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By E. C. W. Perryman

On electropolishing, high-purity Cu-Sn and Cu-Sn-P alloys with more than 5 to 9 pct Sn were found to contain many grain boundaries with a ridge-and-furrow profile. The effect was not eliminated by solution treatment and was present at the new boundaries in recrystallized material. It could be produced by diffusing tin into the 3 pct Sn alloy and it is concluded that the effect is due to enrichment of certain boundaries in tin, or possibly in an impurity present in the tin, in solid solution. IN the hot working of tin bronzes, especially those with moderately high tin contents, considerable difficulty is frequently encountered from intercrystal-line weakness, which results in cracking at the edges in sheet on strip rolling and in the unsupported regions of the rod in rod rolling.' These difficulties are not at all pronounced with up to 3 pct Sn, but at 5 pct Sn impose serious limitations and at higher tin contents, especially if the phosphorus content is also high, they may become very severe. In some work carried out at the laboratories of The British Non-Ferrous Metals Research Association it was found that a notable lack of ductility in tension at elevated temperatures, associated with intercrystal-line failure, was characteristic of tin bronzes even of relatively high purity. That the intercrystalline fracture is not due to a brittle or molten impurity phase at the grain boundaries was shown by the fact that the temperature at which intercrystalline fracture first occurred decreased with decrease of rate of straining. Tensile tests on some commercial tin bronzes, reported by Goetzel,² show a similar fall in ductility with increasing temperature. As no visual evidence had been obtained showing that the grain boundaries of the tin bronzes were different from those in copper, a more detailed microscopical examination was carried out, and the results of this are given in the present report. Several workers"' have observed that electrolytic polishing is a powerful tool for detecting small amounts of a second phase and in particular for detecting high solute concentrations, "equilibrium segregation," at grain boundaries. Since it had been found that the suggested solutions for electropolishing bronze and the standard solutions for brass and copper did not give satisfactory results it was first necessary to find a suitable electropolishing solution.' Experimental Procedure Materials Used: The cast and wrought materials used for this work were the same as those used for the mechanical tests referred to above. They comprised 3, 6, and 9 pct Sn alloys without phosphorus and the same three basic alloys with 0.03 and 0.4 pct P. A 5 pct Sn alloy without phosphorus, of similar purity, was also examined. The basis materials were Chempur tin, high purity 15 pct phosphor-copper and cathode copper, and spectrographic analyses are given in Table I. Treatment: The cathode copper was first melted under charcoal, degassed by plunging marble chips beneath the surface, and cast through a coal gas flame into sand molds to produce a number of small ingots which after machining were of a suitable size for subsequent vacuum melting. Chill cast bars of the alloys, approximately 1¼ in. in diameter, were then made by melting and casting in vacuo, the tern-

Jan 1, 1954

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide 'pest' ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,' comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By Erwin Pink

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

Jan 1, 1970

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-' and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.' An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By R. B. Porter, R. P. Porter, R. A. Lothrop

Changes became necessary in dredging methods employed in Idaho through passage of the Dredge Mining Protective Act (1954). Among other provisions, the law requires dredge operators to construct settling ponds of sufficient capacity and character to reasonably clarify the water used in the mining process before such water is discharged into the stream. Porter Bros. Corp., a placer mining company with many years operating experience in Oregon and Montana, became interested in strategic mineral placers in Idaho in 1950 when it was learned that prospectors had discovered a radioactive mineral deposit in Bear Valley Creek, 95 miles northeast of Boise. The company acquired mining leases and proceeded with exploration and development work on the property. After extensive research had resulted in the determination of successful separation processes, contracts were negotiated with the federal government and deliveries of columbium-tantalum and uranium concentrates commenced in 1956. The mining operations are located in a primitive area of Idaho among salmon spawning grounds and crystal-clear mountain trout streams. To avoid involvement in a very controversial issue, it appeared advisable for the company to develop water treatment procedures exceeding those requirements stated in the Idaho Dredge Mining Protective Act. Operation: The company operates one 6 cu ft continuous bucketline dredge and one 4 1/4 cu ft continuous bucketline dredge on the property. The dredges are jig-equipped, with feed being screened to 3 in. by trommels. The screening and gravity concentration methods satisfactorily separate the heavy minerals from companion clays, sand, and gravel. However, this separation of the heavy minerals requires water from the dredge pond with a minimum content of silt and colloids; therefore, water for dilution is added continuously to the dredge pond to suppress solids buildup. Discharge of this highly turbid water to maintain the proper pond level would ultimately result in an excessive silt load in Bear Valley Creek. To prohibit the turbid pond water from flowing directly into Bear Valley Creek, it was necessary to isolate the dredging area. Main by-pass canals were constructed along each side of the dredge pond and numerous secondary canals were dug for diverting seepage and snow runoff. One by-pass canal, extending more than two miles along the west side of the valley, diverts the main stream as well as tributaries entering from the west; a canal east of the dredge area diverts streams entering from that direction. At the beginning of operations in 1956, the dredge pond effluent was filtered through tailings and settled by use of coagulents in a series of lagoons. The filtrate was then discharged directly into the stream. Although this procedure gave satisfactory results in conformance with the state law, ice buildup and lagoon freezing hindered the efficiency of the process during periods of low temperature. For this reason, testing began in 1956 on a water treatment process that would operate efficiently under the extreme weather conditions encountered in Bear Valley. Development of Water Treatment System: Porter Bros. Corp. established the following requirements for effective continuous treatment of dredge pond effluent to the stream which, at low flow conditions, effluent to the stream which, at low flow conditions, would not result in a turbidity exceeding 25 ppm in the stream, 2) produce a sludge sufficiently dense to minimize disposal area requirements, 3) be semi-portable to follow dredge movements, 4) be capable of operating at low temperatures, and 5) be capable of handling a variety of capacities and turbidities.

Jan 1, 1961

By Herbert Hoover

IT is always a pleasure for me to join in the Ameri-can Mining Congress, for not only has my own professional life been closely linked with the industry, but the Secretary of Commerce is specifically enjoined in the organic act creating the office to promote and foster the interests of the mining industry. And it is a vital part of our national life. It is one of those indus-tries without which. the nation could not go on for a week. It ranks second only to the agricultural industry in its contribution to our raw materials. Its production amounts to nearly 6 ½ billions annually, providing direct support to probably ten millions of our people through employment to about two million workers. But the in-dustry has a greater importance than even these figures indicate, for with agriculture, forestry, and water power it furnishes the raw materials upon which the whole work of our civilization rests. When the raw ma-terials of our mines emerge. from manufacture with the added expenditure of labor and capital upon them, they have a wholesale value of over fifteen billions of dollars. And in this, the second stage of their application, they give employment to another two million workers and support to about ten million more of our people. A large portion of these manufactured commodities must filter through the retail trade; their total value when delivered to the consumer exceeds twenty billions of dollars. And from this distribution arises the support of many more millions of our people. It is estimated that the products of agriculture when they reach . the consumer, with transportation, manu-facturing, and distribution costs added, have about the same value as the mineral industries-each of them thus contributing about one-quarter of our total na-tional income. No other continent has demonstrated its possession of such a magnitude of minerals as has ours, and such a bountiful distribution over our whole land. But our mineral resources differ in one essential from our other natural resources-they are not renewable. Agricul-ture, forests, and water power replenish their supplies from season to season. Some people conclude from the non-renewable character of the mineral supply that they must shortly be exhausted. The practical question is ,one of time, and time in these matters needs to be measured in generations, and apprehension of exhaus-tion needs to be tempered with many probabilities in-cluding the advance in technical methods of extraction. In some of our minerals, such as coal, iron, and building materials we can, through a knowledge of their geologi-cal structure and occurrence, make fairly good estimates of our reserves. We. know that they will outlast many generations of Americans. In non-ferrous metals and oil, geology affords us no great basis for an estimate of future supply. We only know of the occurrence of minerals of this type by actual exposure of them, and we can thus make no estimates except upon reserves which have been proved by actual development by the process of mining. To develop them ahead merely for national satisfaction of assured future supply would imply an unbearable waste of capital. The consequence is that in these groups there is never a demonstrable assurance of more than a few years' supply ahead of us. Yet we have never failed from year to year to find new deposits and extension of old deposits.

Jan 1, 1928

By J. G. Kura, P. D. Frost, L. W. Eastwood

THE preparation and general properties of mag-nesium-lithium base alloys have been described in earlier papers.l,2 Lithium forms solid solutions with pure magnesium, lowers its density, and improves its formability. The improved isotropy and better formability of these alloys are attributed to the ability of lithium to convert the magnesium lattice from hexagonal (alpha phase) to body-centered-cubic (beta phase) structure. This change in structure is, however, accompanied by some limitations which make it difficult, if not impossible, to combine all the desirable properties in one composition. The most important of these limitations is the tendency of the high-strength alloys to overage and lose strength at temperatures of the order of 150" to 200°F. A study was made of the effects of composition and heat treatment on the age-hardening character- istics of the alloys. Stability of properties was determined by hardness and tensile testing of the alloys at room temperature after various periods of exposure to elevated temperatures. Precipitation-hardening curves are shown for a number of magnesium-lithium-zinc alloys in fig. 1. All the alloys were solution treated at 700°F and aged at 200°F. The reason for using the drastic quench, toluene at —105°F, was to reduce the rapid precipitation of the hardening phase which takes place at room temperature. Previous experience has shown that a hardness of about 90 to 95 Rockwell E is indicative of yield strengths in the range of 35,000 to 40,000 psi. This is a desirable strength level for magnesium-lithium base alloys with specific gravities of the order of 1.65 or less. Although the hardness level is raised by large zinc contents, a corresponding decrease in the cold formability of these alloys occurs with increasing zinc content. Thus, alloys containing up to about 10 pct Zn and having hardnesses of the order of 70 to 75 Rockwell E may be bent over a very small radius; however, the 16 pct Zn alloy requires a bend radius of more than 8T. The hardness relationships illustrated in fig. 1 can be explained by the partial phase diagram shown in fig. 2. The zinc-free magnesium-lithium alloys are entirely body-centered cubic (100 pct beta phase) when the lithium content of the binary is 10.3 pct or higher. When zinc is added, the boundary between the beta and alpha-plus-beta fields at 700°F is shifted to lower lithium contents. In addition, the solubility of zinc at 700°F decreases with decreasing lithium content. It is shown by a study of micro-structures that the limit of solid solubility of zinc in the 6Mg/Li* matrix at 700°F is about 19 pct. It is believed from a study of the aging curves that this limit is about 2 to 3 pct at 200°F. Zinc additions up to about 2 pct increase the hardness and strength of the magnesium-lithium base solid solution. Larger additions of zinc effect further hardness increases, but precipitate during prolonged aging at 200°F. Alloys having 14 to 20 pct Zn precipitation harden extremely rapidly during quenching, even when quenched in toluene at —105° F. The high-zinc alloys overage at 200°F but are capable of maintaining reasonably high hardnesses for periods up to 1000 hr.

Jan 1, 1951

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Ihor A. Kunasz

Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. However, with the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, presently exploited by Foote Mineral Co., and the Great Salt Lake of Utah, to be exploited by the Great Salt Lake Chemicals Corp., have been defined as major sources of lithium. Also a lithium-bearing brine has been discovered in Chile. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close down their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938. Its ionic radius is 0.60A and its charge is + 1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO)/Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns. 1955). Genetically, the pegmatites are associated kith neigh- boring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their respective distance from the granitic bodies to which they are genetically related (Mulligan, 1965). Lithium is also found in small proportions in a variety of rocks. The average lithium

Jan 1, 1975

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By P. Dayal, L. S. Darken

THE migration of carbon in austenite under the influence of an electric current has been observed qualitatively several times.14 Lebedev and Guterman5 recently have reported quantitative measurements; their method consisted of welding a low-carbon to a high-carbon wire, passing current, and later estimating the carbon distribution metal-lographically. We believe the method reported in this paper is superior in principle since electrolytic migration and ordinary diffusion are not necessarily coupled as in the weld method; also for the first time the extent of migration is determined by combustion analysis for carbon. A uniform tubular specimen (S.A.E. 1045 or 1095) was mounted as illustrated in the figures. the whole assembly being in an atmosphere of purified nitrogen. Direct current (129 to 226 amp at 0.65 to 1.0 v) served as source both of heat and of potential gradient for carbon migration. The duration of experiment was 7.5 to 12 hr, during which time the temperature was controlled (±10°C) manually. The experimental conditions are indicated in the first five columns of table I. With this experimental arrangement, the temperature initially has a maximum value at the central plane. Also, in this vicinity (by virtue of the symmetry), the carbon entering any volume element is equal in quantity to that leaving; the loss or accumulation of carbon occurs near the electrodes since the carbon moves uniformly near the center and is "frozen" at the cold ends. Hence, providing the time of experiment is not sufficiently long to seriously influence the conditions at the central plane, carbon crosses this plane only under the influence of the electrical potential gradient and not under the influence of temperature or concentration gradient. The amount of carbon which has crossed this plane was determined by combustion analysis of the two halves of the specimen. The results of these analyses are shown in the sixth and seventh columns of table I. It will be noted that substantial amounts of carbon migrated from the anode portion to the cathode portion (except at 920°C, which temperature was too low to exhibit the effect in the allotted time). In spite of precau-tions taken, considerable decarburization occurred as may be seen by comparing cols. 8 and 5. In three cases (indicated by asterisks in table I) the specimen was ground on one side, polished, and examined metallographically before analysis. One specimen was normalized and re-examined. Micrographs of selected areas in specimens 4 and 6 are shown in figs. 1 and 2, respectively. Evidence of carbon migration from the anode toward the cathode is quite apparent. Fig. 2 shows abundant graphite as well as cementite in a region near the cathode. The temperature of this zone is estimated at about 800°C. In fig. 1, particularly in the micrograph on the extreme right (the right side of which is of unaltered carbon content), there is evidence of slight depletion of carbon in the immediate vicinity of the cathode as contrasted to the general increase in carbon of the cathode half of the specimen. Although this may be attributed in part to decarbur-ization, it is believed that it is occasioned also by thermal diffusion—migration (of carbon) from a cool to a hot zone4—a phenomenon superimposed upon the electrical migration. Evidence of carbon migration was visible particu-larly during the course of the high-temperature,

Jan 1, 1951

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division's Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930's. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By R. Stefanko

The use of strain gauges and compression pads for an underground bolt installation in a central Pennsylvania coal mine revealed that satisfactory anchorage could not be maintained in the shale stratum that constituted the immediate roof. Comprehensive laboratory tests resulted in a new shell designed with an increased area of contact and smaller surface serrations. Retightening of the bolt was also found to be beneficial for maintenance of high load values. Roof bolting in coal mines has progressed very rapidly in the last decade, and today this method of support is in general use. There are many theories concerning the functions of roof bolts, but the importance of beam building is indisputable. Proper tension in the bolts minimizes shearing along bedding planes and creates a thick, competent beam from individually weak layers. Bolting must be accomplished immediately upon exposure of the roof, and bolt tension must be maintained if roof failure is to be prevented. Seams are being mined today with roof bolt support where conventional timbering was not effective.' The widespread use of continuous mining equipment was made possible by roof bolts which permit long supported spans free of obstructions. Since adequate anchorage is the key to successful bolting, better methods for determining the efficiency of anchorage are continually being sought. Attempts have been made to measure bolt loads, thus assessing anchorage efficiency by employing sensing devices between the bolt head and roof. 3-s None of the techniques appears to be very accurate, and all have at least one serious deficiency. The greatest efforts are being directed toward the standardization of the pull test.6" Nevertheless, the author believes that the pull test is only one criterion for establishing the efficiency of anchorage and not necessarily the most important one. The conventional pull test involves the short-term application of forces, whereas the success of roof bolt installations is dependent upon the ability of anchorage to sustain relatively long-term forces. Therefore, it would appear that the time-dependent function of the anchor is the single most important parameter for the success of roof bolting in many types of rocks. UNDERGROUND TESTS Strain gauges and compression pads were employed to measure bolt loads in a central Pennsylvania coal mine.8 Bolting had been employed only sporadically in the shale top since dubious benefits were obtained with this type of support. Table I shows some typical results from this investigation. Anchorage losses were extremely variable among the bolts, but all showed a considerable degree of bleed-off. The tests indicated that anchorage efficiency was extremely low in this type of shale. The results confirmed that bolting under these conditions was practically worthless, and thus a waste of material and labor. Probably even more important, bolting constituted a hazard when reliance was placed upon it for support. Certainly the complete lack of confidence in roof bolting, which was apparent in the mine personnel, was justifiable since the bolts did not accomplish their purpose. PRELIMINARY LABORATORY BOLT TESTS The extreme losses in bolt tension that were detected in underground installations prompted a comprehensive study to assess the causes. However, preliminary studies were first made to determine the combined stresses in a roof bolt and to prove conclusively that the observed bleed-off phenomena were due to anchorage: slippage and not to some other physical manifestation. In all of the ensuing tests

Jan 1, 1962

By William H. Spice

For the year 1943, exploratory drilling in South Central Texas continued on the sharp decline that started during 1942. Of the 3 counties comprising this district, as now revised to include the same area as is covered by District No. I, Oil and Gas Division, Railroad Commission of Texas, I5 counties are producing oil or gas. Only 29 exploratory wells were drilled during 1943, as compared with 51 exploratory wells in 1942, or a decrease of over 40 per cent. One new oil field and one new gas field were discovered during the year and a new horizon was discovered in an existing oil field. This cornpares with two new oil fields and an extension to an existing gas field in 1942. The one new oil field, South Washburn, in southeastern La Salle County, was discovered by Quintana Petroleum Corporation's No. I-D South Texas indicate in April 1943, flowing 4 bbl. per day, 48" A.P.I. gravity oil with an estimated 4 million cubic feet of gas from Wilcox sand at 6030 ft. This well i's the result of an extensive seismograph survey of the area. It is about 434 miles southwest of the same company's Green Branch field and by the end of the year one dry hole had been drilled to the southwest of this discovery. The one new gas field, which was not named, was located in eastern McMullen County by Edwin M. Jones' No. 102 Ezzell, in November 1943, for an estimated 8 million cubic feet of gas from shallow Jackson sand at 1222 ft. NO addi- tional wells have been drilled in this area, which may also be considered as an extension to the South Calliham field. The one new producing horizon was discovered in the South Campana field in southeastern McMullen County, by Argo Oil Corporation's No. 2-G Edrington, in January 1943, flowing 55 bbl. per day, 21' A.P.I. gravity oil with 40 per cent water from Government wells sand at 2609 feet. None of these discoveries were of major importance and subsequent development in these new areas has proved to be disappointing. Produc'tion for the district during 1943 totaled approximately 6,985,000 bbl. from about 3430 producing wells. This is an increase in production of about 5 per cent over 1942, but a decrease in producing wells of about 10 per cent under the number of wells producing in 1942 for the same district. Average production per well was 5.4 bbl. during 1943 as against 4.8 bbl. during 1942. Approximately 5,320,000 hhl. of this total production, or 76 per cent, was produced by the four Edwards lime fields, Luling, Branyon, Salt Flat, and Darst Creek, which are from 22 to 14 years old. The remaining production came from the 43 other active oil fields in the district. Drilling in the proven fields maintained approximately the same level as for 1942, with a total of 36 wells drilled. Of these operations, 21 were oil wells, one was a gas well and 14 were dry holes. This is a slightly better proportion of producers than for 1942. Washburn field had the greatest number of new producing wells drilled during the year, with a total of 10.

Jan 1, 1944

By William H. Spice

For the year 1943, exploratory drilling in South Central Texas continued on the sharp decline that started during 1942. Of the 3 counties comprising this district, as now revised to include the same area as is covered by District No. I, Oil and Gas Division, Railroad Commission of Texas, I5 counties are producing oil or gas. Only 29 exploratory wells were drilled during 1943, as compared with 51 exploratory wells in 1942, or a decrease of over 40 per cent. One new oil field and one new gas field were discovered during the year and a new horizon was discovered in an existing oil field. This cornpares with two new oil fields and an extension to an existing gas field in 1942. The one new oil field, South Washburn, in southeastern La Salle County, was discovered by Quintana Petroleum Corporation's No. I-D South Texas indicate in April 1943, flowing 4 bbl. per day, 48" A.P.I. gravity oil with an estimated 4 million cubic feet of gas from Wilcox sand at 6030 ft. This well i's the result of an extensive seismograph survey of the area. It is about 434 miles southwest of the same company's Green Branch field and by the end of the year one dry hole had been drilled to the southwest of this discovery. The one new gas field, which was not named, was located in eastern McMullen County by Edwin M. Jones' No. 102 Ezzell, in November 1943, for an estimated 8 million cubic feet of gas from shallow Jackson sand at 1222 ft. NO addi- tional wells have been drilled in this area, which may also be considered as an extension to the South Calliham field. The one new producing horizon was discovered in the South Campana field in southeastern McMullen County, by Argo Oil Corporation's No. 2-G Edrington, in January 1943, flowing 55 bbl. per day, 21' A.P.I. gravity oil with 40 per cent water from Government wells sand at 2609 feet. None of these discoveries were of major importance and subsequent development in these new areas has proved to be disappointing. Produc'tion for the district during 1943 totaled approximately 6,985,000 bbl. from about 3430 producing wells. This is an increase in production of about 5 per cent over 1942, but a decrease in producing wells of about 10 per cent under the number of wells producing in 1942 for the same district. Average production per well was 5.4 bbl. during 1943 as against 4.8 bbl. during 1942. Approximately 5,320,000 hhl. of this total production, or 76 per cent, was produced by the four Edwards lime fields, Luling, Branyon, Salt Flat, and Darst Creek, which are from 22 to 14 years old. The remaining production came from the 43 other active oil fields in the district. Drilling in the proven fields maintained approximately the same level as for 1942, with a total of 36 wells drilled. Of these operations, 21 were oil wells, one was a gas well and 14 were dry holes. This is a slightly better proportion of producers than for 1942. Washburn field had the greatest number of new producing wells drilled during the year, with a total of 10.

Jan 1, 1944

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.