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By Lewis W. MacNaughton

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wil-barger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1940 The encouraging outcome of exploration and development in Montague and Cooke Counties and generally greater activity throughout the district resulted in the drilling of some 1700 wells during 1940, about 350 more wells than were drilled in 1939. Approximately 1250 of these tests were completed as oil wells. Production likewise increased during I940 to the extent of 8 million barrels more than the 25 1/2 million barrels produced in 1939. In spite of this large increase in production, known oil reserves again increased substantially. As is usually characteristic of this district, the new reserves were from a large number of fields, none of which were of such magnitude as to be important to the oil industry. Nevertheless, the Fargo field, Wilbarger County, deserves mention as one of the more important discoveries in this district during 1940. Following seismic surveys, the hmerada Petroleum Corporation located its No. I Goodpasture in sec. 35, block IS, H. and T. C. R. R. Co. survey, and drilled it to a total depth of 6717 ft. This well was completed in July 1940 through perforations in the casing from a pay between 3230 and 3252 ft. for an initial production of 241.5 bbl. on an 8-hr. pumping test. Other potential producing horizons were found in the Pennsyl-vanian at depths of 3960 to 3995 ft., 4208 to 11.234 ft., 4407 to 4422 ft., and in the Ordovician at 6300 ft. Wells completed to date in the several Pennsylvanian horizons have an average daily potential of 600 bbl. of oil. Although no wells have yet been completed in the Ellenburger dolomite (Ordovician), the discovery well swabbed I5 bbl. per hour from this formation before plugging back for completion in an upper horizon.

Jan 1, 1941

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

Jan 1, 1970

By K. J. Anusavice, R. T. DeHoff, A. G. Guy, T. B. Lindemer

As one oi the approacizes to understanding multicorn-ponent dimsion, an expevinzental sturly is being jnade of tracer diffusion in the copper corner of the CLI-Ni-Zn syste?n, out to 30 at. pct each of nickel and zinc, and in the 150°C range oJ temperature just below tlze solidts te?rlperature. The reslts obtained using the Znm isotope are reported heve, while studies with nickel and copper isotopes are planned for a future paper. The fifteen alloys investigated were melted in sealed wear lubes, sroaged, homogenized, and then analyzed, using the conventional isotope-plating plus lathe- sectiorzing teclzniqlte. The data obtaiued show that the difJusion coeflcient of the zinc isotope increases titlz increase in zinc content, and decreases t'itlz incease in nickel content. The correlation xith solidus temperature is particularly strong. Diffirsiui-ties ranged fro u sq cm per sec nt tlze Iiigh-zinc, low-nickel compositions. The activation energy /or tracer diffusion ravied j.or 31.000 to 54,000 calper mole. It is now generally recognized that diffusion data and theories are needed for multicomponent systems, where extensive practical developments and even some theoretical studies have already been made. For example, much recent work on precipitation from solid solution has been concerned with ternary solid solutions such as A-M-Z' while Zener relaxation has been studied on Au-Ag-Zn alloys,' although adequate diffusion data are available for neither of these systems. Actually, the only ternary systems for which systematic diffusion studies have been begun, in addi- tion to the one reported here, are CO-i-cr3 and Cu-A-Au. Since the theory of multicomponent diffusion is still in the stage of active development5 it is important to distinguish the various kinds of diffusion data that can be determined. An oversimplified approach, widely used prior to 1950, was to determine the influence of a third element, such as nickel, on the diffusion behavior of a binary alloy, such as CU-Z. Later it was recognized7 that four diffusion coefficients can be used to describe ordinary interdiffusion in a ternary system, while as many as six coefficients may be required to include the Kirkendall effect. It is likely that the number of independent coefficients will be shown to be less than four and six, respectively, through the application of the thermodynamics of irreversible processes.5 The simplest type of diffusion in a multicomponent system is tracer diffusion, since each component is characterized by its own tracer-diffusion coefficient in an alloy of a given composition. Thus, in a ternary alloy there are three tracer-diffusion coefficients, each a function of composition and temperature. The present research program is a study of tracer diffusion in the copper corner of the Cu-Ni-Zn system out to 30 at. pct each of Ni and Zn in a 150°C range of temperature just below the solidus temperature. The

Jan 1, 1967

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

CONTENTS DAVIS, CARL R., WILLEY, J. L., and EWING, S. E. T.-Recent Developments in the Fine Grinding and Treatment of Witwatersrand Ores. Discussed by Charles E. Locke, H. W. Hardinge, H. N. Spicer, G. M. Brown, Justice F. Grugan, R. C. Canby 1 WEINIG, A. J., and BOWEN, MAX W.-Determination of Dissolved Oxygen in Cyanide Solutions. Discussed by A. L. Blomfield, M. F. Dycus, A. W. Bull.... 4 LEPSOE, ROBERT.-Precipitation Efficiency of Zinc Dust in Cyanide Process. Discussed by G. M. Brown, Charles E. Locke 5 Recent Developments in the Fine Grinding and Treatment of Witwatersrand Ores Discussion of the paper of CARL R. DAVIS, J. L. WILLEY, S. E. T. EWING, presented at the New York Meeting, February, 1925, and issued as Paper No. 1386-B, with MINING AND METALLURGY, December, 1924. CHARLES E. LOCKE, Cambridge, Mass.-In this country, we have come to think that we should use smaller size of feed in our ball-mills. I will admit that a ball-mill is not comparable to a tube-mill, as conditions may not be the same, but there we have an unusual demonstration of the advantage of a coarser feed. Further investigation along this line is going to lead to some valuable results. The authors have overcome the difficulty of this coarse feed by taking out what I would call the difficult lumps, It is not clear from the paper whether many of these difficult lumps' may not be 'reduced portions of their grinding media. H. W. HARDINGE, New York, N. Y.-The idea is not exactly new because in 1911 they used the miner to reduce the finer material. We proceeded three or four years using many tons, about 15 tons. or nearly the same proportion of ore to grinding medium. Another thing to be taken into account is the hardness of the ore being ground. In South Africa, the transportation costs must be, taken into account. They are also making progress in the method of using tube-mills and ball-mills instead of stamps. Experiments are to be conducted with 10-ft. diameter mills there, with the object of increasing the mass action and agitation which, as has been demonstrated under different circumstances, increases the overall efficiency.

Jan 6, 1925

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By Paul A. Schafer

BALATOC mine, the principal gold-producing mine in the Philippines, is 10 miles southeast of Baguio, in the Cordillera Central of northern Luzon.1 The region is a deeply dissected plateau, ranging in altitude from 3000 t0 5000 ft. above sea level. The rocks consist chiefly of granodiorite, diorite, and remnants of metamorphosed sediments, cut by dikes of andesite porphyry and quartz-diorite porphyry. All are intruded by a volcanic breccia plug, oval in horizontal section, about 3200 ft. long and 2300 ft. wide, which is the north central part of the mineralized area. Three main vein systems have been developed (Fig. 1): q6, 231 and 364, which strike about N.70°E. and dip 5o to 90°S. Each system is a braided zone consisting of many individual components. They are disturbed by a series of premineral faults or shear zones striking about N.45°E. Twelve of these produce important effects on the persistence, character, and quality of veins. From west to east the faults are named (after claims): Hog, Big Gun, Bull, Pine, Lolita, Bar No. I, Bar No. 2, Curt, Sun, Helen, Itoe, and Frog. They are early breaks formed prior to the N.70°E. vein fractures. Mineralization occurs on them but, with several prominent exceptions, they are too low grade to mine. A number of northwesterly striking faults complete the structural pattern. Although they are relatively abundant, the effect on the veins is so small that they do not present any problems in mining or development. All of these faults that have been observed are later than the N.70°E. veins and offset them to the left. NORTHEAST FAULTS The early northeast faults* are notably continuous in spite of their small displacements, 20 to 100 ft. Frequently they appear so weak that their importance is masked and their identity clouded. The gouge along any of these faults may vary from exceedingly weak at one point to very strong at another point only a short distance away. In other words, the amount of gouge depends on the changes of attitude of the fault plane, and is no indication of the extent of the movement. Places where walls are spread apart are filled with gouge squeezed from tight places. Also, mineralization sometimes obscures fault gouges by replacement. The mineralization of northeast faults has produced several important ore bodies; namely, 231 west on Pine fault and q6 vein on the same fault. To a smaller extent, Lolita, Curt, Bull, Bar No. I, and Sun

Jan 1, 1942

By H. D. Outmans

A method has been developed for determining the relative water wet-tability (fraction of the surface wet by water) of porous media. This method involves the adsorption of methylene blue dye from an aqueous solution onto the solid surfaces of rock contacted by the injected dye solution. Experiments on Berea snndstone cores have shown that water-wet cores adsorb a large amount of dye from solution. In oil-wet cores, however, the injected aqueous dye solution is prevented from contacting the adsorptive surfuces by a film of oil and virtually no dye is adsorbed. This method was tested by experiments on mixtures of water-wet and oil-wet sand. Using the dye adsorption method, it was possible to determine quantitatively the fraction of water-wet and oil-wet sarzd in such mixtures. The dye adsorption test is readily applied to determinitrg the relative water wettability of fresh oilfield cores. The cores are not extracted before testing. Observed values of the wettability of field cores tested to date have varied from 100 to 6 per cent water wet. INTR OD UCTIO N Recent articles1 ' have emphasized the important role that wettability plays in almost all phases of reservoir rock behavior. It has been shown that wettability has a profound effect on the interstitial water saturation, residual oil saturation, capillary pressure, relative permeability, waterflood behavior, and resistivity index of oilfield cores. A quantitative investiga- tion of the effect of wettability on these core properties is severely handicapped by the lack of a simple technique for measuring the wettability of a porous medium. If such a technique were available, it would provide investigators with a means of gaining insight into the distribution of phases within a core. A number of qualitative methods of estimating wettability are known. These include contact angle measurements, flotation tests and studies of displacement pressure: imbibition7 and relative permeability data.' Using these tests, it is usually possible to classify a core as water-wet, oil-wet, or some intermediate degree of wettability. One recently proposed method involving measurement of nuclear magnetic relaxatione offers promise of determining quantitatively the fractional wettability of cores. The equipment is rather elaborate and necessary treatment of the cores before testing probably alters the natural wettability. This latter point also applies to most of the cited qualitative methods. This paper presents a new technique for determining water wettability of cores; it is based on measurements of the dye adsorption capacity of the core. This method has the advantage of requiring relatively simple equipment and involves minimum handling of the core before testing. It is important to distinguish between the various concepts of wettability referred to in the literature. The term "wetting" is defined by Bartell as that phenomenon which occurs when a solid and liquid phase come in contact in any manner so as to form a solid-liquid interface. A preferentially water-wet solid is defined by Jennings in terms of the advancing contact angle in the solid water-oil systems. Brown and Fatt regard fractional wettability as the fraction of the total surface area that is preferentially oil-wet or water-wet. However, none of these definitions adequately describes the type wettability measured by the dye test. This calls for the introduction of a new term, "relative water wettability", which we define as the fraction of the total surface area of a core contacted by injected water. DESCRIPTION OF METHOD The ability of a porous medium (especially the clays) to adsorb large quantities of surfactants, dyes, etc., is well known. It is reasonable to assume that a substance can be adsorbed from solution onto a solid surface only if the solution contacts the surface. In this connection Shapiro" has shown by experiments on silica gel that completely dry gel will adsorb methyl red dye from a benzene solution. On the other hand, if a film of water more than several molecules thick is present on the silica gel, the adsorption capacity of the gel for the dye is drastically reduced. Thus, a study of the dye adsorption capacity of cores should give some clue as to the fluid distribution on the surface of the core. TEST OF METHOD As a qualitative check on this theory, dye adsorption tests were run on similar Berea sandstone cores (Table 1, Cores 1-5). Cores saturated initially with water and flooded with 0.01 per cent aqueous methylene blue adsorbed 0.58 mg dye/gm of core. Similar cores saturated initially with water, driven to irreducible water with oil, and then flooded with the same dye solution also adsorbed 0.58 mg dye/gm of core. Another core, treated with a 5 per cent Dri-Film solution, dried and saturated with oil (Soltrol) adsorbed no dye when the dye solution was injected. These tests confirm

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By J. C. Bokros, A. S. Schwartz

The irradiation-induced densification of pyrolytic carbon has been shown to take place by a simple first-order rate process. The values of the densification constant, kd, for isotropic carbons are 1.0 x 10-22, 1.4 X 10-22 and 2.8 X 10-22 (nut)-1 at irradiation temperatures of 520o, 670°, and 1000oC, respectively. The apparent activation energy obtained from the temperature dependence of kd for isotropic carbons is about 0.2 ev. Estimates of the maximum stresses that develop in isotropic carbons owing to shrinkage onto an unyielding support show that stresses in excess of 15,000 psi may be avoided during irradiatian at 600" and 1000°C if the initial coating density is kept above 1.5 and 1.9 g per cu cw, respectively. If a carbon coating on an unyielding support is not completely isotropic, stresses may continue to build up at high neutron exposures after densification is complete because of continued anisotropic distortion. Stresses in excess of 15,000 psi from this source may be avoided during irradiation at 1000°C if' the Bacon anisotropy factor is kept below 1.3. A variety of applications of carbon and graphite in nuclear technology has stimulated numerous studies of the effect of neutron irradiation on these materials One of the most interesting problems associated with the use of carbons and graphites in the high fast neutron fluxes of nuclear reactors arises as a consequence of the neutron-induced dimensional changes that occur during irradiation. Energetic neutrons displace car- bon atoms from their lattice positions; and, depending on the temperature, the interstitials and vacancies produced migrate to form clusters, recombine, or are annihilated at dislocations or crystallite boundaries. The competition of various sinks for the point defects results in structure-sensitive bulk-dimensional changes that vary with temperature in a complicated way. This paper deals with the neutron-induced dimensional changes in turbostratic carbons that are being used as coatings on nuclear fuel particles. Details of the structure of these carbons and the variations of their structure with deposition conditions have been reported.'-3 It has been shown in previous work that the neutron-

Jan 1, 1968

By F. F. Aplan

For the past year, MBD has been engaged in a lively discussion on a name change for the Division. To complicate things, more than one name change has been proposed! There has been much discussion on the subject, as anyone who has attended the Annual MBD Business Meeting or read [jE] knows. The position of many of our members is well known. There is, however, one group that has not been heard from. These are the future members-the present students and those even younger who are yet to elect our profession. As one who has traversed the academic-industrial interface several times, I think I am qualified to speak for this group. Before going further I think it wise to state unequivocally that our Division should adequately represent our profession. The whole profession is just too small to chop into a plethora of pieces: "I'm not a mineral processing engineer, I'm an ore dresser-well, actually, I specialize in comminution, specifically in grinding, mostly in autogeneous grinding-primary autogeneous grinding that is-and my 'thing' is really iron ores, taconites, mind you!" Enough to confuse even those that keep the faith, and certainly we can't build a profession on such narrow pieces. Either an employer can hire a professional who knows the entire profession or he can't. As more and more companies search out opportunities in the mining and metallurgical fields and as environmental considerations bring into question even our technically well proven processes and procedures, there is a greater need than ever be- fore for a well-rounded mineral processing engineer well versed in all of the process possibilities. What is needed is one who can take an ore-or municipal trash for that matter-and produce there from a valuable product by the most appropriate means. It doesn't really matter if this is done physically, chemically or thermally.

Jan 1, 1971

By N. J. Grant, A. W. Mullendore, Y. Ishida

Creep tests were performed at 500°F on polished specimens of A1-3 pct Cu at stresses of 2000, 4000, and 6000 psi. The effects of the size and distnbution of the second phase were studied in connection with the mechanisms of deformation, especially grain boundary sliding. Although the amount of grain boundary sliding varied considerably for the different heat treatments, yestriction of grain boundary sliding is not due primarily to precipitate on the grain boundary. NUMEROUS prior investigations of grain boundary sliding, notably those of McLean, 1 Rachinger, 2 Rhines, Bond, and Kissel, 3 and Brunner and Grant,4 have established the importance of this phenomenon in the deformation of pure aluminum and its solid-solution alloys at elevated temperatures. An extension of this kind of study to the case of a simple two-phase structure is an important step towards understanding the deformation behavior of more complex alloys. A two-phase A1-3 pct Cu alloy was selected for this study. The creep behavior of alloys in this system has been studied by Sully and Hardy,5 by Underwood, Marsh, and Manning,' and by Pelloux, Chaudhuri, and Grant.7 In these studies, the prior heat treatments were such that some precipitation took place during the tests in most cases. Pelloux, Chaudhuri, and Grant7 studied the creep of A1-2 and 3 pct Cu alloys in the overaged condition. Their results indicated that the structure most effective in promoting high-temperature strength consisted of a fine, closely spaced grain precipitate and large, widely spaced particles on the grain boundary. The present work consists of quantitative meas- urements of grain boundary sliding during creep of an A1-3 pct CU alloy with four different precipitate distributions. The aims were to quantitatively define the role of the second phase on grain boundary sliding, and to obtain information regarding the mechanism of grain boundary sliding. MATERIALS AND PROCEDURE A high-purity A1-3 pct Cu alloy, kindly supplied by Alcoa, was used in this investigation. The composition of the alloy in weight percent was as shown in Table I. This composition is such that A12Cu exists as a second phase at temperatures below 850°F. A homogeneous grain size of 0.6 to 0.8 mm was obtained by annealing the machined test bars for 5 min at 1000°F, furnace cooling to 930°F, and homogenizing for 5 hr. Following the recrystalli-zation and homogenizing anneal, four different heat treatments shown in Fig. 1 were utilized. The F7 and F5 treatments utilize a furnace cool to the aging temperature while Q7 and Q5 have a water quench from the homogenization temperature before aging. Figs. 2 to 5, and Table 11, show the size and shape of precipitate dispersions obtained with the above heat treatments. The heat treatments produce variations in the dispersion both in the grains and along the grain boundaries. Precipitate particles along the grain boundaries are rounded and large (about 1.5 p diameter) in the F5 and F7 structures (Figs. 3 and 5). The grain boundary precipitate was somewhat smaller (0.9 p diameter) in the Q7 structure and no grain boundary precipitate was detected in the Q5 structure using light microscopy. The pre-

Jan 1, 1964

By Fred W. Stiefel

This paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct. † This part of the tunnel is 15 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 17 to 19 ft. in diameter. It lies at a depth of 400 ft. below sea level, with a maximum overburden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotives, each of 13 gross tons and having a maximum speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 750,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using concrete presented a problem of hading a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 CU. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles. Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. Choice of Locomotives In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. Proposition No. i The 90-hp. storage-battery locomotives the (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1943

By Fred W. Stiefel

This paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct. † This part of the tunnel is 15 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 17 to 19 ft. in diameter. It lies at a depth of 400 ft. below sea level, with a maximum overburden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotives, each of 13 gross tons and having a maximum speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 750,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using concrete presented a problem of hading a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 CU. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles. Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. Choice of Locomotives In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. Proposition No. i The 90-hp. storage-battery locomotives the (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1943

By Helmut Thielsch

METALLOGRAPHIC specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production " requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and photography in electron microscope and (5) interpretation. PREPARATION OF METAL SURFACES Usual metallographic polishing is generally satisfactory. It is important though that the final polish be applied very care- fully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside from superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the same for 20 min. in a solution containing 8 grams cupricsulphate in 40 C.C. of concentrated HCl and 40 C.C. of H20 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by 10 min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By J. C. Branner

(New York Meeting, February, 1012.) DURING the past two or three years I have seen statements regarding the first discovery of fullers' earth in this country that seem to require correction or modification. One appears again in the Mineral Resources of the United States for 1909, part II., p. 738, where it is said that ? fullers' earth was first discovered in the United States at Quincy, Fla., in 1893." In this connection the following bit of unpublished history concerning fullers' earth in the State of Arkansas is worthy of attention. In April, 1891, when I was State Geologist of Arkansas, a Swede named John Olsen, formerly a copper-miner in Michigan, but then living south of Little Rock, brought me a sample of what he thought was fullers' earth. He reported that it was from near the town of Alexander, the locality being 1 S. 13 W., section 8, SW. quarter of the SE. quarter. My chemist, Dr. R. N. Brackett, analyzed the material, and reported: Per Cent. Silica, . . SiO2., . 63.19 Alumina, . AL2O3, . 18.76 Iron, . Fe203 7.05 Lime, . Ca0 0.78 Magnesia, . . MgO 1.68 Potash, . K2O 0.21 Soda, . . Na2O 1.50 Loss on ignition, . 7.57 100.74 Water at 110° to 115° C. = 7.84. Another sample from about the same locality, also brought by John Olsen, on analysis by Dr. Brackett gave

Jul 1, 1912