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By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By P. G. Shewmon, F. R. Winslow

An experimental method is describedfor Ihe determination of the derivative of the surface free energy (y,) with surface orientation using symmetric bicrystals. The method measures the equilibrium root-angle of grain boundary grooves for the same grain boundary on two different surfaces. In contrast to previous methods, the presence of annealing twins is not necessary. Results on silver at 900°C indicate that ??s/?3 is 0.014y, on the (loo), 0.075y, on the (111), and < 0.004?s on the (110). DURING an investigation of the kinetics of grain-boundary grooving on silver&apos; values of the derivative of the surface free energy ?s with respect to orientation were needed. Previous investigations of these so-called torque terms show that, for low-index planes in copper2 and nickel,&apos; a finite derivative exists even near the melting point. These two studies give the only previously published values of the torque on low-index metal surfaces. These investigators measured the equilibrium root angles, both greater than and less than 180 deg, along the lines where a twin boundary intersects a free surface. The technique described here is suitable for materials which do not have annealing twins, and enables the surface for study to be chosen instead of having to work in a direction normal to the twin trace on the surface. The purpose of this paper is to describe this new technique and to report the values found for the (111): (100), and (110) surfaces of silver. To check the technique proposed above, a series of 99.99 pct Ag bicrystals were used. These bicrystals were grown from the melt by a modified Bridge-man technique so that a low-index direction was parallel to the growth direction. Two orthogonal faces were studied on each bicrystal. One of these contained the low index or simple plane normal to

Jan 1, 1963

By W. B. Hickman, J. J. Pickell, B. F. Swanson

Many physical properties of the porous media-immiscible liquid system are dependent upon the distribution of fluids within the pores; this in turn, is primarily a function of pore structure, liquid-liquiri interfacial tcnsion and liquid-solid wetting conditions. The cnpillary pressure hysteresis process provides a means of investigating the influence of pore structure upon fluid distribution for consistent sur/acc conditions. Invcstigntiot2s indicate that residual non-wetting-phase saturations /ollozuir,g the imbibition process (i.e.,wetting phase displacing nor2-wctting phase) are dependent upon both pore structure and initial non-raetting phase saturation and suggest that residual fluid is distributed as Discontinuous ,globules, one to a few pore sizes in dimension, thrnugh the entire range 01 pore sizes originally occupied. It clppears that air-mercury capillary pressure dala adequntely rellect the distribution of fluiris in a water-oil system when strong wetting condition preliczil. An oil-air counter-current imbibition technique has also been found to provide a rapid rneans of obtaining residual-initial saturation data. In a majority of cnses, rcsidual saturations detf-rniinecl from the oil-air or air-mercury process reasonably approximate residual oil saturation following water drive of a strongly water-wet medium. INTRODUCTION A reliable estimate of recoverable reserves depends not only on the amount of original oil-in-place but also on pore geometry and distribution of fluids within the pores. A critical parameter determining the recovery from a reservoir under waterflood, for example, is the amount and distribution of residual oil within the various rock types present. The purpose of this paper is to investigate the mechanism of capillary trapping and assess its importance in laboratory measureqents of residual oil saturation. The degree of wettability of a reservoir rock is recognized as an important factor in waterflood or imbibition experiments. In this paper, however, only the water-wet case has been considered. Considerable experimental evidence1 suggests that for water-wet rocks, capillary forces predominate in tile distribution of fluids and that viscous forces in the range normallv of interest in the reservoir have a minimum influence on residual oil saturation. It follows that if the ultimate recovery is controlled by pore geometry, a unique residual non-wetting phase saturation should exist for a given set of initial conditions. Two laboratory procedures.found to be extremely useful in the study of pore structure and degree of fluid interconnection at various saturations are decribed. Although air-nercury capillary injection curves have been used2 previously to characterize the drainage case, the withdrawal or imbibition case can provide valuable supplementary data. The air-mercury process, however, has several disadvantages; it is difficult to run in a sufficiently accurate manner, mercury does not always act as a strongly non-wetting liquid and in the air-mercury process the sample is rendered unsuitable for future analyses. An alternative process is described in which air is the non-wetting phase and naptha, hentane, octane or toluene is the wetting phase. INTERFACIAL TENSION AND CAPILLARY PRESSURE Interfacial tension between immiscible fluids is due to the difference in attraction of like molecules as compared with their attraction to molecules of the neighbouring fluid. This net attraction results in a tension at the interface. To extend the interface; thus, interfacial tension s can also be thought of as free surface energy. Interfacial tension is normally expressed as dynes/cm, and interfacial energy is measured in ergs/cm2 hence, both have dimensions ml A 2 and are numerically equal.

Jan 1, 1967

By W. M. McKewan

Jan 1, 1962

By R. J. Lytle, E. F. Laine

The in situ high frequency electrical conductivity and permittivity of Colorado oil shale were recently measured. The measurements were made at 45 MHz (45 million cps) by transmitting from one borehole to two receiving boreholes, all boreholes in line. A differential measurement using the received signals was used to calculate the conductivity and permittivity.

Jan 1, 1983

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By H. J. Levinstein, H. J. Guggenheim

RbFeF3 is a transparent ferromagnet with a large faraday rotation which permits the direct observation of magnetic domain structures in bulk crystals. If the position of dislocations within the crystal were known a study of domain wall dislocation interactions would be possible. In this paper an etch pitting solution is described which gives a one-one correspondent between the etch pits and the dislocations intersecting the (100) surfaces of RbFeF3 crystals. In addition, RbFeF3 is shown to have sufficient plasticity so that known arrays of dislocaticms can be put into the crystal. It is concluded that RbFeF, is an ideal material for the investigation of domain wall dislocation interactions. THE influence of lattice defects on the motion of domain walls in ferromagnetic materials has been studied extensively both theoretically and experimentally.4 The experimental data obtained has been qualitative in nature due to the lack either of a quantitative knowledge of the magnetic domain array in the material or of the nature of the dislocation configuration in the material. At room temperature RbFeFJ has the cubic perovskite structure. It is ferromagnetic below 86°K.5,6 It is also transparent and has a large faraday rotation in the magnetic state.7 The domain structure of this material is observable in three dimensions in crystals which are millimeters in thickness.&apos; Since RbFeF3 satisfies the requirements of having an easily visible three-dimensional magnetic domain structure, it was of interest to determine if the dislocation structure of the material could be determined and if the material was sufficiently plastic so that dislocations could be introduced into the as grown crystals. This is a report of the results of that investigation. EXPERIMENTAL PROCEDURE The crystals of RbFeFs used in this experiment were grown by a technique described elsewhere.5 In order to obtain flat strain-free surfaces, the samples were first cut to the crystal orientation desired and the surfaces were polished by employing standard metallographic techniques. The samples were then immersed in a solution of 1 to 3 g of KOH in 100 ml of water. This solution removes the damaged surface layers uniformly leaving a film on the surface of the sample. Etch pits are obtained by immersing the sample in an approximately 50-50 solution of 30 pct peroxide and concentrated acetic acid. The film formed during the KOH treatment turns deep red in color in the etching solution and flakes off the sample. The etching time required depends upon the pit size desired and

Jan 1, 1970

By J. L. Jorstad

The hypereutectic Al-Si alloys 390 and A390 have wear characteristics superior to any of the more common aluminum casting alloys. This excellent wear resistance, coupled with good mechanical properties, high hardness, and low coefficient of thermal expansion, has made these alloys candidates for the all-aluminum internal combustion engine, the application for which they were primarily developed. A390 alloy is intended for sand and permanent mold casting, and requires a lower iron ccxltent (0.5 pct maximum) than its die casting companion 390 alloy (0.6 to 1.1 pct Fe). The 17 pct nominal silicon in these alloys provides sufficient quantities of the hard primary silicon phase to assure a high degree of wear resistance, yet little enough of this phase, to minimize the casting and m achining problems associated in the past with the hypereutectic alloys. The mechanical and physical properties of 390 and A390 alloys are competitive with the best of the common aluminum casting alloys with the exception of low ductility. This low ductility is not considered a detriment, since in many applications these alloys replace cast iron. Corrosion resistance is similar to the standard alloys 380 and 333. Numerous parts, of varying degrees of complexity, have been cast of alloys 390 and A390, including engine blocks and heads. The deviations from normal good handling and casting practices that are required for the alloys are those associated with the presence of the primary silicon. To obtain optimum strength and machinability, the molten alloys should be treated with phosphorus to refine the primary silicon phase. Care must be exercised to properly control the pouring temperature and rate in order to minimize primary silicon growth and segregation. AUTOMOTIVE engineers have for years recognized the advantages of lighter weight and better heat transfer that aluminum could offer as material of construction for engine blocks. These advantages alone, however, are insufficient justification for acceptance of aluminum engines by the automotive industry. To be acceptable, an aluminum engine first must pass all tests to which cast-iron engines are subjected, and, in addition, must represent no cost penalty in manufacturing. None of the conventional aluminum casting alloys have sufficient wear resistance to withstand the tests to which cast iron is subjected as a cylinder bore material, and recent attempts to manufacture aluminum engines with cast-in-place iron sleeves could not compete costwise with the equivalent cast-iron engine. The prerequisite to an acceptable aluminum engine seemed to be a casting alloy with a high degree of wear resistance that would eliminate the necessity of cast-in iron sleeves or liners. The hypereutectic A1-Si alloys 390 and A390 have met this challenge.&apos; Combined with modified pistons and a patented cylinder bore surface finish,2 the performance of these alloys in more than 1300 cold start and cold scuff tests, over 3500 hr of dynamometer wear and endurance tests, and more than 350,000 miles of road tests leaves no doubt as to the feasibility of running on bare aluminum cylinder bores. ALLOY DEVELOPMENT The desirable characteristics of the hypereutectic A1-Si alloys have been recognized for some time. Their excellent wear resistance and low coefficient of thermal expansions have been used to advantage in the production of diesel-type pistons in Europe and to a limited extent in this country. The major contributor to the good wear resistance of these alloys is the extremely hard primary silicon phase in the microstructure. Although the percent silicon used experimentally has been much higher, most commercial alloys have ranged from about 14 to 25 pct. Generally, as the silicon content is increased, wear resistance increases, and the coefficient of thermal expansion decreases. With increases in silicon, however, machinability and cast-ability tend to suffer. The development of a satisfactory aluminum engine block material at Reynolds involved the testing and evaluation of many alloys, covering a wide range of silicon contents and numerous variations of iron, copper, magnesium, manganese, and other alloying additions. Castability, mechanical and physical prop-

Jan 1, 1969

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By J. Szekely, Robert J. Fisher

A formulation is Presented and solutions are given for the problem of transient heat conduction in a sphere that undergoes a spatially uniform radiative heat exchange with its environment. The solutions were obtained by the numerical integration of the appropriate Partial differential equation and are Presented in a graphical form by Plotting a dimensionless average temperature against the Fourier number with the radiation number as a paranreter, for various initial sphere and environment temperatures. In addition to these numerical results asymptotic analytical solutions are also given. PROBLEMS involving the transient heating or cooling of droplets and particles frequently arise and are of importance in metallurgical operations. Spray refining, vacuum degassing, high-temperature gas-solid reaction systems, and pebble heaters are but few of the numerous examples that may be quoted. The practical interest in these problems from a design or operational point of view is to evaluate the change in the particle temperature with the time given its physical properties, initial temperature, and that of the environment. At the high temperatures encountered the principal mode of heat transfer between the particles and their environment is by thermal radiation; in case of vacuum degassing due to the very low thermal conductivity of the gas space the convec-tive components are negligible and radiation is the only heat transfer mechanism. Although much work has been done on transient heat conduction problems, the special class mentioned here, in which thermal radiation is specified at the bounding surface, received little attention to date. One contributory factor to this situation may be the nonlinearity of the radiation term in temperature, which in general precludes the use of analytical techniques and requires numerical or analog solution of the appropriate differential equations. In fact the only solutions of general nature that are available at present pertain to semi-infinite media and slabs.&apos;-3 The work on which the paper reports forms part of a program aimed at the theoretical and experimental study of transient radiative heat exchange between particles and their environment. The purpose of the present paper is to develop a formulation and solutions to the problem of transient heat conduction in a sphere that undergoes a spatially uniform radiative heat exchange with its surroundings. The solutions, obtained by the numerical integration of the appropriate differential equations, will be presented graphically, by plotting dimensionless parame- ters covering the range of variables relevant to metallurgical interests, thus affording a ready reference for design calculations. In addition to these results, approximate analytical solutions are also given which represent asymptotes, corresponding to extreme values of the variables mentioned. FORMULATION Consider a spherical particle of radius, a, initially at uniform temperature, Ti (T measured on the absolute scale), having a thermal conductivity, k, density, , specific heat, C, and thermal diffusivity, a. At time = 0 let this particle be exposed to an environment which is at a temperature T, and subsequently let there be a purely radiative heat exchange between the particle and the environment resulting in a spatially uniform heat flux at the surface. If in addition to the above we make the assumptions that the sphere is a gray body radiator, homogeneous, isotropic, and opaque, and that the physical properties are independent of temperature, conservation of heat in the sphere may be written as follows: The boundary condition contained in Eq. [3] states that the initial temperature of the sphere is considered uniform, equalling Ti, whereas Eq. [4] is readily obtained from symmetry considerations. Eq. [5] expresses the continuity of the heat flux at the surface of the sphere, or in other words the condition that the rate of heat exchange between the sur-

Jan 1, 1969

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies&apos;-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday&apos;s law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5&apos;= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.&apos;-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By H. E. Cline

A criterion for stability of a lamellar structure in two-phase alloys ulas derived froflr perturbation analysis of the steady-state solutions for eutectic growth. Both the mass and thermal diffusion were considered with boundary conditions for coupled lamellar growth. The concept of an effective liquidus slope was introduced. Excellent agreement was found with the experiments of Mollard and Flemings and the theory predicted a range of compositions on one side of the eulectic composition in which stable growth may occur with zero temperature gradient. The lamellar structure was found to be more stable than predicted by simple constitutional supercooling. The effect of impurity additions was also considered. DIRECTIONALLY solidified eutectic alloys may have a structure consisting of parallel plates or rods. It is important to know the range of composition and growth conditions that produce this ideal composite structure. Breakdown of the planar solid-liquid interface during growth may lead to a dendritic or cellular structure as in single-phase alloys. In the case of single-phase alloys, the concept of constitutional supercooling1 may explain breakdown, but in two-phase alloys the concept is no longer valid because the melting point is not given by the liquidus of one phase. Both phases must be considered in the mass and thermal diffusion problem. In the following theory a boundary condition at the solid-liquid interface was determined by using the steady-state equations of Jackson and ~unt&apos; to relate the average temperature and composition of the liquid at the interface. Then a sinusoidal perturbation in the shape of the interface was introduced to test for stability as in the analysis of Mullins and ~ekerka.~ The wavelength of the important perturbation was assumed to be much larger than the lamellar spacing, h, and the perturbation was assumed not to change the lamellar spacing, A. Both the mass and thermal diffusion equation were used with averaged quantities at the boundary to determine whether the perturbation grows or shrinks in time. A stability criterion was determined by considering the case in which the perturbation remains stationary. An example of Pb-Sn alloys was used to illustrate the validity of this theory. I) THEORY A) Temperature at the Interface. The temperature of the interface in coupled two-phase growth is close to the eutectic temperature TE even for alloys off eutectic composition. It is assumed that the interface is in local equilibrium and one expects the temperature at the intersection of the liquid phase and the solid phases a and 0 to be near the eutectic temperature. The interface is undercooled because of curvature and the deviation of the composition in the liquid from the eutectic composition. The average interface temperature Ti for steady-state growth of a lamellar eutectic with a plane interface was determined by Jackson and Hunt&apos; as given in their Eq. [17c]. Instead of using the ratio of the lamellar widths hp/h, as a parameter, the volume fraction of the 0 phase, +, will be used as it simplifies the algebra. The average interface temperature using this notation becomes: The average temperature of the interface depends on the volume fraction of the 0 phase, +, which may be related to the composition of the solid or the bulk composition of the liquid Co by: where C, and Cp are the average compositions of the solid phases. In steady-state growth, the composition of the solid is equal to the composition in the liquid far from the interface. The variation of the average interface temperature with composition is illustrated in Fig. 1 for the case of Pb-Sn alloys with a 10"4 cm lamellar spacing as calculated from Eqs. [I] and [2]. The interface temperature goes through a maximum at a composition near but not exactly at the eutectic composition. There is no reason why the composition corresponding to the maximum temperature should be equal to the eutectic

Jan 1, 1969

By John E. Miller

The Miller Number System is a well established method of measuring the relative abrasivity-friability of slurries, resulting in data that can be used in the selection of pump type and in forecasting wear-life of pumps and pipelines in slurry service. 1,2 Then after the pump type is selected, a Flow Analysis is determined by computer using pump design and operating parameters. This is used to determine pulsation control, suction requirements and stabilization, etc.

Jan 1, 1977

By Rossiter W. Raymond

The 12th of April, 1877, witnessed the celebration, at Freiberg, Saxony, of an event profoundly important for the ancient mining industry of that district, and full of interest to mining engineers throughout the world—namely, the connection of the famous Roth-

Jan 1, 1879

By L. D. Fetterolf

The New Jersey Zinc Zompany operates at Depue, Illinois, an integrated zinc smelting plant using tie vertical retort reduction process. The overall operation comprises green concentrate roasting, sintering, vertical retort smelting and metal refining. In the roasting operation, the fine concentrate is pelletized, the dried pellets fluidized and autogenously roasted with air in a “fluid column” with minimal formation of dust requiring recirculation. The roasted pellets and any associated roaster dust are agglomerated in a rotating drum and laid down, in combination with coal for fuel, on a Dwight-Lloyd sintering machine which converts to a semi-fused mass - a physical state more suitable for vertical retort smelting. The smeltins plant of 27 vertical retorts rated at 8 T zinc each per day on average requires the following major processing steps - mix preparation and briquettine, briquet coking, vertical retort reduction, vapor condensation and slab casting of metal. A portion of zinc production is converted to 99.99+ percent purity by boiling and fractional distillation in columns consisting of externally heated, superimposed trays of high-conductivity refractory.

Jan 1, 1970

By M. Guney, A. R. Bell

In Mindola mine on the Zambian Copperbelt, there is a plan to extend the current production level of 1.2- 1.5 km (3,900-4,900 ft) with five additional production levels. Research work indicated that the present total heat output of 38.6 MW will inevitably increase to 63.2 MW in 25 years. Estimated WE and DB temperatures, representing the total heat generation in stope faces and development headings during these same periods are predicted to increase to 33.8/40.2°C (93/104°F) and 35.3/42.1°C (95/108°F) respectively. It is assessed that the nominal refrigeration capacity needs to be progressively increased to 9,000 M W.

Jan 1, 1984

RAYMOND M. Howe (author&apos;s reply to discussion*).-Dr. Unger states that magnesite will hardly supersede dolomite in fettling after a heat; that it is hard to believe a slag composed of oxide of iron containing about 6 per cent. of phosphorus is the active corroding, agent in a boil in a furnace; and that boiling cannot be said to be the result of the chemical action of a high-phosphorus slag on a basic bottom. These are well-established facts that no one would venture to question. The authors were misinterpreted in the statement that "in the summary, it is claimed that magnesite low in lime, or of greatest purity, ranks first in resistance to slaking," etc. On the contrary, the position has been taken throughout that while a low lime content is advantageous, the presence of several per cent. of iron oxide (an impurity), is necessary in order to confer the proper bonding and sintering properties in dead-burned grain magnesite to be used for furnace hearths. We cannot subscribe to the view that pure magnesia is no better fitted for a refractory than pure lime,&apos; nor that the pure natural varieties of magnesite; such as Grecian or Washington, must necessarily be burned with silica and oxide of iron to produce a satisfactory material. On a small scale, pure magnesia has been satisfactorily used as a refractory in the form of crucibles. In the production of dead-burned grain magnesite from the Grecian or Washington mineral, iron oxide is added but the addition of silica is neither customary nor desirable. It is possible to manufacture brick of good quality from both the Grecian and the Washington material without adding either silica or iron oxide, providing they are burned at a sufficiently high temperature. This is regularly done on a commercial scale both in America and abroad when brick of. exceptionally high refractoriness or special purity are desired. The following analysis is of an English brick of Grecian magnesite which is extremely low in all impurities.1

Jan 6, 1919