Search Documents

By E. D. McMurry

INTRODUCTION Before discussing the use of the free piston; it may be well to explain briefly the type of gas lift valves with which the loo] is designed to function. The gas lift valve ii nothing more or less than a small back pressure regulator. It; construction consists of an outer hous ing covering a seamless metallic bellows in such a way as in form a sealed pressure vessel or pressure dome. To the bellow* in attached a stem and to this stem is attached a .rating member. When the valve is run into the hole, a pre-delermined pressure charge is placed in the pressure dome. As shown in Fig. 1. the valve is furnished in four different major assem-blies. to accomplish good results in different types of wells. The valve is mounted on a pup joint (Fig. 2a) : the eoin-plele assembly is entered into the tubing siring at the desired location. Each valve is furnished with a revere flow check valve (Fig. 2-b) to eliminate any back wash through the mechanism. Valve action is as follows: At any time the casing pressure is allowed to exceed the pressure forces within the pressure dome of the valve, the valve simply opens and passes gas from the rasing annulus into the tubing. When the casing pressure forces arc allowed to bleed to a force less than the pressure force within the dome, of the valve. the valve closes. With this type of construction. it is possible to open and close the valve or valves at will from the surface, the medium of the gas pressure in the rasing annnlus. The cycle of operation is governed by a tine cycle motor valve, commonly referred to as a gas lift interutitter or gas life surfacr controller (Fig. 3). In actual practice. after the well is unloaded only one valve is in operation . . . all other valve.: remain in the closed position. On pre-determined time cycles, it is possible to open and close this operating valve at will, and to pass the desired amount of gas through this valve wheneler needed. This method of gas lift is widelv used and has been found In be very efficient. However, it has long been known that even greater efficiency would be obtained if it were possible to place Piston between the injected gas and the fluid head. The free piston which will be discussed here was designed to accomplish this end and has been found to do so with very satisfactory results. DESIGN AND OPERATION OF THE FREE PISTON Basically. the free piston consist- of a telescoping assembly in which are incorporated the various control and operating parts (Fig. A set of sleeve valves which are opened and closed by movement of the telescoping section is contained in the. tool. A cross section of the free piston is shown in Fig. 4-11, 'rile main body cotain- a seamless monel bellows of the same type as that generally used in pressure charged gas lift valves (Fig. 4-c), and a valve core to permit placing a pressure charge in the bellows before the free piston is placed in service. The bellows is the main control unit of the free piston and performs two function: 1. It governs the opening and closing of the sleeve valves. a.: dictated by the producing activities of the well in which the piston is operating. 2. In its normal position, it holds a rubber packer in an elongated position to permit passage of fluid between the packer and the tubing walls. The lower section of the free piston contains a hydraulic shock absorber which cushions the return of the tool to its

Jan 1, 1953

By William Schriever

The flow of a gas-free liquid through a spherical-grain sand has been investigated by S1ichter.l By theoretical considerations involving a rather large number of approximations he arrives at the following flow-formula: V = CPd2At NLB{1 - m) where V is the volume of liquid delivered in time t through a cylindrical column of sand of length L and cross-sectional area A by a pressure-drop P when the sand grains of diameter d are packed to a porosity m and the coefficient of viscosity of the liquid is n. C and B are constants which were determined from geometrical relations; B was in reality a function of . Values of B(l — m) for various values of m were given in a table. In the same Annual Report of the U. S. Geological Survey, King reported the results of his experiments on the flow of water through porous media. He found that there was a departure of about 86 per cent. from a linear relationship between rate of flow and pressure, for a specimen of Dunnville sandstone for pressure drops not exceeding 60 cm. of mercury. The specimen was approximately 4 cm. in diameter and 5.1 cm. in length. Over the same range of pressure he found a departure of 45 per cent. for a specimen of Madison sandstone. For unconsolidated sands he found departures as great as 49 per cent. for pressure drops of 70 cm. of mercury; for pressure drops not exceeding a few inches of water he obtained a close approximation to a linear relation. He also investi-

Jan 1, 1930

By G. Koves

The behavior of case-hardened AISI C-1213 free -machining steel under complex impact-fatigue -wear load conditions was investigated. The inherently poor dynamic properties of the steel are mainly affected by the stress distribution in the case, component shape, and tempering. Cold-riveted components showed unexpectedly high dynamic strength compared to basic parts. A compromise beatment—which provides good dynamic properties, reasonable wear resistance, and fair riveting characteristics—zuas developed. A number of mechanical components in data-processing machines are made of free-machining carbon steel. Although, selected primarily due to manufacturing requirements, components made of these grades frequently undergo complex heat treatment and must sustain impact-fatigue loads. A typical free-machining steel is the AISI C-1213 grade, which is a resulfurized and rephosphorized open-hearth steel. While the undesirable effects of sulfur and phosphorus on the mechanical properties are well-known, data on dynamic properties are scarce.1"3 Rapid rotating or oscillating motion while carry- ing a high cyclic load requires a combination of wear resistance with high endurance limit and impact toughness. The inherently poor dynamic properties of the free-machining steel are further degraded by the machining, which introduces local stress-concentration areas. While the heat treatment (usually case hardening) improves some mechanical properties, it necessarily impairs others. Another problem arises when components, such as studs, must be fastened by riveting. The high crack-sensitivity of the free-machining steel, especially in the presence of a hardened case, makes this operation difficult. In view of the preceding considerations, it is of interest to investigate the behavior of a typical component under complex impact-fatigue-wear loading conditions in order to explore the effects of material, machining, and heat treatment, to obtain specific data on the dynamic characteristics of free-machining steel, and to arrive at a process which would adequately utilize the inherent qualities of this material. EXPERIMENTAL PROCEDURE To simulate actual service conditions, a typical component was selected, based on frequency of application, complexity of load, and processing difficulties. The dimensions and shape of the component—a stud used in many electromechanical document-handling machines—are shown in Fig. 1.

Jan 1, 1964

By J. L. Christie, W. R. Webster, R. S. Pratt

Since the delivery of our paper on Some Comparative Properties of Tough-pitch and Phosphorized Copper,1 a new brand known as "oxygen-free high-conductivity copper" (brand OFHC) has become available to consumers. It was thought desirable to make a comparison between the properties of this material and those of the materials covered by our original paper and its discussion. Preliminary tests had indicated some notable differences. A billet of oxygen-free high-conductivity copper was taken from regular production. A chemical analysis of the particular billet was not made, but the producer of the material has given as typical the analysis shown in Table 1. The

Jan 1, 1933

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

By Harold R. Larson, John F. Elliott

The standard free energies of formation of several nzetallic sulfides have been measured by a reversible electromotive-force cell employing stabilized zir-conia as the electrolyte. The oxygen potential at the cathode was fixed by the use of pure oxygen gas at 1 atm. It was established at the anode by bringing to equilibrium the reaction between the sulfide and oxide species present. Thus, Gf: for the sulfide could be obtained from the cell potential and the standard free energies of formation of the oxides participating in the reaction. The results in calories per cam rnole for the temperature range 850" to 1100°C are: Use of the reversible electromotive-force cell having an oxide-ion electrolyte to obtain the standard free energies of formation of some of the more stable metallic sulfides offers a convenient experimental method that is very productive. It also avoids some of the problems inherent in the experimental methods' for such studies which rely on precise determination of gas compositions, particularly if these compositions lie near the limits of our capabilities for accurate chemical analyses. The reaction equilibrium between the lowest sulfide of a metal, SO2 at a fixed pressure, and an oxide of the metal has a characteristic oxygen potential. For example: and for metals whose lowest sulfide is much more stable than the oxides of the metal, the equivalent reaction might be:

Jan 1, 1968

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By L. M. Pidgeon, W. Curlock

FREE energies of formation of zinc sulfide and magnesium sulfide had previously been estimated to an accuracy of ± 5.0 kcal per g mol. In the present work, these values were determined experimentally. As the determinations of the free energies of formation of zinc sulfide and magnesium sulfide presented different problems, separate experimental procedures were employed for each. ZINC SULFIDE It is difficult to measure the free energy of formation of either zinc sulfide or magnesium sulfide by measuring their decomposition pressures directly, as they are very stable compounds. An attempt was made by Jellinek and zakowski3 to study the equilibrium. zns(s) + H2(g) = Zn(g) + H2S(g) [I] They passed hydrogen over zinc sulfide and analyzed the gases leaving the reaction zone for H2S. They were unable to determine the true partial pressures of the H2S by this method, as some of the H2S on being cooled from the reaction temperature, reacted with the zinc in the gas to produce ZnS. Consequently, they were unable to establish any true equilibrium data for reaction [I]. More recently,' the equilibria ZnS(sphaledte) + Fe (s) — FeS(s) + Zn(g) [2] and ZnS(sphalerite) + 2Cu(s) — Cu2S(S) + Zn (g) [3] were studied. As the standard free energy of formation of Cu2S is known to * 3.0 kcal, and of FeS to ± 1.0 kcal, it should be possible upon performing equilibrium studies on reactions [2] and [3] to deduce the standard free energy of formation of ZnS (sphalerite). However, as both of these equilibria involve 2 solid sulfides, and as it is possible for these sulfides to dissolve in one another, it is necessary first to ascertain the activities of the various sulfides in these solid phases.

Jan 1, 1959

By A. Josefsson

The transition temperatures of 0.01 to 0.02 pct carbon steels are shown to be strongly influenced by cooling rate in the a range, quenching from A, causing a very low transition temperature even after strain aging. In a titanium-stabilized steel and in a steel with 0.05 pct C this effect is absent. NORMAL mild structural steels usually show a structure of more or less pure ferrite, as a matrix, in which cementite grains or pearlite are embedded. Of these components, ferrite is by far the most interesting one as far as ductility and brittle (cleavage) fracture are concerned. Obviously, pear-lite and carbide are by no means necessary for a cleavage crack to nucleate and grow in the ferrite, as steels with a very low carbon content (Armco iron with 0.02 pct C) have an impact transition temperature just as high as semikilled steels with 0.26 pct C.1 Although it has been argued that a very embrittling effect is to be expected from cementite, precipitated as continuous films along the ferrite grain boundaries,'. " the micrographic evidence for a direct causal connection between the brittleness and these films does not seem to be very convincing. On the other hand, it has been stated that cementite particles in ferrite are able to stop ferrite cracks.4,5 In any case, the properties of the ferrite itself seem to be of overwhelming importance to the ductility of steels, justifying a thorough study of steels consisting of ferrite of different compositions, but principally free from pearlite, which means a carbon content below 0.02 pct. Such investigations have been carried out using the impact transition temperature as a criterion of the tendency to brittle fracture and have given some rather unexpected results. One result is the profound influence of carbon on the transition temperature of the steel in normalized condition. If the carbon content is reduced from 0.02 to 0.015 pct and below, a nearly discontinuous decrease in transition temperature appears even with high percentages of such elements as phosphorus and nitrogen present. This will be reported elsewhere." The present paper deals with another effect of carbon upon transition

Jan 1, 1955

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By Matti J. Saarivirta

The relative machinabilities of the precipitation-hardenable Cu-0.9 pct Cr, Cu-0.25 pct Zr, and Cu-0.9 pct Cr-0.25 pct Zr alloys are improved from 18 to 80 pct by 0.75 to 1.25 pct Pb. The Lead also improves the tensile strength, hardness, ad resistance to softening of the Cu-Cr and Cu-Cr-Zr alloys. When the alloy containing 0.7 to 2.2 pct Cr, 0.10 to 0.25 pct Zr, 0.75 to 1.25 pct Pb, and balance copper is solution-annealed at 1000°C (1830°F) and then aged at 525°C (Y75°F), tensile strength of 65,000 psi, 16 pct elongation, 62Rb hardness, and 84 to 87pct IACS electrical conductivity are obtained. The copper base Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys have high electrical and thermal conductivities, high strength and resistance to softening at elevated temperatures, but their machinability is poor, i.e., close to that of the pure copper. In the manufacture of various components such as welding electrodes or electrical and thermal conductors it is ofter desirable that the alloy have good machinability for high production rates and long tool life. Thus, alloys that combine these properties may be used not only for existing applications, but for new ones where good machinability is a requirement. This investigation was undertaken to improve machinability without impairing other desirable characteristics of the Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys. These commercial alloys contain about 0.4 to 1.2 pct Cr, 0.10 to 0.25 pct Zr, and balance copper. Lead was selected as an element that should improve the machinability and possibly other characteristics of the alloy. WORK PROCEDURE This investigation began with a study of the effect of lead on the hardness, tensile strength, electrical conductivity, and machinability of the binary alloy containing 0.10 to 1.30 pct Cr and balance copper. This was followed by an investigation of the effect of lead on the Cu-0.1 to 0.4 pct Zr and Cu-Cr-Zr alloys. The alloys were made from initially oxygen-free copper and for comparison some castings were made from phosphorus-deoxidized Lake Copper. Commercially pure chromium, zirconium, and lead were used for alloying. In melting the chromium was added to molten copper at 1400°C (2550°F), the heat held for 15 min at temperature, and the temperature then lowered to 1350°C (2460°F) when the other elements were added. The alloys were held for 15 min at this temperature and cast into a cast-iron mold. One-kilogram, 3-in.-diam castings were made. An argon cover was maintained during melting and casting to prevent oxidation. The chemical compositions of the alloys are shown in Table I. The micro structure and properties of the alloys were studied in the cast and wrought conditions prior to and after various solution-annealing and heat-treating cycles. The relative machinability was determined as a function of the lead content and compared with the free-machining Cu-lpct Pb alloy. To determine the machinability, 13/16-in.-diam cast specimens were cut by a machine hack saw using a constant cutting speed of 50 fpm, a fixed feed force, and a new blade for each alloy specimen. Molybdenum highspeed steel saw blades, 0.032 in. thick with 14 teeth per in., were used in all tests. No cutting fluid was used. Five tests were made on each specimen and the average elapsed time per test was taken as a measure of the relative machinability for that alloy. The variation of cutting time for each alloy was less than 110 pct.

Jan 1, 1969

By Harold B. Fell

MANY oil producers are in disagreement with the idea held by some that an increase in the price of crude oil would be unlikely to stimulate much production and that we will be obliged to draw upon foreign sources of petroleum to supplement our domestic production as the years go by. Supporting our con trary opinion are numerous facts and figures. The most recent official estimate of the maximum efficient rate of production from the oil wells of the United States is 5,271,000 bbl per day. The Economics Advisory Committee of the Interstate Oil Compact Commission estimates, assuming certain supplies from imports and from natural gasoline and benzol, that crude oil require-

Jan 1, 1947

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author's hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland's postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H', X-, or R', OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,' both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.' In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By Reynold Q. Shotts

The small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive ac-in of coke in the form of ''trees,, or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of labora- tories1,2,3,4,5 are one method of approach to the problem Of selecting stoker coals- As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that Others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simp1e measure Of the tendency Of a a to form coke in a fuel bed. Although possessing all Of the disadvantages Of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects Of swelling properties upon combustion.7 Ostborg, Limbacherand Sherman, have shown that the test can Predict, roughly, the tendency Of coke to accumulate in the fuel bed Of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1949

The Pennsylvania State College, Mineral Industries Experiment Station, State College, Pa For publications address the Director The Pennsylvania State College through the Minerals Research Experiment Station has issued 10 Bulletins and three Technical Papers, from which the following have been selected as of greatest interest to mining engineers and geologists: Bulletin 1, An investigation of the properties of smitliing coals (1922), free; 2, Petrography of the Mica Pendotite Dike at Dixonville (1926), free; 4, The Helderberg Group from cen¬tral Pennsylvania to southwestern Virginia (1929), 25 cents, 5, Bentonite in Pennsylvania (1929), 10 cents, 6, Production data on Appalachian oil fields (1930), free; 8, Oil field waters of Pennsyl¬vania (1930), free; Technical Paper 2, Condition of water in coals of various ranks.

Jan 1, 1933

By Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964