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[United Engineering Society WALTER H. ALDRIDGE J. VIPOND DAVIES J. V. N. DORR Engineering Societies Library Board SYDNEY H. BALL ALEXANDER C. HUMPHREYS GEORGE C. STONE JOHN H. JANEWAY Engineering Foundation Board H. M. BOYLSTOX J. VIPOND DAVIES GALEN H. CLEVENGER]

Jan 1, 1928

By J. W. Spretnak, G. Sachs

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By G. Sachs, J. W. Spretnak

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By Walter S. Weeks

The process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the JouleThompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. C, Specific heat of air at constant volume, B.t.u. per lb. per deg. F. C, Specific heat at constant pressure, B.t.u. per lb, per deg. F. T1 Absolute temperature of air in pipe, deg. F. T8 Absolute temperature of air outside after expansion and mixing and coming to rest. j Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone', the giant Kirkuk field in Iran', the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By Paul A. Farrar, Harold Margolin

The Ti-Al-V system has been delineated from 50 to 100 wt pct Ti and front 600 to 1400°C by X-ray and ntetallographic techniques. Isothermal sections were delineated at 600, 700, 800, 900, 1000, 1100, 1200, 1300, and 1400°C. X-ray and metallographic evidence indicated the presence of two phases and in addition to those reported by previous investigators of the ternary system'-3. T HE titanium-rich region of the Ti-Al-V system as originally proposed by Rausch et UZ, and Jordan and Duwez3 was based on the binary Ti-Al diagram as proposed by Bumps et uZ. As additional phases have been shown to exist5-' in the region previously thought to be all a, the titanium-rich region of the Ti-Al-V system is open to serious question. Therefore, in order to determine the effect of the indicated changes in the Binary Ti-Al system on the ternary Ti-Al-V system the present investigation was initiated. EXPERIMENTAL PROCEDURE The experimental procedures in this investigation are the standard techniques used in the study of titanium-alloy systems which have been described in detail previously.1° Consequently, only details pertinent to the present work are discussed. The alloys employed for the delineation of this system were prepared from titanium obtained from the Bureau of Mines (73 BHN) 99.99 pct Al and 99.7 pct V, by the consumable arc-melting technique. The titanium was premelted into buttons of 25 g because spattering during the first melt caused uncontrollable loss of alloying constituents. Typical analyses of the material used have been reported elsewhere Attempts to hot roll the alloys prior to heat treatment were made on the first series of alloys prepared, but as the area of extensive hot workability was fairly restricted, see Table I, this practice was discontinued. The times of isothermal annealing are given in Table 11. A preliminary heat treatment of 96 hr at 1000°C was used prior to heat treatment at lower temperatures. The standard techniques used for polishing specimens involved belt-grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch. In the low-alloy region it was found that the oRo etch, developed by Ence and Margolin,o gave better contrast between phases. Where this procedure did not differentiate between phases clearly, the method of stain etching developed by Ence and was used. It has been previously reported15 that filing of titanium alloys is not desirable for producing X-ray powders, since the powder becomes contaminated by the file material. Therefore, for those samples not brittle enough to Crush, the procedure described below was used. The specimen was wrapped in molybdenum sheet and placed in a vacuum system and evacuated to 0.03 p. Palladium-pur if ied hydrogen was then admitted to the system until a partial pressure of 5o Cm of H was reached. The specimen was heated in the system to the temperature of original heat treatment and was slowly cooled over a period of 3 hr to 400°C while the partial pressure of hydrogen was maintained. The sample was removed from the system after it had completely cooled and was crushed to a powder of 230 to 270 mesh. The powder, wrapped in molybdenum sheet, was dehydrogenated at the temperature of original heat treatment until a partial pressure of 0.03 p was maintained in the system for at least 1/2 hr. The tube containing the powders was quenched in iced brine while still connected to the vacuum system. After dehydrogenation, the powder, except for the

Jan 1, 1962

By Helmut Thielsch

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

Jan 1, 1946

By Eleanor Haslem, Carl A. Zapffe

THE present investigation has three principal purposes: I. To develop a method for measuring hydrogen embrittlement that avoids certain errors complicating previously used methods. 2. To explore in a preliminary way some of the fundamental factors controlling embrittlement. 3. To apply the measurements specifically to stainless grades of steel, whose sensitivity or insensitivity to hydrogen embrittlement has never been clearly defined. SELECTING A TEST METHOD Hydrogen embrittlement is a condition of low ductility resulting from excessive absorption of hydrogen by the steel at some period in its history, and may be revealed by almost any test involving cold deformation. Tensile tests, impact tests, and bend tests are commonly used for detecting hydrogen embrittlement; although numerous other tests, such as cold-upsetting or extrusion, could be used. The simplicity of using a wire specimen for cathodic and acid pickling tests, and the especial adaptability of the bend test to wire specimens, led to selection of the bend test for the present research. Bend tests usually have been of three general types: (I) fatigue, (2) reversed bend, and (3) single bend. The first two types, though widely used, are inaccurate because their measurements are counteracted by an aging effect; and the third type has not been developed to its fullest utility. The effect of cold-working in removing hydrogen is well known. During a bend test hydrogen can be observed escaping from the convex side simply by coating the specimen with oil; and any technique employing flexing or reverse bending may therefore have its measurements masked because the mechanical action reduces the embrittlement during the test. This factor is so important that even elastic flexing of a hydrogen-charged wire specimen should be avoided before testing if accurate measurements are desired. DEVELOPING A MACHINE FOR MEASURING HYDROGEN EMBRITTLEMENT As for the single-bend test, its theory is good, and recovery caused by mechanical work is kept to a minimum. With a given degree of hydrogen embrittlement, a specimen will break at a given angle if the bending is applied unidirectionally and uniformly. The radius of the bend must be kept constant; and the rate of bending should be a constant, slow enough to allow reading of the breaking angle, and yet rapid enough to prevent significant recovery from the escape of hydrogen during bending. A simple apparatus (Fig. I) was constructed using a type H Foxboro drive unit A, which is a synchronous motor with a gear-reduction ratio of 600 to I. A cord, fixed at one end to a wooden pulley B on the drive shaft of the motor, follows the pe-

Jan 1, 1946

H. RIES, Ithaca, N. Y.-The part of Mr. Fiske's paper that interests me especially is that portion dealing with the raw materials, and the tests that were applied to the raw materials in order to determine their value in advance, if possible, because that, I believe, is a step in the right direction. For a number of years I have done my best to persuade different consumers of clay to develop standard methods for testing raw materials. We have in this country a large variety of clays which can be used for a great many different purposes, but in many cases the consumers either have no standard methods for determining the value of those clays in. advance, or if they have they do not publish them; consequently it often puts the clay miner at a disadvantage. If, for example, manufacturers of different types of refractory materials would state publicly just what physical tests their raw materials have to meet, it would, I believe, help them to find more easily the materials that they are looking for, and the clay producer would also be benefited. It would also encourage him to have his clays tested in advance, so that samples could be accompanied by certificates of physical tests that would be of convenience to the manufacturer. At the present time, in this country there are certain types of clay which seem to be rather scarce. There apparently are not many deposits of clay that are exactly suited for the manufacture of zinc refractories. So, too, there are not many deposits of clay that are suited for the manufacture of glass-pots, or the blocks for glass tank furnaces, or clays that can be used for graphite crucibles. Now, in many cases, no standard series of tests has been developed. I am also gratified to see that Mr. Fiske considers the tensile strength. tests of value. Some years ago the American Ceramic Society appointed a committee to draw up a series of recommendations covering standard tests. These recommendations were especially for the use of State geologists and the U., .S. Geological, Survey. Among the tests that were considered was the tensile-strength test, which Mr. Fiske has mentioned in his paper. Unfortunately, a majority of the committee turned it down, and the test was therefore not officially approved, but two of us, who formed the minority, believed in it. Since then the other members of the Committee have come to see that that is an important test to make and Mr. Fiske has emphasized it in his paper.

Jan 1, 1918

By R. M. Asimow

The magnetization curves for specimezs containing superparmagnetic particles are considered. It is shown that the curves may differ from a Langezlin function because of particle anisotropy, particle interactions , and the presence of a size distribution of particles. The various causes of particle anisotropy are considered, and magnetization curves for specimens with cubic and uniaxial anisotropy are presented. The magnetization curves depend on the In the particle-size below 100A it is quite difficult to obtain quantitative size and shape information on precipitate particles. All of the available techniques have their limitations; however, quantitative applications of superparmagnetism have not been developed as fully as possible due to a lack of analysis of the complete magnetization curve. With such an analysis it appears possible to obtain from a single magnetization curve of a specimen containing randomly oriented SPM (superparamagnetic) particles a quantitative volume distribution and a description of the particle shape.* sign of the anisotropy energy and in the case of a negative uniaxial anisotropy (prolate spheroids) the resulting curves may differ very considerbly from a Langevin function. A graphical technique is developed whereby it is possible to separate out the effects of the size distribution, the particle interaction, and the particle anisotropy. Thus it is possible to obtain quantitative values for both the particle shape and the size distribution. Langevin function2 I/Is = ctnh(HVIs/k T)-k T/HVIS [ 1 ] where I, is the saturation magnetization, V the particle volume, H the applied field, T the particle temperature, k the Boltzmann constant, and I the magnetization in the direction of the applied field. Such behavior is rarely if ever observed in actual systems. One explanation for this is that the SPM particles do possess a significant anisotropy and thus the magnetic energy associated with the particle depends on the direction of magnetization in a more complicated way than for the isotropic particle of Eq. [I]. In general the magnetic energy E of an isolated SPM particle embedded in a nonmagnetic matrix can be expressed as a sum of several contributions: E = Eh + Ed+Es+Ec [2] where Eh is the external field energy, Ed the energy resulting from the particle demagnetizing factor, E, the magnetostriction energy, and E, the crystalline anisotropy energy. In each term we consider only the part dependent on the orientation of the magnetization vector and the particle axes as the shape of the magnetization curve will be determined by these contributions. Following the same procedure used in deriving the Langevin function,

Jan 1, 1965

By Joseph C. Kieffer

THE Duquesne property of the Callahan Zinc-Lead Co. is about 20 miles east of Nogales, in southern Arizona. One mine is near the mill, but most of the mill feed is hauled in by truck from a number of small mines. The same sulphides are found in all the ores, in general, but the amounts vary considerably. All ores contain silver, copper, lead and zinc minerals but one mine ships ore high in silver and lead and low in copper and zinc; while another mine ships ore high in copper and zinc, and low in silver and lead. The common sulphides are galena, carrying most of the silver; chalcopyrite; sphalerite, carrying iron in solid solution; and pyrite, in a gangue consisting of limestone, quartz and garnet. Mineralization is fairly coarse. At the present grind of about 66 per cent minus 200 mesh most of the sulphides are liberated. A small amount of chalcopyrite is locked up with the sphalerite and cannot be liberated at an economic grind, and the copper carried into the zinc concentrate with the sphalerite accounts for the comparatively poor recovery of copper in the copper-lead concentrate. PRODUCTION OF TWO CONCENTRATES The milling problem, which was complicated by the extreme variation in the grade of the feed, was first attacked with the idea of producing a silver-copper-lead concentrate and a zinc concentrate, both with satisfactory grades and recoveries. By February I94I, it was felt that these objectives had been attained, when the grades of the various products and the recoveries were as shown in Table I. [ ] A rough outline of the flowsheet and reagents used is as follows: Minus ¾ -in. feed to a 7-ft. by 36-in. Hardinge ball mill working in closed circuit with a 36-in. Wemco classifier. The classifier overflow passes to the second cell of an 8-cell bank of No. 18 Special Denver Sub-A flotation machines (volume, 22.5 cu. ft. per cell). A rougher concentrate is removed from the second to the fifth cells inclusive, and returned to the first cell, which is the cleaner. A scavenger concentrate is removed from the sixth, seventh, and eighth cells, and returned to the third cell. Consump

Jan 1, 1942

By George S. Evans

CERTAIN American operators believe that desulphurizing in the ladle offers a means of increasing blast-furnace and open-hearth yields with the possibility of improvements in quality of the steel. In fact, several producers have experimented with practically all of the known desulphurizing agents, including both standard grades of the alkalies and special preparations that have been offered from time to time during the past several years. Some of these are regularly being used today in large-scale commercial operations, with good results. Also, it is the practice to treat off-sulphur casts in the blast-furnace ladle at a number of plants. It is not known, however, that anyone in the steel industry (American) has ever adequately equipped a plant for desulphurizing blast-furnace metal in an efficient manner as regular operating practice. The purpose of this paper is to illustrate the importance of correct equipment and proper handling for obtaining uniform and efficient results. As will be shown, at the temperature of molten iron the alkalies are instantly neutralized by any free slag present, dissipating their desulphurizing value. Entrained silicates are rapidly washed out of the metal bath by the highly basic soda slags and will be satisfied ahead of desulphurizing reactions with FeS. More or less of the reagent will always be used up through reactions with the refractory lining. Desulphurization will be limited to the action of the free alkali then remaining in the slag. Causes for the erratic results generally found with desulphurizing tests in blast-furnace transfer ladles would include, among other things, variations in the quantity of furnace slag coming down with the metal, and differences in the percentage of kish and entrained silicates in the different casts. As the alkalies instantly unite with any free slags or silicates present, these, with any kish coming off, both dilute the reagent and reduce the surface contact between the slag and metal, thereby retarding the desulphurizing reactions.

Jan 1, 1938

E. O?C. Acker Truman H. Aldrich Walter H. Aldridge Anson W. Allen John H. Allen W. Lawrence Austin W. S. Ayres David Baker John Henry Banks Alonzo F. Bardwell Robert Bentley Andrew A Blair Walter M. Brodie Fredrick Burbidge H.H. Burden Charles Butters

Jan 1, 1939

By N. W. Lord

There hare been made at one or two places in Ohio, during the last year or two, some irons of rather unusual phosphorus-percentages. The first of these which I had occasion to examine came from Moxahala Furnace, in Perry county. The furnace was built originally to smelt an ore found in large deposits near its furnace in the " black band" horizon. The deposit was easily exposed by simple stripping;" it was from six to eight feet thick, being a blne carbonate ore, very free from silica. This ore yielded, on analysis, from two to 3 per cent. of phosphorus, when carefully sampled. The furnace company had trusted entirely to old analyses made on "outcrop" ore, well weathered, and received all other results with indifference. The result of the first run of the furnace was an iron in large whitish-gray crystals, and so brittle that it could be pulverized in a mortar. This iron contained 4.90 per cent. phosphorus. A limited quantity only was made, which was gradually disposed of as a great ('softener" to foundries. The Moxahala Furnace was subsequently run on Lake Superior ore mainly. The second case of such iron occurred last summer at Mt. Vernon Furnace. A deposit of what was locally known as "Hallelujah" ore, was opened for the furnace. This ore was a blue carbonate, similar to the first-described. The iron made was pure tin-white in color, and showed large crystals without a trace of the grain of ordinary pig-iron. It was sopposed at the furnace to be spiegeleisen, and was sent to me to be

Jan 1, 1884