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By R. G. Lazzell

THE British are worried about the postwar possibilities of their coal mining industry. Indeed, there are causes for this worry, with the aver- age 1943 cost of production at about $5.40 per long ton, compared to $3.20 in 1938. Average production per man day has dropped from 1.12 in 1938 to 1.03 long tons in 1943. As a comparison, production per man day in the United States is approximately 5 long tons. The average day wage in the British mines is now a little aver $4; in 1938 the average day wage was about $2.25. Great Britain produced 227 million long tons in 1938 from their deep mines, and in 1943 production was 194.5 million, with an additional 4.5 million from strip mines. To meet present wartime needs, output is being supplemented by the production of strip- mined coal, an industry that did not exist prior to the war. Strip mining is now producing at the rate of 15 million long tons per year.

Jan 1, 1944

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By Richard R. Zupp, David A. Stevenson

A theoretical treatment of austenitic Fe-C-Z solutions (where Z represents a substitutional solute) was developed by extending a solution model which was previously applied to austenitic Fe-C alloys. The model assumes that each carbon atom in the solution excludes H interstitial sites from occupancy by other carbon atoms rmd thai otherwise the assembly of carbon atoms is equivalent to a modified Langmuir lattice gas. The results of the treatment provide theoretical justification for a phenomenological expression previously developed to represent the influence of substitutional solutes on the thernlodynamics of carbon in austenitic Fe-C-Z alloys. The expression is: where Kz is a parameter which characterizes the Fe-C-Z system at a given temperature and Xz and xj are the concentrations of substitutional solute and interstitial carbon expressed as atom ratios. The parameter, Kz, was associated with the differ- A number of investigators have measured the influence of various substitutional solutes on the carbon activity in austenitic Fe-C-Z alloys, where Z represents any substitutional solute. Experimental information is available for alloys containing the following substitutional solutes: Mn,' Si,' Ni,2-5 CO,'-', Cr,5, 9-11 CU,4 Al,= v,11, 12 and Ti.13 This information is essential for studying many phenomena in Fe-C-Z alloys, particularly diffusion and diffusion-controlled phase transformations For example the pffprts nf various ence between the interaction energies between carbon atorns and host-lattice atoms in the Fe-C-Z solution and the corresponding energies for the Fe-C solution. The carbon activity in a ternary Fe-C-Z alloy, ac, was obtained in terms of the composition of the alloy and the single parameter, Kz: where y° is the Henry's law constant for the binary Fe-C solution. Both y° and H crm be determined from the data for Fe-C solutions, without recourse to any experimental data for Fe-C-Z solutions. The theoretical treatment was extended to alloys containing several substitutional solutes. By neglecting interactions between the substitutional solutes, an expression for the carbon activity in multicomponent alloys was obtained in terms of the Kz values characterizing ternary Fe-C-Z systems. substitutional solutes on the rate of pearlite growth is explained14 on the basis of their effects on carbon diffusion, which result from their influences on the carbon activity in the solid phases. In addition, recent studies have emphasized the dependence of the pro-eutectoid ferrite transformation15 and other diffusional processes in austenite16 on the influence of substitutional solutes on the carbon activity in austenite. They have indicated the need for suitable analytical expressions to represent such influences. The present authors previously developed general phenomenological expressions to represent the equilibrium partitioning of carbon between Fe-C alloys and Fe-C-Z alloys.'2 The expressions are applicable to all the austenitic Fe-C-Z alloys for which experimental data are available, and are sufficiently simple to recommend their general application. For alloys in

Jan 1, 1969

By J. F. K. Brown

ANTHRACITE in 1943, in common with the coal industry as a whole, passed through a year of wage negotiations that seemed endless. In the early months discussion of the United Mine Workers' demands was taken up and carried on continuously until May, finally reaching an impasse when the Union refused to continue at work, while submitting their demands to the War Labor Board. Thus a strike threatened, averted by the Federal Government taking over the industry, effective May 1, by order of the President. An office of the Bureau of Mines was established in Wilkes-Barre under the direction of J. J. Forbes, Mineral Production Security Division, as regional manager, who conducted operations until September, 1943, when the collieries were turned back to the operators. But the miners did not agree with the War Labor Board's award rendered in the fall, resulting in a recurrence of the previously threatened strike. again averted by Government control. In addition to the major upsets, a number of individual suspensions occurred at various mines. In spite of these drawbacks, to which might be added the difficulty of obtaining equipment and the scarcity of man power, the industry by November was only little less than a million tons short of the previous year. and in all probability, finally produced but little less than in 1942. This little less. however, was greatly missed in the market.

Jan 1, 1944

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By R. W. Fountain, W. D. Forgeng, G. M. Faulring

Precipitation of the phase Co3Ti (Cu3Au type) from a Co-5 pct Ti a11oy has been investigated using single-crystal X-ray diffraction techniques. Oscillation and transmission Laue patterns of specimens aged for short-time periods at 600" C indicate the formation of titanium-rich and titanium-poor zones coherent with the {100} matrix planes. Longer aging times at 600° C establish that the equilibrium phase also forms on the {100} matrix planes as platelets. These observations are corroborated by electron metallography; electron diffraction studies show the phase Co3Ti to be ordered. A probable sequence of the precipitation reaction is discussed. A previous publication by two of the present authors reported on the phase relations and precipitation in Co-Ti alloys containing up to 30 pct Ti.1 The results of this investigation established the existence of a new face-centered cubic inter metallic phase, ranging in composition from about 17.0 to 21.7 pct Ti at temperatures below 1000° C The decomposition of the fcc supersaturated solid solution was studied employing hardness and electrical resistivity measurements. The changes in hardness upon precipitation in alloys containing 3, 6, and 9 pct* Ti were found to be associated with an initial increase in hardness followed by a plateau and then a second, more pronounced hardness increase. Investigation of this behavior by electrical resistivity measurements suggested that two different kinetic processes were involved, which, when interpreted in terms of the kinetic relation,2-4 indicated that initial precipitation was in the form of thin plates. On continued aging, the plates impinged during the growth process. The general features of these findings have been confirmed by Bibring and Manenc,5 while, in addition, they report the phase to be ordered. The present investigation was undertaken to provide more definite information on the structural relationships between the precipitate and the matrix. EXPERIMENTAL PROCEDURE Single crystals of a (20-5 pct Ti alloy were prepared from the melt employing the Bridgman technique. Poly crystalline rod, 1/2 in. in diam, prepared from vacuum-melted material, was machined to 3/8- in. diam to remove any surface contamination that may have resulted from hot-working. The crystals were grown under a purified hydrogen atmosphere in high-purity alumina crucibles heated by induction. Considerable difficulty was encountered in attempting to grow monocrystals because of the high melting point of the alloy and the high solute concentration. However, one crystal about 6 in. long was obtained which was essentially a single crystal except for one or two very small grains around the periphery. The as-grown crystal was solution heat-treated for 24 hr at 1200°Cin a purified argon atmosphere and water-quenched. One-quarter-in. slices were taken from each end of the solution heat-treated crystal for chemical analyses, and the remainder of the crystal was mounted and oriented by the back reflection Laue Method. The chemical analysis of the crystal was as follows: Pct Ti Pct 0 Pct C Pct N Pct H Pet CO 5.29 0.08 0.004 0.002 0.0003 Balance By proper tilting of the crystal, it was possible to obtain slices 1/32 in. thick of [loo] and [110] orientation. The solution heat-treated crystal slices were sealed in silica capsules for the aging treatments, with titanium sponge placed at one end of the capsule to act as a getter. All slices were water-quenched from the aging temperatures, the capsules being broken under the water to ensure a rapid quench. Thinning of the slices for transmission X-ray studies was accomplished by a combination of mechanical and electrolytic techniques, the final thickness being about 0.1 mm. Laue patterns of the solution heat-treated crystal indicated that no strain was introduced by the thinning technique. ELECTRON METALLOGRAPHY After X-ray examination, the structural changes attending the precipitation were followed by examination of direct carbon replicas of polished and etched surfaces of the single-crystal slices and extracted phases. The earliest indication of significant structural change was observed after aging at 600°C The structure of a heavily etched, solution-treated crystal is shown in Fig. l(a). Aside from the etch pit pattern, no regularity of background structure is observed. On the other hand, in the background of the specimen heated for 500 hr at 600°C, the etching pattern shows a directionality indicating the influence of minute precipitate particles, Fig. l(b). On electrolytic dissolution of this specimen in 10 pct HC1 in alcohol, a large volume of very small, flattened cubes

Jan 1, 1962

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-' proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible 'References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By R. L. Fleischer, W. F. Hosford

Tensile data for coarse grained aluminum Polycrystals suggest that the "grain size" effect is not due to dislocations piled up at grain boundaries but rather is primarily a relative size effect due to surface crystals being weaker and less confined. STUDIES directed at interpreting hardening of poly-crystalline metals normally identify their strain hardening properties with those in some particular type of single crystal.1"4 The recent recognition in face centered-cubic metals of a nearly linear stage with rapid hardening occuring at comparable rates for both polycrystals and single crystals, suggested that the same process or processes determine both cases and hence that there exists some justification for the use of single crystals to understand polycrystals. Further evidence for the above view may be found by an approach initiated by Chalmers:5 By using bicrystals of controlled orientation it is possible to begin to assemble a polycrystal and also to study grain boundary effects in detail. In this way it has been found that a single grain boundary affects easy glide but not the subsequent stage II hardening.6 This result suggests that a sensitive way to observe grain boundary effects in polycrystals would be to vary grain size and measure easy glide. As will be seen, easy glide is only possible for coarse-grained samples, and hence the results will serve to fill in the gap in measurements between single crystals and bicrystals on one hand and fine-grained polycrystals on the other. One problem inherent in comparing single crystals with polycrystals is the uncertainty as to what slip systems are acting in a polycrystal. To compare the two types of samples, rates of shear hardeninn---L. on the acting -planes are needed. and these may be computed only if it is known what particular systems are active. The acting systems were examined for a coarse-grained polycrystal and it will be shown that the systems supplying the preponderance of slip can be determined with little ambiguity. EXPERIMENTAL PROCEDURE Twelve samples of aluminum were prepared by chill casting into a heated graphite mold, followed by annealing at 635° ± 5°C for 24 hr with an 8-hr fur- nace cool, and finally either etching7 or electropol-ishing.' The samples, with a 7 to 10 cm length between grips and 4.4 by 6.6 mm in cross section, were deformed at a strain rate of about 3 10 -3 . per min in a tensile device which has been described elsewhere.5 The composition was reported by Alcoa as 99.992 pct Al, 0.004 pct Zn, 0.002 pct Cu, 0.001 pct Fe, and 0.001 pct Si; nine samples were deformed while immersed in liquid helium and three in air at room temperature. The stress-strain curve for one of the samples (P-1) deformed at 4.2 "K has been reported previ~usl~.~ This sample was selected for determination of active slip systems. Eighteen of the crystals were examined by optical microscopy to determine the angles of slip line traces and by X-ray back reflection to determine orientation. By this means the slip planes were determined and the resolved shear stress factors for possible slip systems could be computed. Finally each sample was sectioned so that after etching, the number of crystals could be counted for each of ten newly exposed surfaces. The average of these ten values will be termed n, the number of crystals per cross section. Values of 11, varied from 1.9 (nearly bamboo structure) to 12.7. Sketches of typical cross sections appear in Fig. 1. RESULTS AND DISCUSSION: SLIP SYSTEMS 1) Determination of Acting Slip Planes—The stress axis orientation and operative slip planes in eighteen crystals of sample P-1, as determined by slip line traces and crystal orientation, are summarized in Fig. 2. For one of the crystals two planes had a common trace. so that the traces alone did not distinguish which plane or planes were slipping. However it was found that the stress resolving factor for the primary system was 0.386, .while that for the most stressed system in the other plane (indicated bv the dotted arrow) is 0.138. It will be assumed tgerefore that only the primary plane acted. Since the orientations were determined after extending the samples 4 pct, the stress axes may be rotated from their original value by as much as 2 deg in some cases. It is interesting to note that in five crystals only one slip plane acted, in eight two acted, and in five three planes were observed—an average of two slip

Jan 1, 1962

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 *ABBOTT, CHARLES W., Min. Engr. Pioche, Nev. ?08 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94 *AOTT, ROBERT R., Met. Engr., Peerless Motor Car Co., Cleveland, Ohio. '12 || ARAHAMS, ALEXANDER I., Student.. .67 E. 93rd St., New York, N. Y. '13

Jan 1, 1917

By Nelson B. Russell, Donald C. Bond

The effects of various antifreeze agents on the formation of hydrogen sulphide hydrate have been studied. On a molar basis the relative lowering of Tm (the maximum temperature at which solid hydrogen sulphide hydrate can exist in equilibrium with the given solution) for the various agents is: sodium chloride 1.00, calcium chloride 1.71, methyl alcohol 0.57, ethyl alcohol 0.68, ethylene glycol 0.73, diethylene glycol 0.73, sucrose 0.87, dextrose 0.71. On a weight basis the relative lowering of TM is: sodium chloride 1.00, calcium chloride 0.91, methyl alcohol 1.08, ethyl alcohol 0.89, ethylene glycol 0.69, diethylene glycol 0.41, dextrose 0.23, and sucrose 0.15. Introduction The solid hydrate of hydrogen sulphide, H2S.6H20,1 is in equilibrium with water and liquid hydrogen sulphide at 85°F at a partial pressure of hydrogen sulphide approximately equal to the vapor pressure Of hydrogen sulphide at that temperature. At temperatures below 85°F, in the presence Of excess hydrogen sulphide (greater than the amount required to react with the water present) the hydrate is in equilibrium with liquid hydrogen sulphide at approximately the vapor pressure Of hydrogen sulphide. In the presence of excess water, the solid hydrate is in equilibrium with liquid water, containing dissolved hydrogen sulphide, at a pressure lower than the vapor pressure of liquid hydrogen sulphide at the same temperat~re.2 The lower the temperature, the greater the difference between the decomposition pressure of the hydrate and the vapor pressure of liquid hydrogen sulphide at that temperature. Conditions conducive to the formation of solid hydrogen sulphide hydrate may exist in wells producing a gas containing a high percentage of hydrogen sulphide under high pressure, or in the lead lines from such wells. This paper gives the results of tests made with various antifreeze agents which might be useful in decomposing the hydrate or in preventing the formation of the hydrate of hydrogen sulphide Apparatus Fig , shows a diagram of the apparatus used. The sample under observation was contained in a glass tube 34 cm long, having a 6 mm id and a wall thickness of 2.5 mm. The lower end of this tube was closed- with a plug of butyl rubber. The upper end of the tube was connected to a diaphragm gauge, with a stainless steel diaphragm, a manometer, a vacuum pump, and a cylinder of hydrogen sulphide, The tube was held nearly horizontal, with the liquid resting along the lower side of the tube. It was found that when the tube was held in a vertical position, it broke with ex. plosive violence as soon as it became filled with solid hydrate. Presumably this was caused by the expansion which occurred on solidification of the hydrate. The difficulty disappeared when the tube was held in an inclined position during the tests.

Jan 1, 1949

By F. S. McNicholas

In the first big blast at Climax, a "loop back" (three-wire system) was used (Fig, I), with the idea of securing a wiring system that would give to all series the same amount of current. Single-phase, 60-cycle, 13,800-volt power was furnished to the blasting transformers, each of which has a rated capacity of 600 amp. at 480 volts. Two blasting leads were taken from these transformers, giving a blasting current of single phase, 60 cycle, 480 volts, with an instantaneous capacity of more than 600 amp. The blasting switch was on the secondary leads from the transformers, to avoid lag in energizing them.

Jan 1, 1940

By F. S. McNicholas

In the first big blast at Climax, a "loop back" (three-wire system) was used (Fig, I), with the idea of securing a wiring system that would give to all series the same amount of current. Single-phase, 60-cycle, 13,800-volt power was furnished to the blasting transformers, each of which has a rated capacity of 600 amp. at 480 volts. Two blasting leads were taken from these transformers, giving a blasting current of single phase, 60 cycle, 480 volts, with an instantaneous capacity of more than 600 amp. The blasting switch was on the secondary leads from the transformers, to avoid lag in energizing them.

Jan 1, 1940

E. T. Turkdogan (British Iron & Steel Research Assoc., London, England)—I would like to suggest a different method for the treatment of the authors' data on the Si-0 equilibrium in liquid iron. Because the activity coefficient of silicon dissolved in iron is influenced by the concentration of silicon as well as that of oxygen, the equilibrium constant K2 of reaction 2 becomes a function of metal composition, and, as shown in Fig. 1, a plot of log KP1 at 1600°C against the weight percent of silicon gives a smooth curve. A similar curve is obtained when log Kzl is plotted against the oxygen content of iron. Before

Jan 1, 1955

By F. S. McNicholas

IN the first big blast at Climax, a "loop back" (three-wire system) was used (Fig. I), with the idea of securing a wiring system that would give to all series the same amount of current. Single-phase, 60-cycle, 13,800-volt [ ] power was furnished to the blasting transformers, each of which has a rated capacity of 600 amp. at 480 volts. Two blasting leads were taken from these transformers, giving a blasting current of single phase, 60 cycle, 480 volts, with an instantaneous capacity of more than 600 amp. The blasting switch was on the secondary leads from the transformers, to avoid lag in energizing them.

Jan 1, 1938

By WILFRED SYKES

THE story of the rolling of strip steel is not limited to any one plant or individual or group of individuals. It is a story with many ramifications. First of all, it should be understood that the strip mills we are considering are continuous mills, in that the steel passes directly from one mill to the other in a more or less straight line. Continuous mills are not new; in fact, they have been used for many years in the rolling of a few simple shapes. They were, however, driven by one motor through jackshafts, and as a result the speed of each roll stand had a fixed relation to that of every other stand in the series. This in turn fixed the reduction that could be made in each stand. The mill could produce simple things, but was not satisfactory for the production of the variety of strip now required. It was, therefore, necessary to get away from the restrictions of that kind of drive. To accomplish this, the designer could either separate

Jan 1, 1936

By T. Yoshioka, Paul A. Beck

SILICON, germanium, and tin occur with both the white tine-type structure and the diamond cubic structure. In the latter form these elements are semiconductors; in the former they are metallic. The metallic form of germanium and silicon is obtained only under high pressure.' For all three elements the transition from the semiconductor to the metallic state is accompanied by a decrease in the atomic volume of somewhat more than 20 pctily2 Table I. At such a large compression the widening of the s and p bands is sufficient to make the energy gap of 1.1 ev, or less, of the semiconductor disappear, giving rise to the metallic state.*

Jan 1, 1965

By Walter von der Linden

A description is presented of the mining conditions of four longwall shield type support installations in the Pittsburgh seam in northern West Virginia and southwestern Pennsylvania. Details of roof control and operating procedures, production and performance data, and equipment description and basic engineering specifications are given for these four longwall installations. The range of mining heights was between 150 and 250 cm (60 and 95 in.). The major accomplishment of the shield supports in all four faces was the provision of an almost 100% availability for coal cutting; i.e., the face-down time due to roof control problems and support maintenance requirements was minimal.

Jan 1, 1978

By Robert H. Richards

While yet in correspondence with the heads of the several mining schools for the purpose of bringing the details of my Address into the best form for publication, a severe illness overtook me, and before I had recovered sufficiently to turn my attention to matters of this character the Address had been printed in its imperfect form for volume xv. of our Transactions, and the type had been distributed. The incorporation of the later corrections, in the form of a Supplement, became a necessity. To simplify the corrections as much as possible to the reader, every paragraph which has been revised in any way is here reprinted in full.

Jan 1, 1887