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By J. W. Spretnak, H. R. Ogden, A. G. Imgram

The effect of working reduction, stress-relief annealing, and recrystallized grain size on the tensile and notch-tensile properties of molybdenum and Mo-0.5 Ti was studied. It was found that increasing the amount of working reduction increased the strength and reduced the tendencies toward brittle behavior. Stress -relief annealing did not alter the strength but lowered the transition temperature. Increasing the recrystallized grain size lowered the strength and raised the transition temperature. The notch -unnotch strength ratio began to decrease with decreasing temperature at temperatures below those at which the notched ductility fell to zero for all of the micro structural conditions investigated. BEING bcc metals, the refractory metals in Groups Va and VIa (V, Cb, Ta, and Cr, Mo, W) undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures. Previous research has shown that molybdenum and tungsten not only have higher transition temperatures than columbium and tantalum but show a marked sensitivity of transition temperature to structure as well.' Recrystallized materials become brittle at considerably higher temperatures than is the case with material having a worked or fibered micro-structure. Evidence of structure sensitivity has also been detected in columbium- and tantalum-base alloys containing appreciable amounts of molybdenum or tungsten such as F-48 (Cb-15W-5Mo-1Zr) and Ta-10w.2 This paper describes the results of research conducted to further evaluate the effects of metal. lurgical structure on the low-temperature tensile and notch-tensile properties of molybdenum and Mo-0.5Ti. The effects of rolling reduction, stress-relief annealing temperature, and recrystallized grain size were studied. Considerable progress has been made in explaining the fundamental mechanisms of the flow and fracture characteristics of bcc metals. Several of these concepts are helpful in interpreting the data obtained in this study. Brittle fractures occur when the highly temperature-sensitive yield strength equals, or exceeds, the temperature-insensitive brittle cleavage fracture stress.3 The rapid increase in yield strength with decreasing temperature, characteristic of all bcc metals, is therefore of primary concern. petch4 has described the yield strength, ay, (stress required to initiate plastic flow) of bcc metals by the expression where ai is the frictional resistance to slip, Ky is a constant numerically equal to the slope of a a vs curve, and 2d is the average grain diamefer. The oi term itself is thought to be composed of a temperature-insensitive component dependent on impurity content and second-phase particles and a temperature-sensitive component dependent on the Pierls-Nabarro force.5 This equation has also been demonstrated to hold for the flow stress (stress required to maintain continued plastic flow).' Brittle-crack nucleation is thought to occur by the coalescence of dislocations piled up in slip planes at sessile dislocations or twin and grain boundaries.7,8 These proposed mechanisms require that a large number of dislocations be released into the active slip planes so that sufficiently large stress concentrations are produced at the dislocation pile-ups to enable coalescence into a micro-crack. Therefore, at least a microscopic amount of slip must occur in some grains to facilitate initial crack formation. Cottrell 7 has predicted that brittle fracture, nucleated by slip, should occur when where ty is the shear yield strength, ß = 1 in un- notched xension, u is the shear modulus, and y is the effective surface energy. This equation incorporates the Griffith concept of fracture that a crack will propagate if the decrease in strain energy equals or exceeds the increase in surface energy.

Jan 1, 1964

By David J. Mack, T. V. Philip

The effects on the Cu-A1 eutectoid transformation of the addition of a third element from the second long period and from Group IIB of the periodic table, were studied by isothermal transfomation techniques. The valency of the third element shows the most pronounced effect on the eutectoid decomposition. With some exceptions, the atomic size factor of the third element shows some consistent effects on pearlite nucleation and growth. The atomic concentration or the electronegative valency of the third element shows wo consistent effect on the eutectoid decomposition. Addition of the third element helps spheroidization of pearlite. SINCE the pioneering work of Davenport and Bainl on the eutectoid decomposition in steel by the isothermal transformation technique, an enormous amount of data has been accumulated on the eutectoid transformation characteristics of commercial steels. While the eutectoid reaction in steel is of tremendous industrial importance, it appears to be quite unique among the eutectoid reactions. Though the metal-lographic structures developed in the Fe-C and Cu-A1 eutectoids are similar, it is now evident that the two eutectoid reactions are quite dissimilar. The eutectoid decomposition in the Cu-A1 system is more complicated partly due to the appearance of transitional phases in addition to the equilibrium phases. * The first isothermal studies of aluminum bronzes were made by Smith and Lindlief2 and later by Mack,3 Klier, and Grymko,4 and recently Hayne 5,6 A few other systems, structurally analogous to the above, have been studied by the same technique.7-10 Kasberg and Mack1' studied the effects of iron on the transformation of commercial aluminum bronze. The effects of manganese and nickel on this aluminum bronze and those of iron, manganese, and nickel on the binary Cu-A1 eutectoid have been recently studied.12 The object of the present investigation was to study, by isothermal transformation techniques, the effects (with respect to the fundamental factors of alloy formation) of the addition of a third element on the transformation of a Cu-Al eutectoid alloy, 11.8 pct Al. The third elements chosen for the purpose were silver, cadmium, indium, tin, and antimony from the second long period, and beryllium, zinc, and cadmium from group 11B of the periodic table. They were added in nominal amounts of 0.5, 1.0, and 2.5 pct by weight to a eutectoid Cu-A1 alloy. These third elements were expected to show the effects of electron valency, atomic size factor, and electronegative valency effects on the binary eutectoid transformation. PFLEPARATION OF ALLOYS AND PROCEDURE All alloys were made as 400-g heats by induction melting in a graphite crucible with a graphite lid. The molten alloy with a layer of graphite powder on top was stirred at regular intervals by a graphite rod. When the melt was judged to have acquired sufficient superheat, a pinch of common salt was sprinkled on top and any crust scraped off to one side. It was then chill cast into a 5/8 in. rod. The alloys with silver were prepared by remelt-ing the high-purity Cu-A1 eutectoid alloy used by Mack3 with high-purity silver (99.99 pct pure from Hardy and Harmon, Inc.). In the preparation of all the other alloys, polished electrolytic copper shot (from Belmont Smelting and Refining Co.) and high-purity aluminum (99.99 pct pure from Aluminum Co. of America) were used.

Jan 1, 1962

By W. L. Phillips

Nickel alloys containing approximately 0.5, 2.0, and 6.0 at. pct of Os, Pd, Ru, and Rh were Prepared by vacuum melting. Tension tests were carried out at 25°, 500°, 800°, and 1000°C; stress-rupture tests were carried out at 650° and 800°C. The room- and elevated-temperature tensile strength, as well as the stress-rupture life, increased for the same atomic percent in the order palladium, rhodium, ruthenium, osmium. The ductility decreased with increasing concentration or temperature for a given concentration. The results are discussed in terms of solid-solution theory. BOTH solid-solution strengthening and weakening have been observed in alloys. The simple rules which have been suggested to explain alloy strengthening are subject to several exceptions and deviations based on atom size and valency effects. The purpose of the present investigation was to extend the knowledge of the effect of solid-solution alloying on the mechanical properties of several Ni-Pt group metal alloys at room and elevated temperatures. The platinum group metals, osmium, ruthenium, rhodium, and palladium were chosen as the solute elements because of their different valencies and atom sizes. Nickel was chosen as the base material because of the large amount of previous literature available on nickel alloys. EXPERIMENTAL PROCEDURE Grade A Carbonyl nickel powder having the following composition: C, 0.07 pct; Fe, 0.013 pct; Mn, 0.0005 pct; Si, 0.016 pct; Mg, 0.0003 pct; S, 0.003 pct, was purchased from the International Nickel Co. The platinum-group metal powders were purchased from A. D. Mackay Co. The powders were weighed, cone-blended for 4 hr, and vacuum-melted into 1-in.-diam billets, approximately 2 in. long. The ingots were homogenized for 5 hr at 1800°F before being extruded into 1/4-in. rods at 2100°F. The alloy compositions are shown in Table I. Typical impurity values were not significantly different than that of the as-received nickel. All alloys were single phase. The lattice parameter of each alloy after the heat treatment described below is also included in Table I. Each alloy was annealed at 2200°F for 1 hr and air-quenched to comparable grain sizes (ASTM G.S. No. 4-5). The rods were then machined into test samples 0.160-in. diam and 0.750-in. gage length. Tension testing was carried out in an In-stron tension-testing machine at a strain rate of 0.02 in. per in. per min. An extensometer was used to determine the room-temperature yield stress. Stress-rupture testing was carried out in an Arc Weld stress-rupture unit. All testing was performed in air. EXPERIMENTAL RESULTS A) Room-Temperature Mechanical Properties. The 0.2 pct yield stress, ultimate tensile strength, and elongation for all alloys tested at room temperature are plotted as a function of atomic percent solute element in Fig. 1. The ultimate tensile strength for the same atomic percent increases in the order palladium, rhodium, ruthenium, osmium. The yield strength at low concentrations, -0.5 at. pct, increases in the order osmium, palladium, ruthenium, rhodium. At higher concentrations, 3.0 and 10.0 pct, the yield strength increases in the same order as the tensile strength. Both yield strength and tensile strength increase rapidly ini-

Jan 1, 1964

By R. Hastings Keller, Ralph E. Esarey

Oil and gas activities in Indiana during 1943 continued to decline at about the same rate as in 1942. New development, production, and prospecting, all showed the results of Federal regulation, low price for crude oil and shortages of labor and materials. Several local stripper-well operations were shut down, but no large-scale abandonment has occurred as yet. During the year, 277 holes were drilled for oil and/or gas, of which 99 were completed as oil wells, 19 as gas wells and 159 as dry holes. This record was a decline of 21 per cent over last year in the total number of completed tests, 20 per cent in the number of oil wells and 9.5 per cent in the number of gas wells. As in the previous year, most of the drilling (82 per cent) was in the southwestern part of the state, Gibson County ranking first, with 77 completions and 49 oil wells. Posey County was second, with 59 completions and 20 oil wells. The remaining 18 per cent of the drilling was in the old Trenton oil and gas area. The total footage drilled during the year was 482,799 ft., a decline of 18 per cent from the previous year. Of this, 146,559 ft. was wildcat footage. The total initial production of the oil wells completed was 6362 bbl. and of the gas wells was 2,562,000 cu. feet. Three tests in the old Trenton area were drilled into the Cambrian and reported nothing more than tar residue. A Devonian test was to be made in the Griffin field in the Wabash River but owing to the delay caused by Federal restrictions this test did not get started in 1943. It is expected to spud in March 1944. The new discoveries in 1943 were virtually all in the southwestern part of the state, and all, so far, one-well pools, except the North Owensville pool, in Gibson County. The latter was brought in during the month of February and by the end of the year nine wells were producing in the pool, with a reported initial yield of 1260 bbl. per day. By the end of the year it had a daily average production of 401 bbl. and an accumulated production of 39,129 bbl. The average gravity of the oil is reported to be 35.6. On the Ohio-Indiana state line, early in 1943, a new pool was opened up in the old Trenton area. The discovery well was on the Ohio side of the line. An offset well was completed on the Indiana side, with an initial yield of 64 bbl., and settled down to 5 bbl. per day. This well produced 1154 bbl. up to Dec. 31, 1943. There was no further development here, because of the Federal Conservation Order M-68, restricting drilling to one well on 40 acres. The development pattern usually followed in this area is one well to 5 acres. The E. Rogers field was extended by one pool (Table 4). Most of the development in the oil-field pools during the year took place in the Kirksville pool, in Gibson County, and the Caborn pool, in Posey County. The crude-oil production in 1943 was approximately 5,273,000 bbl., a decline of 29 per cent from the previous year. The Griffin field, of Gibson and Posey Counties,

Jan 1, 1944

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

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

Jan 1, 1970

By R. Hastings Keller, Ralph E. Esarey

Oil and gas activities in Indiana during 1943 continued to decline at about the same rate as in 1942. New development, production, and prospecting, all showed the results of Federal regulation, low price for crude oil and shortages of labor and materials. Several local stripper-well operations were shut down, but no large-scale abandonment has occurred as yet. During the year, 277 holes were drilled for oil and/or gas, of which 99 were completed as oil wells, 19 as gas wells and 159 as dry holes. This record was a decline of 21 per cent over last year in the total number of completed tests, 20 per cent in the number of oil wells and 9.5 per cent in the number of gas wells. As in the previous year, most of the drilling (82 per cent) was in the southwestern part of the state, Gibson County ranking first, with 77 completions and 49 oil wells. Posey County was second, with 59 completions and 20 oil wells. The remaining 18 per cent of the drilling was in the old Trenton oil and gas area. The total footage drilled during the year was 482,799 ft., a decline of 18 per cent from the previous year. Of this, 146,559 ft. was wildcat footage. The total initial production of the oil wells completed was 6362 bbl. and of the gas wells was 2,562,000 cu. feet. Three tests in the old Trenton area were drilled into the Cambrian and reported nothing more than tar residue. A Devonian test was to be made in the Griffin field in the Wabash River but owing to the delay caused by Federal restrictions this test did not get started in 1943. It is expected to spud in March 1944. The new discoveries in 1943 were virtually all in the southwestern part of the state, and all, so far, one-well pools, except the North Owensville pool, in Gibson County. The latter was brought in during the month of February and by the end of the year nine wells were producing in the pool, with a reported initial yield of 1260 bbl. per day. By the end of the year it had a daily average production of 401 bbl. and an accumulated production of 39,129 bbl. The average gravity of the oil is reported to be 35.6. On the Ohio-Indiana state line, early in 1943, a new pool was opened up in the old Trenton area. The discovery well was on the Ohio side of the line. An offset well was completed on the Indiana side, with an initial yield of 64 bbl., and settled down to 5 bbl. per day. This well produced 1154 bbl. up to Dec. 31, 1943. There was no further development here, because of the Federal Conservation Order M-68, restricting drilling to one well on 40 acres. The development pattern usually followed in this area is one well to 5 acres. The E. Rogers field was extended by one pool (Table 4). Most of the development in the oil-field pools during the year took place in the Kirksville pool, in Gibson County, and the Caborn pool, in Posey County. The crude-oil production in 1943 was approximately 5,273,000 bbl., a decline of 29 per cent from the previous year. The Griffin field, of Gibson and Posey Counties,

Jan 1, 1944

By M. J. Hordon, M. A. Wright

ReCENT work has indicated that the substantial decrease in the rate of fatigue crack propagation for aluminum observed below a critical vacuum level can be attributed to the depletion of oxygen or water vapor from the vicinity of the fatigue crack opening.' At reduced gas pressures, generally below 10-2 Torr with fatigue strain amplitudes in the range *1 to 2 x 10-3 and cyclic loading rates of 25 to 50 cps, estimated rates of oxide or hydroxide monolayer adsorption on newly formed crack surfaces can fall behind the actual rate of crack extension. Changes in the critical pressure required for the transition in fatigue behavior with changes in temperature, strain amplitude, and cyclic frequency can be interpreted from variations in the adsorption and crack growth rates.'" Although the adsorption model generally appears to explain the enhanced fatigue resistance of reactive metals in vacuum, the specific adsorbing gas species and nature of the adsorption mechanism are uncertain. In addition to the direct dissociation and adsorption of O2 on the metal surfaces,3 the dissociation of H20 and subsequent adsorption of H ions have been advanced for aluminum alloys.4 The present note describes some measurements of the fatigue behavior of 1100 aluminum in reduced partial pressures of specific gases including O2, H2O, and H2 in order to provide additional experimental data. Cantilever-type specimens of 1100-H14 aluminum were fatigued in cyclic reverse bending at constant strain amplitude using a multispecimen vacuum apparatus and procedure described previously.' After initial vacuum evacuation to 1 x 10-7 Torr, the appropriate gas species was bled into the system through a calibrated leak valve. The input rate was adjusted to maintain the desired pressure level under continuous evacuation, thus minimizing possible changes in gas composition during testing. High-purity input gases including 99.9 pct O2, 99.999 pct H 2, and water vapor from triply distilled H 2 O were used to provide residual pressures. Trace amounts of contaminant species were limited by passing the Oz and H 2 input gases through liquid-nitrogen-cooled copper coils prior to entry to the test chamber. Care was taken to repeatedly flush the gas lines and valves before testing to minimize the effect of adsorbed contaminants. Residual gas pressures in the range 10-6 to 5 x x3 Torr were monitored by an NRC ionization gage corrected for each gas species. In the higher-pressure range, 5 x 1CT3 to 5 x 10' Torr, an NRC alphatron gage was used. In operation, eight simultaneous fatigue tests were conducted at a constant strain amplitude of *1.2 x 10 at cyclic bending rates of 25 and 50 cps to give an average fatigue life of 6.5x 105 cycles-to-fracture at standard atmosphere and 3.3 x 106 cycles in 1 x 10"7 Torr vacuum. Representative results for the effect of residual O2, H2O, and H2 contents on the fatigue life are shown in Fig. 1 for tests performed at 50 cps. It is apparent that the presence of either O2 or H2O gas in the system at partial pressures greater than 10"3 Torr was noticeably detrimental to the fatigue life. In contrast, the enhanced fatigue resistance typical of high-vacuum environments was retained with pure H 2 through the pressure range up to 1 Torr. For partial pressures of H2 gas above 1 Torr, the fracture life noticeably decreased. The critical Hz

Jan 1, 1969

By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-&apos;. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5&apos;9 for these high concentrations of phosphorus do not follow Fick&apos;s laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1&apos; that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7&apos;8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By H. R. Thresh, A. F. Crawley

THIS paper reports the results of viscosity measurements on cadmium and indium undertaken as part of a continuing program of liquid metals research at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. For several years this work has continued with support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. In the literature, existing viscosity data for cadmium are conflicting and for indium are scarce. To achieve reliable viscosity values, further work was deemed desirable. Viscosities were measured using an absolute technique applied to an oscillating closed right cylinder of liquid metal. The apparatus, constructed in this laboratory, and the techniques involved in its use have been described in an earlier paper.&apos; In calculating viscosity coefficients from the experimental data. Roscoe&apos;s2 mathematical analysis was used. Because accurate viscosity determinations are dependent on accurate density data, and since the available data in the literature are conflicting, the densities of liquid cadmium and indium were also determined in this laboratory by a pycnometric technique. This increased the control exercised over all the variables contributing to the accuracy of viscosity measurements. For both density and viscosity determinations, cadmium and indium of 99.999 pct purity were used. These materials were obtained from Cominco Ltd. In order to suppress excessive evaporation losses and help prevent oxidation, a technique developed in measuring the viscosity of zinc&apos; was used for cadmium. This involved maintaining an atmosphere of purified hydrogen in the viscosimeter during the rela- tively long periods while the experimental temperature was changed and stabilized between individual determinations of the logarithmic decrement. Then, immediately prior to a decrement measurement. the viscosimeter was rapidly evacuated to a pressure of about 2 X 10-6 torr. On the other hand. with indium. no difficulties arise from vaporization or oxidation. In this case. therefore. the apparatus was held under a constant vacuum of about 2 x 10-6 torr. When all sources of random and systematic error have been evaluated, the technique is considered to yield data accurate within 10.5 pct. The viscosity of cadmium was measured to a maximum temperature of 451.8°C and that of indium to 346.5°C. These temperatures are. respectively. 130° and 190°C above the melting points. Two separate runs were made on indium. The results are given in Table I and, when plotted. yield the smooth curves evident in Figs. 1 and 2. Values of A and C to fit the well-known Andrade1 equation were determined by a regression analysis. The equation is: where n = coefficient of viscosity. i = specific volume. T = temperature in °K Despite its empirical nature. Andrade&apos;s equation has been shown by many workers to describe accurately the temperature dependence of viscosity. During the current research program, this equation has been found to fit the data precisely for all the metals and alloys that have been studied.5,6 The A and C&apos; values for cadmium and indium are given in Table 11. Comparing the magnitude of the present data with those of previous workers,7-10 as has been done in Fig. 1, it is evident that the results of Fisher and Phillips10 deviate markedly from the rest. With the exception of one point from Gering and Sauerwald,7 all other data agree within ±2.5 pct. However, the agreement between the present results and the work of Menz and sauerwald9 is especially good over the entire experimental temperature range. Such agreement may be expected since Menz and Sauerwald&apos;s

Jan 1, 1970

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf&apos;s CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.&apos; This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

By F. R. Brotzen, A. R. Troiano, E. L. Harmon

Precipitation processes leading to drastic property changes are a frequent occurrence in titanium alloys containing large amounts of the retained high temperature P phase. In order to establish the kinetics and nature of these precipitation processes, a series of Ti-V alloys was studied. Time-temperature-transformation diqgrams were obtained for 12.5 and 15 pct V-Ti alloys. These diagrams consisted of two intersecting C-shaped curves: one in the high temperature region for the euilibrium transformation P +u+P, and another at lower temperatures depicting the formation of the meta-stable transition phase, o. Presence of the transition phase retarded the precipitation of the equilibrium a phase. Deformation of retained P resulted in the formation of the o phase. Reversion and retrogression phenomena of the transition phase were observed. A negative temperature coefficient of resistance was found in quenched alloys containing from 15 to 20 pct V. CERTAIN titanium-base alloys can be heat treated to produce appreciable changes in properties. For example, remarkably high hardness values may be obtained by aging or isothermal quenching treatments. Most of the information available to date on the hardening of titanium-base alloys has been systematized recently in an article by L. D. Jaffe.&apos; It was pointed out by that author that the hardening was the result of the decomposition of the retained j3 phase to the equilibrium constituents, a and p, and that this decomposition had many of the characteristics of an age-hardening reaction. Recent work by Frost et al.&apos; 3 has contributed much to the fundamental understanding of the hardening mechanism in titanium-base systems. These authors established the presence of a transition phase in the transformation from j3 to a + j3, which they designated o. The transition phase, in their opinion, was at least partially responsible for the hardening and embrittling effects which accompanied low temperature aging. The present investigation of the mechanism and kinetics of the hardening reaction was carried out for the Ti-V system. Ti-V alloys were ideally suited for a study of the decomposition of j3, since age hardening was known to occur readily in this system." Moreover, no intermetallic compounds occur in this system, Fig. 1, thus simplifying the interpretation of the results. Material and Procedure Alloys containing 12.5 and 15 pct V were prepared by Battelle Memorial Institute from iodide titanium furnished by Watertown Arsenal and vanadium of 99.8 pct purity. Ingots of 8 Ib each were prepared by arc melting in an inert atmosphere with a tungsten electrode and water-cooled copper crucible. Each of the ingots was melted once, forged at 1600°, and rolled at 1400°F. Following this, the ingots were remelted, forged, and then rolled to % in. sq bars, which were subsequently grit blasted, pickled, and wire brushed. Another set of alloys containing nominally 17.5 and 20 pct V was produced by the Research Div., New York University. These alloys were arc melted in an inert atmosphere in lots of 20 g each. Heat-Treating Procedure: Whenever feasible, specimens were heat treated in high vacuum resistance furnaces at pressures below 5x10." mm of Hg. Aging and isothermal quenching treatments were generally carried out in salt baths. Specimens were not attacked by the salt, provided the tempera-

Jan 1, 1956

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By J. Kucera, J. Vreštál

DIFFERENT authors1 &apos; have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-&apos;3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing&apos;s coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me&apos;tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By M. P. E. Desvaux, P. Charsley

OLIP-line observations on copper alloys, using the electron microscope, have been made by a number of workers,13 but this work has been confined to a brass. In a CuAl alloys Koppenaal4 and Koppenaal and Fine5 have made observations with the optical microscope and by the use of interferometry. They found that the observed slip step heights inside the Liiders bands accounted for only 42 pet of the total macroscopic strain. The suggestion was put forward that optically unresolvable slip in other parts of the specimen accounted for a major part of the macroscopic strain. This is surprising since it is known from other workers that slip in a brass is inhomogeneous; i.e., large amounts of slip occur on individual {lll) closelys paced than being shared by a large number of closely spaced planes. Furthermore, a brass and a CuAl alloys with high concentration of aluminum exhibit similar deformation characteristics and slip-line patterns. Prior to investigations into the behavior of copper and a CuAl alloys under reversed stresses in tension and compression, some preliminary experiments have yielded results which the authors think resolve this discrepancy, and throw some further light on the behavior of a CuAl in tension. An experiment was carried out on a 10 at. pet CuAl single crystal, of gage length 7.5 cm, diameter 3.1 mm, and orientation shown in Fig. 3 (inset), for the purpose of resolving the above discrepancy. The specimen gage length was electropolished for 10 min in a 50:50 orthophosphoric acid (SG=1.75)-distilled water system, with 2 v across the cell and a current density of 0.5 amp per sq cm. The cathode was made of copper. After a tensile strain of 0.067 ± 0.001, intense slip was observed over a length 2 cm of the gage length whilst the rest of the specimen was relatively undeformed. In the lightly deformed region, slip bands of mean width 20 /x were spaced about 1 mm apart on average. The transition from the heavily slipped region (usually called a Liiders band) to the lightly deformed region was gradual, the slip-band density increasing as the "Liiders band" was approached. In the latter, the slip bands became so close together that, to the naked eye, the specimen appeared to be continously slipped, and the typical microtopography of this region is shown in Fig. 1. Twelve electron micrographs were taken at random from replicas of the Liiders-band region, and the widths of the slip lines were measured. The slip lines account for an over-all tensile deformation of 7.0 ± 0.7 pet, after allowing for the lengths of the un-slipped regions, which is in good agreement with the macroscopic strain. The distribution of slip-line widths was also measured and is shown in Fig. 3. Since Koppenaal could not resolve slip lines with height less than 540A (limit of resolution represented by dashed line), then it was deduced that he could have measured only about 50 pet of the deformation within the &apos;Liiders Band&apos;. It is concluded, contrary to the suggestion of Koppenaal,5 that virtually all the macroscopic strain is accommodated within the "Luders band" and that there is no need to invoke fine slip distributed uniformly over the gage length.

Jan 1, 1967

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&apos;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&apos;s the result of an extensive seismograph survey of the area. It is about 434 miles southwest of the same company&apos;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&apos; 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&apos;s No. 2-G Edrington, in January 1943, flowing 55 bbl. per day, 21&apos; 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&apos;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&apos;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&apos;s the result of an extensive seismograph survey of the area. It is about 434 miles southwest of the same company&apos;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&apos; 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&apos;s No. 2-G Edrington, in January 1943, flowing 55 bbl. per day, 21&apos; 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&apos;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 N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969