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G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By W. B. Wise, H. D. Attra, W. M. Black

The purpose of this paper is to illustrate a comparatively new approach for solving a problem that has plagued oil producers for many years—how to make the most money with available field production capacity. In a very basic operation such as a top-allowable one-well field, a computer and staff of engineers are not required to determine that the best operation is to produce that well at its maximum for as long a time as it will produce. However, as the problem becomes more complex and the number of wells and number of reservoirs increase, it probably will be a wise choice to devote some engineering thought and calculation time to determine the best way to operate that field on both an ultimate and day-to-day basis. Continued developments in the field broadly referred to as "operations research" have led to a number of useful engineering analyses for optimizing field operational problems. One of these techniques, termed linear programing, is parlicularly interesting because of its potential applications to the study of complex oilfield operating problems. Linear programing is concerned with the problem of planning a complex set of interde~endenl activities in the best possible (optimal) fashion. A field application of linear programing is being used to maximize daily income from a multi-reservoir producing operation. The initial results of this study indicate that the linear programing technique (I) can be applied effectively to field problems, (2) can be used to detect unsuspected avenues for improving operations and (3) can effect a significantly improved means of controlling field operations through the use of the highspeed computer. INTRODUCTION The usual approach for studying complex field operational problems has been to look in detail at several basic plans suggested by judgement and experience and, then, to choose the best plan from those investigated. This approach is entirely satisfactory provided: (1) that judgment and experience alone will reliably pick the best or near the best program as one of the plans to be investigated; and (2), and most important, that the factors which control field production will not change. This paper deals with the large group of field operations which are at least one-step removed from a satisfactory solution using the conventional method of analysis. Problems such as pipeline- and gathering-system design, transportation studies, large field development projects and multi-reservoir producing operations fall in this latter category. To find the best program for handling these problems when the best program is not obvious, a complete optimization study is required, and high-speed computers are required to continually update the program once it is selected. Operations of this type have an extremely large number of possible solutions. However, only one will result in maximum economic return and, more important, this one program must be re-evaluated and adjusted constantly to accomodate such changing field factors as the number of producing days, the price of crude, the discovery of new reserves, declining reservoir pressure with subsequent decline in production and a host of other factors which characterize specific operations. One of the most widely used, direct methods of optimization is a numerical procedure termed "linear programing", which is designed to investigate systematically each of the possible solutions involved in a given problem, determining rapidly and uniquely the optimum answer. As implied by the name, linear programing requires that all field variables be either defined or expressed in a series of interdependent linear equalities or inequalities. These relationships are solved simultaneously, using a form of matrix solutions to determine the optimum values for each producing variable that will maximize net profits. The solution techniques used in a recent field case study is termed the "simplex method" and is discussed in full detail in Ref. 1.

By Edward Judd

THE old Cerro de Pasco smelter at La Fundicion, near Tinahuarea, 9 miles. from the Cerro de Pasco. mines and at an elevation of 14,300 ft., has now been replaced by a thoroughly modern smelting plant at Oroya, the junction point of the company's private railroad with the Central Railway, of Peru. This site has the advantages of being closer to the Morochoca mines, as well as nearer to the port of Callao, and at the same time is 2000 ft. lower in elevation, which benefits not only the cost of transportation but also the tech-nical operation of blast furnaces , and converters. The Oroya smelter was designed with the idea of .smelting about 2500 tons of. ore per day, but having in mind the possibility of increasing its capacity, all departments of the plant can be extended within reasonable -limits; for instance, if it is found that reverber-atory smelting is cheapest, taking into consideration the cost of fine crushing and fuel, it is possible to extend the roaster and reverberatory plants accordingly. The ore handling system is modern, consisting of belt conveyors, reclaiming machines, and electrically driven calcine cars, all requiring the minimum of labor. Waste heat from the reverberatory furnaces is utilized in boilers for the production of power to operate the plant, and the power house is equipped with condensing units to obtain the highest economy. Shop installations for the making of all repairs required for the smelter are unusually complete, includ-ing iron foundry, steel foundry, forging and machine shops, carpenter and pattern shops, and an electrical shop. There is also a plant for the production of all clay and silica refractory brick used in the furnaces; this is situated on the smelter site and is conveniently arranged for receiving raw materials and delivering finished brick to the several departments of the smelter. The laboratory is in a wing. of the general office, which is a two-story brick structure, situated on the smel-ter site.

Jan 10, 1923

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term ''connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;' Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 ' to 10' cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10' cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By Georges Fleming

The new burden preparation plant of ARBED Luxembourg, Belval- Works, which comprises 2 large sinter strands, is equipped with a process computer connected to a comprehensive process control system. The main jobs done by the computer are the control of the raw mix composition, and thus the monitoring of the stacking of the piles at the bed-blending plant, and the optimization of the sintering process. Among the optimization criteria, quality is considered as the most important. The sinter quality, characterized by the mechanical strength and the state of oxidation, is controlled automatically. The control system which we have dev loped is highly reliable; as a result, the standard deviation of Fe++, for the control of bivalent iron, has been narrowed to 0,5 % and the standard deviation of the IS0 + 6, 3 mm index, for the control of the mechanical strength, has been kept within 1 %. Thanks to these results, the combined savings in fuel consumption at the sinter plant and at the blast furnaces have covered the total costs of the optimization project in 2 years. By applying automatic control, the optimum driving range of the sinter plant has been defined and these new guidelines are used for monitoring the sinter production.

Jan 1, 1977

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman's hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By G. S. Cole, G. F. Bolling

Recent experitnents on crystal growth have indicated that thermal convection in the liquid influences the conditions of solidification and subsequent crystal characteristics. However, the important columnar-equiaxed transition in castings has not been examined as a function of this free convection. An experiment is presented here to demonstrate a change in the transition as convection is suppressed. Lead- and tin-based alloys were cast in stainless-steel molds either without special procedures or with thin grids placed horizontally across the tnold diameter in portions of the castings. While the grids allowed some diffusion of heat and mass transport to occur during solidification, massive fluid flow was hindered in the vegiotz of the grids. A larger percentage of columnar grains appeared in the grid region than in other parts of the special castings or than in all regions of normal castings. This structural difference can be explained in terms of thermal convection. THERE is little information about the possible effects of natural convection which may occur during the solidification of a casting. Ruddlel-3 has stated that the movement of liquid metal produced by convection might assist in the transfer of heat, but in the absence of confirmatory evidence he suggested that this idea be treated with caution. chalmers4 considers, but does not assess, the importance of fluid motion in casting, while Tiller5 suggests that, in liquid metals which have extremely high thermal diffusivities, the effects of thermal convection may be negligible. In addition, throughout the literature, there are statements indicating the possible presence of thermal convection but without proofs or evaluations of its influence. Natural convection may be divided into two categories: thermal convection, where liquid flow is due to density differences caused by temperature gradients in the liquid (e.g., liquid near a cold wall falling with respect to hotter liquid further away from the wall); and solute convection, where flow is due to density differences as a result of concentration gradients, see Wagner.6 In most instances thermal convection predominates over solute convection. Nevertheless, even thermal convection has not been studied in any detail and is difficult to handle, since it can vary quantitatively from one experiment to another depending upon the exact positions of heat sources and sinks or the attitude of the container with respect to gravity. In spite of these difficulties it is possible to realize that a higher rate of heat transfer must result with convection than in any situation where conduction acts alone. Thus, the degree of increased heat transfer is the important undecided question in considerations of casting. It will be demonstrated here that a reduction in convective flow leads to a suppression of the columnar-equiaxed transition in a casting and that this suppression is related to a decrease in the degree of heat transfer. Fortunately it is possible to do this by comparative rather than quantitative measures. The insertion of horizontal plates or grids into a simple mold does not appreciably influence heat transfer per se, but in reducing the allowable height through which colder liquid may fall freely it reduces natural thermal convection. This leads to a reduced fluid velocity, a different flow pattern, and an altered heat transfer which can be measured. EXPERIMENTS The alloys were prepared from elements of 99.9 pct nominal purity and cast into an uncoated 2-in.-diameter stainless-steel mold insulated at the bottom with a suitable refractory so as to ensure predominantly radial heat flow during freezing. Casting was performed either in empty molds or in molds containing grids or plates in various configurations . The grids were constructed of aluminum screen (1/32 in. thick) which was cut to the desired shape, cleaned in aqua regia, and coated with a mixture of 2 parts aqua dag graphite -1 part Sauereisen cement mixture, thus supplying a hard, protective, and insulating layer approximately 0.006 in. thick. The

Jan 1, 1965

By W. P. Heineken, A. T. Child

This paper presents the results of a series of experiments made in the metallurgical laboratory of Columbia University, New Pork City. The object of the investigation was to determine, as far as possible, the changes in micro-structure and physical properties caused by short periods of heat-treatment and the longer malleable cast-iron process. It was proposed to do this by means of micro-photographs, heating- and cooling-curves, and tensile tests after the various heat-treatments. I. Micro-Constituents of Iron and Steel. The list of the micro-constituents of iron and steel has grown till now it includes seven different substances, called ferrite, cementite, pearlite,* martensite, austenite, sorbite and troosite. Only the first five of these are mentioned in this paper, to facilitate the understanding of which, the following brief definitions are given: 1. Ferrite (named by Prof. Howe) is, chemically, iron free from carbon. It is the softest of the constituents, and is not colored by etching, except when long-continued. Under the microscope it is easily determined by its regular polygonal etructure; or, if structureless, as in malleable cast-iron, by the ease with which it is scratched. Ferrite appears in mild steel in small amount, in grey cast-iron, and in malleable cast-iron. 2. Cementite (also named by Prof. Howe) is now generally conceded to have the formula Fe3C. It is the hardest of the micro-constituents, having the hardness indicated by 7 of the mineralogical scale; and hence it is always left in relief after

Jan 1, 1901

By A. E. Brugger

SOME 2,000 years ago Pliny is supposed to have said, "Out of Africa always something new." It may perhaps even now be news to a great many that the Belgian Congo has in recent years been producing approximately a quarter of a ton of diamonds annually. For that is what the 1 1/4 million carats, the recovery from 40-odd operating mines, and about 20 or 25 per cent of the world's normal consumption, amounts to. In 1915, first exploitation operations produced less than 50,000 carats from two mines. The rapid expansion of operations following the Euro¬pean war meant a most rapid development of a virgin land. The interior is now reached by air in one day from the mouth of the Congo River, where steamers unload mail and passengers from Antwerp. This trip formerly consumed 4 to 6 weeks by a narrow-gage, wood-burning, railroad around the rapids of the lower Congo and Livingston Falls; by river boat to the heads of navigation, Djoko Punda on the Kasai or Luebo on the Lulua; and thence by caravan of native porters over narrow-trails to head¬quarters on the Tshikapa. Hundreds of miles of automobile roads have been constructed over veldt and through forest, bridging streams and ferrying rivers. The railway from Capetown to the Katanga copper district to the East, once two months away by trail is now reached in 2 or 3 days over fair automobile highway. Native "boys" who a few short years ago wore little more than a smile and a string of beads and to whom a wheelbarrow was a complicated piece of machinery, are today driving Fords, tending boilers and engines and operating electrical equipment, or are capable mine workmen, machinists and artisans, and dressed in all manner of cast-off white man's clothing. Even as late as 1920, due to difficulties of securing and transporting machinery during and just after the war, the crudest hand operations were the rule for the excavation, sizing, and concentration of the diamondiferous gravel. All washing and concentration is now mechanized, using steam or electric power, and where operations are sufficiently large to permit competition with native labor costs, excavation and transportation are also accomplished by machinery.

Jan 1, 1932

By Joseph Hartshorne

EVER since the introduction of the Siemens regenerative furnace, it has been recognized that a certain amount of gas is lost each time the furnace-action is reversed. This loss comes, first, from the gas which passes through the free connection between the stack and the gas-main, which exists during the time the reversing-valve is turning over; and, secondly, from the gas which is in the chamber and flues, from the hearth to the reversing-valve, and which flows back into the stack when the valve is reversed. The amount lost each time is, of course, small; but, since a furnace is reversed from four to six times every hour for, say, 300 days in the year, the aggregate is large enough to be well worth attention. The estimate has been published' that, in Germany alone, the loss from the first of the above causes amounts to 500,000 marks per year. The loss from the second cause is, of course, much greater. A process for saving this entire loss, in use at Teplitz, Bohemia, for about three years, would seem to be of value even in this country, where coal is cheaper and where the small economies are not watched as closely as they are in Europe. This process, invented by Mr. Adelbert Kurzwernhart, late Technical Director of the Teplitzer Walzwerk, has been worked out with thoroughness. The loss from each cause can be calculated very closely for any particular furnace, and the results to be expected from the process ascertained. It can easily be decided, therefore, whether it is worthwhile to adopt it under any given conditions. The amount of chamber-gas lost depends upon,-(1), the cubic contents of the chamber, ports and flues upon one side of the furnace, up to the reversing-valve (deducting, of course,

Mar 1, 1906

By S. E. Bretherton

During the year 1878-79, Anton Eilers, who was then interested in the lead smelting and refining business near Salt Lake City, Utah, made a somewhat radical departure from the regular practice at that time, which was to use but little lime in the slag, with a high percentage of iron. Lime was not only a cheaper flux than iron, but it enabled the metallurgist to make a more siliceous slag, an economical advantage in smelting where the smelting companies had to purchase either iron or lime to neutraiize the excess silica, and penalize the ore shippers accordingly. The larger amount of both lime and silica in the slag also made it of lighter specific gravity, and a better separation of the metals and mattes was secured. This change in the formation of slags for lead smelting was brought about by Anton Eilers, prior to the Leadville mining excitement of 1879.. We must also give Mr. Eilers credit for the general introduction of the hollow water-cooled cast-iron jacket for the blast furnace. Again referring to the use of more lime and less iron in the formation of slags, there is no doubt but that it prevents the formation of a great many so-called "sows" in the lead crucible, such as were made in the early history of lead smelting in the Rocky Mountains; these sows consisted of lead, iron, arsenic, sulphur, copper, and other metals, including gold and silver, mixed with unconsumed fuel, and often, after vain attempts to cut them up or melt them to a suitable size for handling, were buried in the slag dumps to get them out of sight. Another advantage derived from the adoption of high-lime slags when smelting ore containing arsenic is the production of less speiss (a byproduct heavier than matte, resulting from careless operation of the furnace, in the lead being driven out of the crucible and sows built up). This speiss, while usually not as rich in precious metals as matte made at the same time, is too valuable to be thrown away; but it is difficult to treat, and it was thrown away or piled on the slag dumps in the pioneer days of lead smelting in this country. About the time of the introduction of the lower iron and higher lime slags in lead smelting, sulphide ores were encountered in Utah and Colo-

Jan 1, 1916

Andy H. Vassiliou – Introduction Ladies and gentlemen,.good evening and welcome to the Paul F. Kerr Memorial Symposium dinner. I believe we are all here to honor the memory of a great teacher and advisor, and a true friend -- Professor Kerr, or Dr. Kerr, or to most of us who were his students, "Pappy" Kerr. Most of us who attended the Paul F. Kerr Memorial Symposium earlier today at the New York Hilton had the opportunity to read, or listen to, or discuss scientific papers presented in honor of Dr. Kerr. In addition, all of the speakers had the opportunity to reminisce about their association with Dr. Kerr, who was credited as having contributed substantially to their graduate education and the development of their careers. Dr. Kerr's two daughters -- Ruth and Nancy -- who attended the Symposium at the Hilton are also here with us tonight. I think we should keep tonight's festivities on an informal basis since we are all old friends or former students of Dr. Kerr. Some of us may want to say a few words about our experiences at the time we were students at Columbia, and hopefully include some anecdotes relating to Professor Kerr. I would like to invite everyone to do so, but first we have arranged for two of us to be the lead speakers, whom I will introduce in a few moments.

Jan 1, 1985

By N. E. Truitt, D. G. Russell

The transient pressure behavior of a well which produces a single compressible fluid through a singte-plane wrticat fracture has been investigated mathematically. The fracture is assumed to possess infinite flow capacity, to be of limited mdial extent, and' to penetrate the producing formation completely in the vertical direction. Previous studies of vertically fractured wells have been concerned primarily with production rate performance or semisteady-state pressure behavior. This study was undertaken to ascertain the influence of vertical fractures on transient pressure tests such as pressure build-ups and flow tests. In a vertically fractured system, flow in the region nearest the fracture is practically linear, whereas farther away from the fracture essentially radial flow prevails. Thus, transient pressure analyses based on radial flow theory are somewhat inaccurate. As fracture penetration increases radially, kh values calcutated from pressure build-up and flow test curves become increasingly larger than true values. Failure to consider the effect of fracture penetration also introduces inaccuracies into the catculation of fracture length from the apparent skin factor and into the determination of average reservoir pressure. If the total length of the fracture is 20 per cent, or greater, of the drainage radius of the well, corrections must be made to pressure build-up and flow test results. Methods for correcting such results are discussed in this paper. For wells with prefracturing pressure build-up or flow test data, it is possible to estimate fracture length by comparison with postfracturing build-up or flow test results. In new wells or wells without prefracturing build-up or flow test data, fracture length must be estimated to correct the values obtained from analysis of pressure tests after fracturing. Fracturing efficiency calculations should be made whenever possible to provide an estimate of fracture length. Tables of the dimensionless pressure drop as a function of time and fracture penetration are included in this paper. Using these values should permit analysis of other types of transient pressure behavior in vertically fractured wells. INTRODUCTION Hydraulic fracturing has been used quite successfully for over a decade as a completion and stimulation technique in oil and gas wells completed in low-permeability reservoirs During this period a considerable amount of theory has evolved on the performance of hydraulically fractured reservoirs and on more efficient means of artificial fracturing. Although theory has been developed, no rigorous investigation has been made of pressure build-up and flow test behavior in such wells. Prats et al.1 first discussed the performance of vertically fractured reservoirs for the case of a compressible fluid. Their work was primarily concerned with production performance at constant flowing pressure. These authors also considered large-time (semisteady-state) constant production rate behavior for vertically fractured wells; however, transient pressure behavior at constant rate was not investigated. McGuire and Sikora10 and Dyes, Kemp, and Caudle2 employed an electrical analog to investigate the influence of artificial vertical fractures on well productivity and pressure build-up. They found that fractures which extend beyond 15 per cent of the drainage radius away from the well alter the position and slope of the straight-line portion of the build-up curve. They concluded that these effects must be considered both in the determination of the effective permeability of the formation and in any calculations of final build-up pressure. Although these authors did not undertake an exhaustive study of the influence of vertical fractures on pressure build-up performance, their limited results were quite interesting from the standpoint of the effects they demonstrated. In a more recent paper, Scott- reported the results of an investigation of the effect of vertical fractures on pressure behavior, which was conducted with a heat flow model. Scott's results appear to be consistent with those reported in Refs. 1 and 2. However, the effects of different fracture lengths on performance were not investigated. Pressure build-ups and transient flow tests are among the most diagnostic tools available to the reservoir engineer or production engineer. Since a very high percentage of present-day well completions incorporate the hydraulic fracturing technique, a definite need exists for information on the effect of fractures on transient pressure performance. For these reasons we have undertaken a rigorous study of pressure build-up and flow test behavior in vertically fractured reservoirs. The objectives of this study were (1) to obtain synthetic pressure build-up and flow test

Jan 1, 1965

By Percy W. Bidwell

THE statisticians had defeated Germany months before she invaded Poland. With batteries of adding machines they had proved that she was suffering from serious deficiencies in critical food- stuffs and in practically all of the raw materials necessary for the conduct of modern warfare. Their calculations showed that with respect to fats, oils, wool, cotton, hides, petroleum, iron, copper and other metals, the Reich was bound to be at a great disadvantage vis-a-vis the French and British as long as the latter could keep open the lines of sea communication. The conclusion seemed obvious-"Germany can't win." The more cautious of the commentators introduced qualifications as to the length of the war and the tightness of the British and French blockade. They also made a third qualification as to the character of the struggle- whether it was to be a war of attrition or a war of movement. But since the invasion of Norway in April, there is no longer any doubt on this score. It is a war of movement-a war in which fuel, lubricants, and metals are being consumed on a scale never before seen.

Jan 1, 1940

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By William P. Blake

IN southern Arizona and in Mexico the word caliche is in general use to denote a calcareous formation of considerable thickness and volume found a few inches, or a few feet, beneath the surface-soil, upon the broad, dry, gravelly plains and mesas. In western South America the same name is applied to the beds of crude soda-niter (Chili saltpeter). While these deposits of South America and of Arizona are totally different in composition, and have nothing in common, except that both occur in layers in the strata near the surface, it is probable that an explanation of the origin of the calcareous beds may equally apply to the accumulation of sodaniter and other deposits of easily soluble minerals. But the name, taken from the Latin, Calx, is more appropriate to the calcareous beds than to those of niter. Caliche has a wide distribution in the arid regions of Arizona and Mexico. It is usually hidden from view by a slight covering of soil; but it is easily found by digging, and is often revealed by a flow of water during heavy rains. It is practically a continuous sheet, from three to fifteen feet thick, of earthy limestone or travertine, through which the smaller plant-roots find their way with difficulty. The presence of this comparatively impervious layer of cemented earth may account for the absence of trees, or of the larger shrubs, over wide areas. The shrubs which gain a foothold are those whose roots do not extend far downwards, and which do not require much water, such as Larrea Mexicana and the [Cactaceoe]. If trees are planted, it is necessary to break up the caliche by blasting, or at least to crack the upper layers. The top of the caliche is more dense and solid than the lower portions. The surface of this top crust, or layer, is comparatively smooth, though undulating, while the lower portions, under the crust, are irregular, cavern-

Jan 1, 1902

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947