diffusion zone (Cu4Te3 and CuTe). Under compressive loading the third stable phase (Cuz Te) also appears, and its thickness increases progressively with increasing stress. The results are explained on the basis of an incipient Kirkendall porosity which restricts the transfer of atoms from the copper into the diffusion zone. DURING a study of the Kirkendall effect in Cu-Te couples prepared by clamping together the two components, it was found that the diffusion-zone width and shape in the plane of contact were not reproducible. Although the stresses involved in clamping are not normally sufficiently high to affect diffusion rates, preliminary tests established that the Cu-Te system is particularly stress-sensitive. The phase diagram for the system Cu-Te given in Hanssen1 shows that there is practically no solid solubility at either end of the phase diagram. Many areas of the diagram are not fully substantiated, but there appear to be three intermediate phases: Cu,Te—hexagonal in structure, having a grey luster; Cu4Te3—a tetragonal defect structure, having a red-purple luster; CuTe—orthorhombic in structure and having a golden-green luster. The existence of a fourth phase, the X phase at 37 at. pct Te, is considered doubtful. The composition ranges of the three stable phases are small, and are not accurately known. The phase diagram changes little with temperature up to 305°C, at which temperature a polymorphic transformation takes place in Cu2Te. The nature of the Cu-Te phase diagram indicates that the diffusion zone in a Cu-Te couple would consist of a series of layers of intermediate phases. The relative thickness of any one phase will depend on its diffusion coefficient and composition range.' In this type of diffusion couple it is often found experimentally that some phases are not visible at all in the diffusion zone due either to a small diffusion coefficient or to a restricted composition range.3 Since the composition ranges of the phases in Cu-Te are not known, it is not possible to determine diffusion coefficients in this system from a knowledge of the phase thicknesses. Several investigations have been carried out to determine the effect of compressive stress on diffusion rates in multiphase systems. Diffusion couples of Ni-A1 have been investigated by Storchheim et al.4 and by Castleman and Seigle.5 Two phases (ß and ?) appear in the diffusion zone under zero stress and the thickness of both phases is progressively reduced with increasing stress. According to Storchheim et al.4 a stress of 25,000 psi reduces the thickness of the diffusion zone by 50 pct. In a-brass—?-brass couples the thickness of the 0 phase formed in the diffusion zone was reduced by 20 pct at a stress of 20,000 psi.6 In other investigations the compressive load has been observed to increase the width of the diffusion zone. In A1-U, several investigators3,8 have found the width of the whase UA13 to increase with stress. According to casileman,8 the rate of formation of UA13 at 520°C is 75 pct faster at a stress of 20,000 psi as compared with a stress of 2500 psi. In Cu-Sb the effect of stress is greater than in the other systems described. According to Heumann9,10 only one phase (y) appears in the diffusion zone at a stress of 500 psi, but at a stress of 850 psi two phases (y and k) are present. If a diffusion couple containing both y and k phases is annealed at a low stress level, the y phase grows at the expense of the k phase. EXPERIMENTAL The diffusion couples were prepared from electrolytic copper bar stock with a nominal purity of 99.92 pct and from tellurium of 99.7 pct purity. The tellurium proved difficult to machine because of its brittleness and a technique was developed for casting the tellurium into a graphite slab mold and spark-machining specimens from this slab. Both the copper and tellurium were produced in the form of discs 2 in. diam by approximately 1/4 in. thick with surfaces ground flat to 3/0 emery paper. The diffusion apparatus is shown in Fig. 1. Auni-axial compressive stress was applied to the system through a simple lever system. A stainless-steel rod actuated by the lever arm lay inside a stainless-steel tube. The diffusion couple lay on top of the steel rod, and pressure was applied to the couple between the rod and a plug welded into the center of the tube. To ensure a uniform stress across the couple, a hemispherical boss and cup were used to transmit the load to the diffusion couple. A 400-w tube furnace with a uniform hot zone 3 in. long slid around the stainless-steel tube and maintained the assembly at temperature. A thermocouple situated 3 in. from the specimen operated a proportional temperature controller which maintained the specimen temperature constant to ±2°C. Most diffusion runs were carried out at 250C although a few tests were made at other temperatures in the range 235° to 300°C. The specimens were inserted and removed with the furnace at operating temperature, and took only 2 min to reach diffusion temperature—a time small compared with the total diffusion time. All the diffusion experiments were carried out in a hydrogen atmosphere, since consistent results were obtained in hydrogen and nitrogen atmospheres and in

Jan 1, 1967

By W. B. Agocs

IN August 1954 a low altitude test geophysical survey was made in the Green Pond area of Morris County, New Jersey, with a Gulf Research and Development Co. Model II total magnetic field variation magnetometer mounted in a Sikorsky S-55 helicopter. The test was made in this area to compare the results of a high precision, very low altitude magnetometer survey with an existing ground magnetic survey in this area having known magnetite concentrations, so that the method could be used in areas of difficult access for the detailing of airborne magnetometer anomalies of interest in place of ground surveys. The load capacity of the Sikorsky S-55 permitted installation of a recording scintillation counter so that a radioactivity survey would be made simultaneously with the magnetometer survey. The area surveyed is located at approximately 41°00'N and 74o28'W, just south and east of the town of Green Pond, N. J. The outstanding topographic feature of the region is Copperas Mountain, a well defined ridge, maximum elevation 1222 ft, which runs the entire length of the survey. The lowest point in the survey, 810 ft, is in the extreme eastern corner. Topography of the area is shown in Fig. 1. The three major rock units outcropping in the area are all metamorphic: the Pochuck gneiss, which has been divided into two metamorphic facies; the Byram gneiss; and the Green Pond conglomerate. The relative ages of the Pochuck and Byram formations, both pre-Cambrian, are in doubt, but it is believed that the Pochuck is the older of the two.' The Green Pond conglomerate is Silurian.' Distribution of the outcrops and mine locations is shown in Fig. 1. Two facies of the Pochuck gneiss can be distinguished locally—the Copperas Mountain and Kitchell members. The Copperas Mountain member is a hornblende gneiss, and all the mines and prospects in the area are in this unit. The Kitchell is a quartz-plagioclase feldspar gneiss. The Byram gneiss is a relatively nonresistant valley formation which is high in the potash feldspar. The Green Pond conglomerate is a well indurated quartzite-conglomerate which forms the Copperas Mountain and the Green Pond Mountain's ridge to the north. It overlies the gneisses with a strong angular discordance that may be a fault. The geologic structure of the Green Pond area is relatively uncomplicated. The foliation planes of the gneisses dip steeply to the southeast, and the Green Pond conglomerate dips steeply to the northwest. Additional faulting in the area is indicated at the contact between the Kitchell member of the Pochuck and the Byram along the base of the topographic spur extending to the southeast from Copperas Mountain. The magnetite mines of Pardee, Winter, Davenport, Green Pond, Copperas, and the Bancroft shaft are described by Bayleyl and Stampe2.' The ore is in the Copperas Mountain member of the Pochuck gneiss. The magnetite veins are 10 to 50 ft wide and up to 300 ft long, dipping to the southeast at angles ranging from 40" to 75". The locations of these mines are shown in Fig. 1. Dip Needle Survey: The dip needle survey shown in Fig. 2 was taken from a U. S. Bureau of Mines Report of Investigations." The figure numbers below the local, individual map area outlines refer to the figures in the aforementioned reports which were not contoured. The area of the dip needle survey was confined almost exclusively to the outcrops of the Pochuck gneiss. The separation between survey profiles was 100 ft and the distance between stations on the profiles was 25 ft in highly anomalous zones to 100 ft in magnetically flat areas. A total of 16 1/2 miles of traverse was surveyed over an area of approximately 1/2 sq mile with 2050 stations. The magnitude of the magnetic anomalies is difficult to determine due to the lack of information concerning the type of dip needle used and the procedure followed in making the dip needle survey. This latter would include the method of "zeroing" the dip needle and the procedure of reading at the stations, whether on the swing or statically. Calibrations made of the Gurley dip needle, Lake Superior type, show a static sensitivity of 385 gamma per degree in the range from —25" to +35o, corresponding to a variation in the total field of —9600 gamma to +13500 gamma in a total field of 57000 gamma, inclination 72". The sensitivity increases to 16 gamma per degree from a deflection of 60" to 76", and from 76" to 172" the sensitivity decreases continuously to a low of 260 gamma per degree. From the above it may be seen that it is difficult to assign an arbitrary sensitivity for the dip needle used on this survey. However, an estimated value of 100 gamma per degree may be assigned. On this basis, the majority of the magnetic anomalies, whose deviation is +20°, would be 2000 gamma. Locally, west and northwest of the Pardee mine the magnetic anomaly is +50°, or 5000 gamma; in the Green Pond mine area deviations of +75" are observed that would correspond to anomalies of 7500 gamma. The areal extent and width of the dip needle magnetic anomalies is comparable to profile and station spacing. Hence it is concluded that part of the detail may be due to control, and the probable cause of the magnetic anomalies is at or near surface exposures of magnetite concentrations in the form of veinlets and disseminations whose locations correspond to the local magnetic anomalies. On the basis of the magnetics, none of the magnetite concentra-

Jan 1, 1956

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104'c per sec for 0.010 in thick specimens, as calculated from Newton's law of heat flow2 using a heat transfer coefficient of 25 ft-'. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By S. Kobayashi, A. E. Armenákas, C. Mylonas

Earlier work1-4 has shown that commercial mild steels under static loading at the lowest natural operating temperatures fracture in a brittle manner only when damaged by a suitable history of straining. Notched and then compressed plates have fractured in subsequent tension at loads as low as 10 pct of the limit load and precompressed smooth bars at a subsequent extensional strain as low as 0.01. The comparison of the average net fracture stress with the flow limit stress was shown to be an excellent criterion of brittle or ductile behavior of mild steel structures when only loads and general stress levels are known. The present investigation shows that the deformation at fracture is a far more sensitive measure of brittleness than the fracture stress. Both criteria, deformation and stress, are used to determine the amount of uniform precompression of two mild steels, ABS-B and Project E-steel, resulting in brittle fracture under the strong constraint of a subsequently machined severe circumferential groove. The fracture stress equaled or exceeded the theoretical flow limit Ól = 2.680., ('based on the elevated yield stress at each prestrain) up to prestrains of about 0.20 and then fell off to about 1 at prestrains of 0.60. Yet a prestrain of only 0.05 reduced the elongation at the shoulders by a factor of about 4. The total plastic elongation of a region surrounding a sharp notch in prestrained steel deternines whether or not fracture will be initiated in large structures, hence is a direct and realistic measure of the remaining ductility and provides an excellent test of the material's resistance to embrittlement. ALMOST all engineering structures of mild steel which failed in service in a so-called "brittle" manner exhibited appreciable local plastic deformation (more than 1 pct) and a mixture of "cleavage" and "shear" fracture surfaces. Furthermore, the peak local stress in an advancing crack is always high. Such simple criteria as pure cleavage, absence of plasticity, or fracture stress, so useful in other fields, are insufficient to characterize brittleness in engineering structures at ordnary temperatures. The "brittle)' behavior of engineering structures is caused by the limited ductility at cracks or notch regions, as shown by recent work at Brown University summarized and extended in Refs. 1 to 4. It was also shown that the local ductility of mild steel may be catastrophically reduced by a suitable strain and temperature history similar to those which may occur in real structures. Localized yielding begins at the notch roots at low loads but is contained by surrounding elastic regions. The plastic strains are hence small. They increase slowly with the load up to the flow limit or limit load for an ideally plastic material. Unrestricted plastic flow then occurs. At such strains the real material locally st rain-hardens and fractures. With work-hardening materials no flow limit exists, and the transition from low to high plastic strains is gradual but increases more rapidly at loads close to the flow limit of an equivalent perfectly plastic material. When the available ductility is sufficient for reaching the limit load, the behavior is normal or "ductile". With insufficient ductility, fracture will occur at a low load and will be defined as "brittle". Accordingly the sufficiency or not of the ductility at a notch is reflected in the magnitude of the fracture load or average net stress as compared with the limit load or flow limit. The application of this criterion gave surprising results. Service failures under semistatic loading occurred mostly below the limit load, hence were "brittle". On the contrary all static tests with undamaged commercial mild steels reached the limit load in spite of the deepest notches and temperatures below Charpy impact transition (say about -30°F or higher). Notched bars showed no brittleness even under fully dynamic axial loading up to 1.5 x107 psi per sec at -23°F and about 2.5 x l06 psi per sec at -ll0°F, but broke in a brittle manner at -200°F and l03 psi per sec.' To propagate a fracture at low load, experimenters had to trigger it by superimposing a strong dynamic impact at a notch cooled by liquid nitrogen as in the Robertson5 or Esso tests.' Once started the cracks would run through warmer regions of smaller stress. Obviously the ductility of the apparently undamaged commercial steels was "sufficient" in the laboratory tests but not in the service fracture, where it must have been reduced by some embrittling procedure of fabrication or service. These conclusions were confirmed by the achievement of low static stress (brittle) fracture initiation in unwelded steel after a local reduction of ductility by simple prestraining. Symmetrically notched plates of undamaged mild steel cooled below the Charpy V-notch transition range were tested in central static tension: Undamaged plates withstood loads of limit intensity, but when subjected to prior in-plane com-pressive prestraining perpendicular to the notch axis and to accelerated aging, the plates fractured completely or partially at very low static loads, as low as one-tenth of the flow limit.2-4 However, damage could not be easily related to the strongly variable prestrain around a sharp notch. To obtain easier strain measurements, it was decided to use axially precom-pressed bars and bent bars. Final testing was done by

Jan 1, 1970

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By K. M. Rolls, F. W. Reuter, J. Wulff

The superconducting behavior and microstructural characteristics of a nominal Nb-40 wt pct Ti-0.239 wt pct O alloy were studied as a function of ther mo -mechanical processing treatment. Critical current density us applied transverse magnetic field was obtained for 0.010-in.-diam wires at 4.2°Kin steady fields 14 to 110 kG. Both optical metallogvaphy and transmission electron microscopy were used to delineate the micros tructures of the same wires. It wan found that a 1-hr 500°C precipitation heat treatment after cold drawing to final size led to the highest critical current density. Heat treatment at 600°C also led to a high critical current density, but the precipitate differs in kind and form from that at 500°C. The resistire critical field was also found to be sensitive to precipitation heat treatment since the effective composition of the superconducting phase changes. This is discussed in terms of the oxygen in interstitial solid solution. Two types of high-field superconducting wire are at present used in the construction of high-field superconducting solenoids. These types are solid-solution alloy wire such as Nb-Zr and Nb-Ti and composites of the brittle inter metallic compound Nb3Sn. The latter generally have a high super cur rent-carry ing capacity which is difficult to vary if properly made. The supercur rent- carry ing capacity of the former can be varied drastically and often predictably by suitable thermomechanical processing treatments. In general, the critical current density Jc of the solid-solution type of alloy is increased by cold work and by additions of interstitial elements along with aging heat treatments. The imperfections which result are be-iieved to be responsible for the observed increase in Jc. In 1962 Kneip and coworkers1 found that the critical faurrent density of Nb-Zr alloys could be increased by proper heat treatment preceded and followed by cold work. Betterton and coworkers2 using a Nb-25 at. pct Zr alloy found that small additions of oxygen or carbon enhanced the effect of this heat treatment. They suggested that the interstitials present aided precipitation in the alloy, leading to a filamentary structure with superior properties. If the precipitation heat treatment was omitted, interstitial additions had a negligible effect on Jc. wong3 showed that higher heat-treatment temperatures lowered Jc. Walker and co-workers,4 who studied microstructure (by transmission electron microscopy) as well as superconductivity, found that the Jc anisotropy introduced by cold rolling was itself affected by heat treatment. They were unable to clarify the relation between microstructure and critical current density, although evidence of precipitation was indicated. More recent investigation of Nb-Zr alloys,5,6 besides showing that structural defects and fiber ing due to cold work and precipitation serve to raise Jc, also elucidate important optically observable microstructural changes which occur upon precipitation. In these reports, coarsening of the microstructural features was found to decrease Jc. Vetrano and Boom,7 who studied Ti-20.7 at. pct Nb, found that Jc was increased to a maximum by a 415°C, 3-hr heat treatment following quenching from 800°C and cold working. Heat treatments can also affect the resistive critical field Hr. Final-size heat treatments of Nb-Zr wire can lower Hr drastically if gross phase decomposition occurs5'* or moderately if the effects of cold work are eliminated without changing significantly the composition of the phase of interest.3,5,6,8 The percentage of oxygen which can be added to Nb-Zr alloys to enhance Jc is limited by the difficulty of subsequent cold drawing. Since Nb-Ti and Ta-Ti alloys in contrast can tolerate appreciably higher percentages of oxygen, it was decided to investigate the superconducting behavior of various alloys in these systems. The present paper describes the results of adding oxygen to a nominal 40 wt pct Nb alloy as a function of thermomechanical treatment. I) EXPERIMENTAL PROCEDURE A small alloy ingot was prepared from high-purity niobium, iodide, crystal-bar titanium, and Nb2O5 powder by arc melting on a water-cooled copper hearth in a gettered argon atmosphere. The ingot was turned and remelted fourteen times to insure homogeneity. After final melting and rapid cooling, it was machined round to 0.415 in. diam, jacketed in stainless steel, and cold-swaged to 0.117 in. diam. The jacket was removed and swaging continued to 0.051 in. diam followed by wire drawing in carbide dies to 0.010 in. diam. Although it was intended that about 1500 ppm O (by weight) be added, inert gas fusion analysis indicated a 2390 ppm 0 content, apparently due to additional oxygen pickup in the arc furnace. Even so, the alloy was sufficiently ductile to be cold-worked to greater than 99.9 pct reduction

Jan 1, 1967

By Carl Altstetter, Emmanuel deLamotte

The influence of an external stress and plastic deformation on the allotropic transformation of single crystals of a Co-30.5 pct Ni alloy was investigated. Experimental results were obtained from dilatometry, X-ray diffraction, and optical and electron microscopy. The effects of stresses could be conveniently divided into three stress ranges. In range I, from 0 to about 400 g per sq mm, the specimens exhibited a multi-variant phase change on cooling and a considerable amount of retained cubic phase. In range II, from 400 g per sq mm to the elastic limit, hexagonal regions of a given orientation grew in size and the cubic phase disappeared with increasing stress level. In range III, just above the elastic limit, specimens transformed into hexagonal single crystals. It was found that plastic deformation, not applied stress, was the factor which determined whether a single-crystal product was formed. The observed macroscopic shear directions were mainly (112) on cooling, but the behavior was more complicated on heating under stress. To explain these properties of the phase change, a model based on the nucleation of partial dislocations is proposed. IT is well-known1 that, on heating, hcp cobalt transforms into an fcc arrangement by shearing on close-packed planes. The crystallographic orientation relationship of the phases is as follows: the habit plane is (OOO1)hcp ?{lll}fcc and a (1010)hcp direction is parallel to a (112)fcc direction. The temperature at which the transformation occurs in pure cobalt is around 420.C 1,2This temperature decreases with increasing nickel concentration: and at about 30 pct Ni it reaches room temperature. However, many of the transformation characteristics remain essentially the same, particularly the crystallographic features.495 A convenient way of studying the transformation is to alloy cobalt with nickel, thus avoiding the difficulties of doing experiments at the high temperatures needed to transform pure cobalt. Due to the hysteresis of the transformation it is possible to choose a Co-Ni alloy with an Ms temperature below room temperature and an A, temperature above room temperature. Either structure of such an alloy could then be studied at room temperature, depending on whether it had just been heated or cooled to room temperature. The choice of nickel is further favored by the small difference in lattice parameters between cubic cobalt and nickel and the similarity of their physical, chemical, and electronic properties. Co-Ni alloys are reported to have neither long- nor short-range order.6 The main purpose of this work was to investigate the influence of an external stress on the transformation characteristics of Co-Ni single crystals. It may be expected that slip, twinning, and transformation should have many features in common in cobalt, because the (111) planes of the cubic phase operate as slip planes when plastic deformation by slip occurs, they are the twinning planes, and they are the habit planes for the transformation. Many previous investigators7-&apos;6 have concluded that dislocations must play an important role in the nucleation and propagation of the transformation, just as they do for slip and twinning propagation. An external stress will affect their motion, and a study of its influence should yield further information about the atomic mechanism of transformation. The present work extends that of Gaunt and christian17 and Nelson and Altstette18 in both qualitative and quantitative effects of stress. The basic concept underlying all the present theories of the transformation of cobalt and Co-Ni alloys is the motion of a/6<112> partial dislocations over {1ll} planes of the cubic lattice. The ABCABC... stacking of the close-packed planes of the cubic phase can be changed into the hexagonal ABABAB... stacking by the sweeping of an a/6 <112> partial on every second plane. Twinning, on the other hand, requires a shear of a/6 <112> on each close-packed plane. The reverse transformation can be effected in a similar way by a/3 (1010) dislocations moving over every other basal plane of the hexagonal phase. Transformation theories2, 7- 12,14 differ in the details of the nucleation of the transformation and the propagation of the partial dislocations from plane to plane. EXPERIMENTAL PROCEDURE Nickel and cobalt rods supplied as 99.999 pct pure were induct ion-melted together under a vacuum of about 10-5 torr in a 97 pct alumina crucible. An alloy containing 30.5 pct Ni was found to have the desired transformation range, with an Ms near -10°C and an j4s in the vicinity of +10O°C. The ingots were swaged to &--in. rod and electron beam zone-leveled in a 10-6 torr vacuum. This procedure resulted in 12-in.-long single fcc crystal rods (designated I to VII) from each of which several tensile specimens of identical orientation were made. Chemical analysis of the bar ends indicated no contamination or gross segregation and no micro segregation was seen in electron micro-probe scans. Tensile specimens with a 9/32-in.-sq by 1-in.-long gage section were spark-machined from the rods and then electropolished or chemically polished to remove the machining damage and to provide a flat surface

Jan 1, 1970

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR&apos;s (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey&apos; recently has published an excellent review of the development of hot fluid injection processes. Recent publications"&apos; and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey&apos;), but simplifying assumptions make

Jan 1, 1969

By J. E. Johnson

Discussion of the paper of Prof. Henry M. Howe, presented in abstract by Bradley Stoughton at the Cleveland meeting, October, 1912, and printed in Bulletin No. 71, November, 1912, pp. 1181 to 1227. J. E. JOHNSON, JR., Ashland, Wis. :-This material is largely beyond the understanding of most of us practical men, but there are certain portions of that diagram that are of enormous importance. We have been conducting a, very extensive investigation of the quality of charcoal-iron and of all iron, and we have found that this eutectic point here (indicating on chart) is a sort of balance point between the good irons and the bad ones, and I have some slides to show what practical results we have found depending on this point here on the d diagram; and it would be a mistake for men who were -concerned with operation and were getting practical results, to think that these things are of no importance. They are exceedingly hard to understand, and I confess that a great deal of them is beyond me, but there is no doubt that the quality of iron depends to an enormous extent on the location of the carbon content of the iron to the right and left of this point, and the position of that point is dependent upon the silicon, and I wish to make a plea to the practical and operating members of the Institute not to disregard this material on account of its being highly scientific, because I hope to show later that there are matters of the highest practical importance that depend directly upon certain portions of this diagram. HENRY D. HIBBARD, Plainfield, N. J. :-T understand that washed metal, which, is practically pure iron and carbon, does not solidify at one instant, is cast-iron does, but passes through a mushy stage. That has been an enigma as to how and why it did so, and possibly some light might be thrown on it in this connection. BRADLEY STOUGHTON, New York, N. Y.:-If Wittorff&apos;s propositions are accepted, washed metal containing more than 4.1 per cent. of carbon would begin to solidify as liquid plus Fe4C

Dec 1, 1912

Jan 1, 1903

Jan 1, 1918

By AIME AIME

Jan 1, 1926

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Jan 1, 1938