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By Paul Merica

THOSE of you who, like myself, have had the privilege of hearing previous Howe Memorial Lectures will note, and I hope without too much disaffection, that for the first time in this series of lectures iron has been chosen as the subject. I feel sure that the predominant choice by previous lecturers of subjects relating to steel has been principally in deference to the well-known interest this subject held for Professor Howe, and that their choice has not reflected any lack of respect for the material, iron. Nevertheless, in the face of this record, I feel some diffidence in introducing this "Cinderella" of materials into the circle of distinguished subjects hitherto treated by Howe lecturers, which is relieved only by the fact that I hope to be able to present some evidence that this Cinderella has at last undergone some of those magical trans-formations which render her acceptable even in the society of her dis-tinguished sister, steel. Fortunately I can cite the old master himself in support of my choice of subject and recall to you that Professor Howe by no means overlooked or neglected cast iron in the long course of his metallurgical meditations. Indeed his attention was early arrested by a metallurgical aspect of cast iron which he believed and we still recognize as of the most funda-mental importance-namely, the genesis of graphite in gray iron and the means for the control of its quantity and distribution. He made some comments over 20 years ago regarding the nature of J. E. Johnson's oxygenated iron which indicate that even then his thoughts were taking directions which today we are finding it useful to explore in connection with the theory of high-strength iron. Had we had in the subsequent years the continuing benefit of Professor Howe's illuminating consider-ation of this important subject, our progress in the improvement of cast iron would undoubtedly have been even more rapid.

Jan 1, 1937

By C. S. Land

Relative permeability functions are developed for both two- and three-phase systems with the saturation changes in the imbibition direction. An empirical relation between residual nonwetting-phase saturation after water imbibition and initial nonwetting-phase saturations is found from published data. From this empirical relation, expressions are obtained for trapped and mobile nonwetting-phase saturations which are used in connection with established theory relating relative permeability to pore-size distribution. The resulting equations yield relative permeability as a function of saturation having characteristics believed to be representative of real systems. The relative permeability of water - wet rocks for both two- and three - phase systems, with the saturation change in the imbibition direction, may be obtained by this method after properly selecting two rock properties: the residual nonwetting-phase saturation after the complete imbibition cycle, and the capillary pressure curve. INTRODUCTION Relative permeability is a function of saturation history as well as of saturation. This fact was first pointed out for two-phase flow by Geffen et al. 1 and by Osaba et a1.2 Hysteresis in the relative permeability-saturation relation also has been reported for three-phase systems.3 Since saturations may change simultaneously in two directions in a three-phase system, four possible relationships arise between relative permeability and saturation for a water-wet system. The four saturation histories of this system were given by snel14 as 11, ID, DI and DD. I and D refer to the direction of saturation change (imbibition and drainage), with the first letter of the symbol indicating the direction of change of the water phase. As used in this paper, the second letter of the symbol refers to the direction of saturation change of the gas phase, i.e., D and I indicate an increase and decrease, respectively, in gas saturation. Only a few three-phase relative permeability curves have been published. Leverett and Lewis5 published three-phase curves for unconsolidated sand, and Snell4 reported results of several English authors for both drairrage and imbibition three-phase relative permeability of unconsolidated sands. Three-phase relative permeability curves for a consolidated sand were published by Caudle et a1.3 for increasing water and gas saturations (ID). Corey et a1.6 reported drainage (DD) three-phase relative permeability for consolidated sands. Recently, Donaldson and Dean7 and Sarem8 calculated three-phase relative permeability curves from displacement data on consolidated sands, also for saturation changes in the drainage direction. The only published three-phase relative permeability curves for consolidated sands with saturation changes in the imbibition direction (11) are those of Naar and Wygal.9 These curves are based on a theoretical study of the model of Wyllie and Gardner 10 as modified by Naar and Henderson.11 Interest in three-phase relative permeability has increased recently due to the introduction of new recovery methods and refinements in calculation procedures brought about by the use of large-scale digital computers. The scarcity of empirical relations for three-phase flow, and the experimental difficulty encountered in obtaining such data, have made the theoretical approach to this problem attractive. RELATIVE PERMEABILITY AS A FUNCTION OF PORE-SIZE DISTRIBUTION Purcell used pore sizes obtained from mercury-injection capillary pressure data to calculate the permeability of porous solids.12 Burdine extended the theory by developing a relative permeability-pore size distribution relation containing the correct tortuosity term.13 The works of Purcell and Burdine were combined by Corey14 into a form that has

Jan 1, 1969

By Herbert Haas

1. INTRODUCTION COPPER matte is now converted into blister copper at a cost of only $5 per ton of copper, or, based on a 40 per cent. matte, $2 per ton of matte, which is the record of at least one large smelting Works; and it seems hardly likely that a further reduction, large enough to warrant, a change in existing practice, could be made in bessemerizing costs. But the new type of converter here described and the new practice proposed are intended, not so much for the treatment of mattes, as for the extension of, the process to the direct reduction in the copper-converter of pyrite ores

Jan 6, 1914

[The following discussion, comprising both remarks made at the Chicago meeting and contributions since forwarded to the Secretary, is based upon the following papers, presented at that meeting : "Segregation and its Consequences in Ingots of Steel and Iron," by Alexandre Pourcel, Paris, France. (See p. 105, mans. xxii.) " Microscopic Metallography," by F. Osmond, Paris, France. (See p. 243, Trans. xxii.) " Microstructure of Ingot-Iron in Cast Ingots," by Prof. A. Martens, Berlin, Germany. (See p. 37.) " Microstructure of Steel," by Albert Sauveur, South Chicago, Ill. (See p. -546, Trans. xxii.) "Farther Observations on the Relations Between the Chemical Constitution and Physical Character of Steel," by William R. Webster, Philadelphia, Pa. (See p. 113.) "The Heat-treatment of Steel," by H. M. Howe, Boston. Mass. (See p. 466.) Since all these papers were considered together, no attempt has been made to separate the discussion strictly under the several heads.] William R. Webster, Philadelphia, Pa.: I desire to say that in my first paper (Trans., xxi., 766) the actual ultimates were subtracted from the estimated ultimates, whereas in the paper submitted at this meeting the estimated ultimates are subtracted from the actual, thus giving contrary signs. The latter method corresponds with the direct effect. of low and high finishing-temperatures ; that is, a plus difference indicates low, and a minus difference high, finishing-temperature. I make this explanation to prevent confusion in comparing the two papers. Mr. Sauveur has shown that there is a close relation between the size of the grain and the ultimate strength, and also that the size of the grain depends on the temperature at which the material is finished in rolling, and on the chemical composition of the steel. I have shown that there is a close relation between the chemical

Jan 1, 1894

By Walter Crafts

ALTHOUGH many elements reduce the tendency to porosity in steel castings, manganese, silicon, aluminum, calcium, titanium and zirconium appear to be most generally suitable for the purpose. The manganese and silicon contents are usually maintained in a fairly constant range. Sili-con-killed castings often are made to be sound with little or no addition of the stronger degasifiers. In many cases, however, it is more practical to utilize the stronger degasifying elements, aluminum, calcium, titanium and zirconium. Since they greatly modify the composition, shape, and distribution of the nonmetallic inclusions, and thereby the ductility, the strong deoxidizers must be used in such a way as to form the least harmful types of inclusions. As the reasons for failure always to obtain good results have not been obvious, an effort has been made to determine the mechanism of solidification of steels deoxidized to produce certain types of inclusions. Diagrams representing the mechanism of their formation have been constructed from the appearance of the nonmetallic con-stituents and have not only illustrated the limiting features of specific deoxidizing treatments with respect to inclusion formation and ductility, but have also indicated a relation between inclusions and resistance to hot tearing. Three different types of deoxidation treatment have been used for obtaining sound castings with relatively high ductility. The first method is to make and cast the steel under such conditions that deoxidation with silicon and a small addition of a strong deoxidizer assures soundness. The effective addition that will promote soundness without causing the formation of intergranular inclusions varies with the furnace practice and composition, but may be limited to about 0.025 per cent Al, Zr or Ti. Up to 0.10 per cent Ca and 0.15 per cent V are also used for this purpose. The inclusions in these steels are characteristically glassy silicates and round or irregular sulphides. As pointed out by Sims and Lillieqvist,1

Jan 1, 1940

By W. C. Snow

The plant of the Electrolytic Zinc Company of Australasia Limited, situated at Risdon on the estuary of the River Derwent, near Hobart, was designed and erected primarily to produce high-grade zinc from zinc concentrates produced by the mines of Broken Hill, N. S. W. Consequently the metallurgy of the process has been influenced in its development by the peculiar characteristics of the Broken Hill concentrate, which on treatment gives into solution relatively large amounts of cobalt, manganese and silica. The Risdon works (Fig. 1) produces high-grade electrolytic zinc, leaded electrolytic zinc, zinc dust, cadmium, sulphuric acid and superphosphate. This paper, however, is concerned only with the zinc plant and process. Roasting The roasting of raw concentrate is not a major feature of Risdon's process, and in this respect practice is unlike that of most zinc plants. The roasting is mostly done on the Australian mainland at centers where the sulphuric acid made from the roaster gases can be used for superphosphate manufacture. A small amount, approximately 40 tons per day, is roasted at Risdon, acid being manufactured from the gases. The amount that can be roasted there is limited by the acid requirements of the zinc plant and of the superphosphate plant. Roasting is not carried to completion at the mainland plants, and the product, known as preroast calcine, largely constitutes the raw material for the Risdon zinc plant. It contains about 6 per cent of sulphur as sulphide. Roasting is completed at Risdon for reasons that are set out later in this paper. The zinc plant proper is divided into four main divisions: (1) final roasting division, (2) leaching and purification division, (3) electrolytic division, (4) melting and casting division. There are two subsidiary divisions—the cadmium division and the preroast, acid and superphosphate division.

Jan 1, 1937

By M. Muskat, R. D. Wyckoff, H. G. Botset

The flow of liquids through porous media is known to follow Darcy's law which states that the velocity of flow is proportional to the pressure gradient. This law is but a statement of the facts obtained from experimental studies and is, therefore, uncontroversial. It should be men-tioned, however, that it applies only when the flow is viscous in nature and that at excessive velocities which tend to produce turbulence, the velocity is proportional to some power of the pressure gradient, the exponent ranging from 1 to 0.5 as the degree of turbulence increases. However., experiments with media having permeabilities corresponding to those of actual producing horizons show conclusively that the actual flow of liquids in a producing horizon must be viscous except perhaps in the immediate vicinity of a well producing at a high rate. Therefore, one is justified in assuming Darcy's law to hold for cases of practical interest, as will be implicitly assumed in this discussion Given this basic law of flow it is possible, theoretically to obtain solutions to any problem of viscous flow of dead liquids1 by the usual methods of potential theory. However, problems of practical interest often present such complex geometrical configurations of sources and sinks (driving sources and output wells) as to make the analytical solutions extremely difficult or even impossible. It is useful, therefore, to note that Darcy's law is precisely equivalent to the law of electrical conduction, so that the pressure distribution in steady state porous flow of liquids is exactly the same as the potential distribution in an electrical conducting medium.2 This analogy permits the use of electrical models wherein the potential distributions may be measured with far greater facility and accuracy than is possible in actual fluid-sand models. Such electrical models were used in determining the pressure distribution about complex arrays of wells, an example of which will be shown later in the discussion of the 5-spot flood. One phase of the porous flow problems which is of considerable practical interest involves the tracing of an advancing fluid front. Thus,

Jan 1, 1933

By G. Howell Clevenger

FORMERLY great divergence of opinion existed in regard to the influence of copper in steel, as affecting its various physical properties. More recently the investigations of Stead,1 Breuil,2 Wigham,3 Burgess and Aston,4 Ball and Wingham,5 Miiller,6 Dillner,7 and others have shown fairly good agreement in the major points. Copper steel has been shown by these investigators to possess special properties which make it valuable for certain uses. The general range of composition of the useful alloys of copper and iron, and of copper, iron, and carbon, has been quite definitely established, for the former by Burgess and Aston,8 and for the latter by Breuil 9 and Stead.10 Stead 11 has removed one difficulty in reconciling certain of the earlier data by calling particular attention to the influence of carbon in copper steels. Another point which caused confusion in the earlier investigations, particularly in regard to " red-shortness," was the presence of sulphur. Failure to note the presence of sulphur often led to attributing " red-shortness " to the presence of small amounts of copper. Turner 12 has called attention to the fact that where copper exists in an iron ore it often occurs as the sulphide, so that the presence of copper in steel made from such ores might also, necessarily, mean the presence of sulphur. It is evident that the effect in this case might be quite different than where pure copper was added.

Jan 10, 1913

By Linda Lee, R. E. Reed-Hill, C. R. Smeal

Four fcc metal surfaces, etched to make them responsive to polarized light, have been studied with an electron microscope. Jones'prediction that these surfaces are grooved has been verified. Optical-goniometer measurements made on commercially pure nickel indicate that the groove walls are poorly defined (100) facets. Surface mientations close to either 4001 or {ill).- show no extinctions on the polam'zid-light microscope. An explanation is offered for this orientation dependence. It has also been deduced that polarized-light extinctions on a grooved cubic-metal surface should not be used directly in crystallographic-orientation determinations. The nature of the etching solutions that produce these surfaces is considered. A cubic-metal surface may be made responsive to polarized light in two basic ways."' In one, an anodic film, believed anisotropic, is formed on the surface. A plane-polarized-light beam, at normal incidence, should be reflected from this type of film with an ellipticity that varies with grain orientation. Under crossed polarizers of a polarized-light microscope, each grain may be distinguished from its neighbors by a difference in reflected-light intensity. An alternate treatment,' more generally applicable to cubic metals and of principal concern here, involves etching of grain surfaces. The characteristic features of this surface were first deduced by Jones3 from light-microscope observations. She concluded that, in general, grain surfaces were furrowed so that light was reflected from two parallel sets of etched facets. A grooved surface produces elliptical polarization of a plane-polarized beam because the beam does not strike groove walls at normal incidence. Jones also observed that the furrows must have faces inclined to each other by approximately 90 deg, since the light returns along the incident path, and that a grooved surface should show four maxima and minima of reflected-light intensity during a 360-deg stage rotation of the polarizing microscope. Positions of maximum extinction were predicted to occur when groove axes were parallel to either polarizer or analyzer vibration directions. Because of the limited resolving power of Jones' optical microscope, her deductions were primarily indirect. Proof of the correctness of her conclu-sions, as demonstrated by the electron microscope, will be given as well as evidence concerning the crystallographic nature of the etch furrows and the types of etching solutions that produce them. EXPERIMENTAL PROCEDURE During a comprehensive study of hot plastic deformation in nickel and nickel alloys, an etch was evolved that produced a surface with an excellent polarized-light response on Nickel 200 ("A" Nickel). The etching solution and associated metal-lographic procedures are given in Table I. In evaluating this etch, a study was made of the topological features of the etched surface and their relation to the underlying crystalline structure. As part of this investigation, large crystals (2 mm average diameter) were grown in a 1-cm-sq Nickel 200 specimen. After the surface was etched, the crystallographic orientations of ten grains were determined by the standard back-reflection Laue technique of Gren-inger.4 Maximum extinction positions during a microscope stage rotation were also measured for the ten grains. Groove-wall positions on the surfaces of the ten grains were measured with a two-circle optical goniometer. The technique was essentially that of Barrett and Levenson.5 Several grain surfaces were photographed with a Philips Model 100A electron microscope. All specimens were replicated with collodion, or collodion backed with formvar and chromium shadowed at 18 to 20 deg. The basic material was Nickel 200. However, an electron-micrographic study was also made of surfaces developed by polarized-light etches on other fcc metals (90-10 a brass, Monel 400, and lead). All etching procedures are given in Tables I and 11. EXPERIMENTAL RESULTS Fig. 1 shows typical electron micrographs of three different fcc metal specimens and an optical micrograph of a fourth. All photographs show a grooved structure corresponding closely to Jones'3 predictions. Also, as noted by Jones, extinctions were always observed when groove axes were either parallel or perpendicular to the microscopes' vertical cross hair. The symmetry of the grooves, with respect to the twin boundaries in Fig. 1, implies that furrows have a crystallographic basis. The coarse-grained Nickel 200 specimen was used to study this basis. Facet Orientation. The poles of the ten Nickel 200

Jan 1, 1964

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper' on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.' In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.' The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1'9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By Frank T. Sisco, Selma F. Hermann

gancse constituent in the alpha grains. Nickel produces a structure of alpha plus cutectoid almost identical with that of the normal aluminum bronze (Fig. 38), except for the rod-shaped nickel constituent in the alpha grains. Silicon produccs a light structure with small regular needles, possibly a modified form of beta. Fig. 45 shows the alpha plus beta structure of the normal 10 per cent. aluminum alloy as quenched. Manganese produces large grains of beta with alpha as a tiny constituent scattered throughout the spceimen. Silicon, on the other hand, produces all alpha, with free silicon present. One per cent. iron produces alpha plus beta, with a tiny constituent present in the alpha grains. Five per cent. iron introduces twins in the alpha and a nodular iron constituent in both the alpha and the beta. Figs. 50-58 include the structures of the alloys with 8 per cent, aluminum, tempered at 400" C. and at 650" C. Fig. 50 is the normal structure as drawn at 400" C!. It consists of large grains of twinned alpha plus a very small amount of beta. One per cent. silicon increases the amount of beta enormously, but when tempered at 650' C, the beta degenerates to a hard blue network constituent. One per cent. cobalt results in a structure of exceedingly fine-grained, twinned alpha, heavily mottled. Nickel produces large soft grains of alpha with a dot constituent in some of the grains, when tempered at 650" C. Manganese, when tempered at 400" C. produces alpha grains and shows the decom-

Jan 1, 1931

By Charles W. Dickson

Jan 1, 1904

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By A. J. Teplitz, R. J. Goodwin

A new type water shut-off for use in air drilling has been developed. The method has been 99 to 100 per rent effective in several different formations of inter-ranular-type porosity. Since costs for materials, time and equipment used are relatively small, the process should extend economies of air drilling to many new areas. The treatment involves a new technique for forming a water-inroluble precipitate within the pores of a rock. Advantage it taken of the difference in mobility of a liquid and a gas in porous media to achieve the greatest volume of precipitate in a given pore. Reactants selected for the laboratory (2nd field tests were aluminum sulfate solution and gaseous ammonia. This process has been tested in both intergranular and fractured-type porosities. It has consistently shut-of between 99 and 100 per cent of the water flowing from formations having intergranular-type porosity and perrlreuhilities ranging from a few millidarcise to over a darcy The treatment is not particularly suitable for shutting-off water from fractured formations although plugging of the order of 50 per cent or greater has been achieved in all such applications. Among advantages of the treatment are: (I) no reaction waiting rime after a relatively short placement time, (2) a low mate-rials cost of about $3/f1 of hole treated, (3) use of common service-type equipment for treatment, and (4) no unusual requirements for mixing and placement. INTRODUCTION In rotary drilling with air or gas it has been possible to increase bit life by tenfold and more than double rate of penetration over corresponding performance when drilling with mud. These factors have amounted to as much as 22 per cent savings on total cost of drilling a well. However, these advantages are rapidly lost when water is encountered in an air- or gas-drilled well because water interferes with the removal of cuttings from the hole and also gives rise to other difficulties. In attempting to combat water troubles, operators have commonly resorted to such measures as mist drilling, treatment with cement or chemicals, converting to conventional mud drilling, or setting casing. In many cases these measures have either been costly or ineffective. In an effort to overcome this problem, studies were undertaken to develop an effective and economical water shut-off technique for use in formations possessing inter-granular-type porosity. Extensive laboratory experimentation finally led to a unique method for producing a water-insoluble precipitate within the pores of a sandstone. The unique part of the treatment is use of a liquid and a gas to form the precipitate, and in this case the reactants used were aluminum sulfate solution and gaseous ammonia. The reaction between these two materials is shown in the following equation. Al2 (SO1)3 - 18 H20 6NH2? saturated Water- Solution Cat 2A1(OH)3 . n H20 3(NH4)2SO • n H20 Solid Solid That is, a solid precipitate consisting of aluminum hydroxide and ammonium sulfate is formed when ammonia reacts with aqueous aluminum sulfate. The aluminum hydroxide is insoluble in water and the ammonium sulfate, though soluble, can only be removed from the formation pores by diffusion—an extremely slow process. Although the precipitate formed by the reaction is not particularly firm, great strength is not needed for a precipitate to bridge and plug intergran-ular-type porosity. A flow path in such a system is extremely tortuous and involves a great variety of pore

By W. H. Herrnstein, J. B. Clark, E. C. Utley, A. J. McEvily

The ratio of the endurance limit (10&apos; cycles) to tensile strength of age-hardened aluminum alloys is approximately 0.3, whereas the ratio for annealed alloys is about 0.5. The lower value for the age-hardened alloys has been associated with the instability of coherent precipitate during cyclic loading, but it has not been definitely established whether this instability is due to overaging or reversion during cyclic loading. The results of the present investigatzon support the reversion viewpoint. In this work specimem of 2024-T4 aluminum alloy were aged for 16 hr at 150°C after cycling for 10 pct of the life at 25.000 psi. These specimens were then tested to failure and exhibzted a marked increase in fatigue life. It is proposed that during the early stages of fatigue in this alloy dislocations cut through the coherent precipitate and bring about the reversion of the precipitate. Subsequent aging at 150ºC induces reprecipitation in the precipitate-free zones so that the weakened regions are strengthened and the fatigue life is extended. It Is recognized that the fatigue strengths of precipitation hardened aluminum alloys are unusually low relative to their tensile strength.&apos;-= This feature is illustrated in Fig. 1 where it can be seen that age-hardened alloys have lower fatigue ratios (the ratio of the fatigue strength to the tensile strength) than those in the annealed or cold worked state. Further, as shown in Fig. 2, the more an alloy is dependent upon precipitation hardening for its total strength, the lower is the ratio of the fatigue strength to the tensile strength. This state of affairs has been associated with an instability of the metastable metallurgical structure of precipitation hardened aluminum alloys during cyclic loading. Evidence2 in support of this view is that the fatigue ratio increases in these alloys as the test temperature is lowered, thereby indicating that thermo-mechanical instability, rather than some other factor such as a non-uniform distribution of precipitate, is the factor responsible for the low fatigue ratio at room temperature. Two mutually exclusive proposals have been ad- vanced to account for this instability. Hanstock has proposed that overaging takes place during cyclic loading, and in support of this view, Broom et a1.2 have indicated that an overaging process might be promoted by the large numbers of vacancies which are created during cyclic loading. The creation of vacancies by radiation4 has been shown to lead to rapid overaging. Hanstockl obtained visual evidence of overaging in an aluminum alloy after cyclic loading, but in this instance it has been pointed ou? that because of the high frequency used (60,000 cpm) the observed effect may have been due to normal high temperature precipitation around energy dissipating cracks. Efforts to discern visual evidence of overaging in this alloy at lower test frequencies were not successful.3 The alternative postulate3 is that reversion takes place during cyclic loading and leads to localized soft spots at which fatigue cracks are readily initiated. Evidence for this process has recently been provided by Polmear and Bainbridge5 who demonstrated metallographically that regions depleted of precipitate were created during cyclic loading of an aluminum alloy. Inasmuch as precipitate particles bordering the depleted region had not grown in size, it was concluded that the solute atoms which had constituted the missing particles had gone back into solution. No mechanism for the reversion process was presented. The present study was undertaken to investigate further the conditions leading to instability during cyclic loading, and to determine whether reversion or overaging had taken place as a result of cyclic loading. BACKGROUND AND TEST PROCEDURE In order to differentiate between the processes of reversion and overaging, rest periods at an elevated temperature, which ordinarily would insure additional precipitation, were used in this investigation. It was expected that after a period of cyclic loading an elevated temperature rest period would result in a decrease in the remaining life of the specimen if overaging were occurring during cyclic loading, whereas in the case of reversion, reprecipitation would occur and the fatigue life would be extended. Such an expectation is based on the assumption that the crack-nucleation phase is a significant portion of the total fatigue life, and that such a treatment is of influence in the crack-nucleation stage and is relatively unimportant thereafter.

Jan 1, 1963

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

The greatest mining center in the state of Utah is the incorporated town of Bingham about twenty-five miles southwest of Salt Lake City. The principal industry of this vicinity, prior to the early fall of 1863, was lumbering and the first saw-mill in the state was built near the mouth of Bingham Canyon. Early in the fall of that year. George B. Ogilvie discovered gold and shortly afterward the first mining district in the state was organized. Some writers place the discovery of gold in the canyon in the late fifties. If this be so, however, the matter was kept extremely quiet because no mining was engaged in until after Ogilvie&apos;s discovery. Bingham was a placer mining camp, producing about one million dollars&apos; worth of dust and nuggets from placers up and down the canyon and in Bear Gulch until early in the seventies, or about ten years after the discovery of gold, when a large body of argentiferous lead ore was discovered and soon after heavy shipments were made from a half dozen or more properties.

Jan 1, 1925

By Henry S. Munroe

The earliest accounts we have of Japan represent the country as having great mineral wealth, especially of precious and useful metals. Marco Polo, the Venetian traveller, in the thirteenth century, writes of "Zipangu:" " They have gold in greatest abundance, its sources being inexhaustible. The king does not allow of its being exported. To this circumstance we are to attribute the extraordinary richness of the sovereign&apos;s palace. The entire roof is covered with a plating of gold.. .. The ceilings of the halls are of the same precious metal; many of the apartments have tables of pure gold of considerable thickness, and the windows also have golden ornaments." Marco Polo also gives an account of an unsuccessful Tartar expedition against Japan, prompted by the supposed great wealth of the country. Columbus also, as well as many other explorers, were attracted and encouraged by these prevalent reports of the wealth of the islands of Zipangu. Kaempfer, writing in 1727, speaks of the great mineral wealth of Japan, and especially of the abundance of gold, which, he says, is found in many provinces. The Portuguese and Dutch, while they had trading-posts in Japan, furnished tangible evidence of the truth of the early reports. Between 1550 and 1639 the Portuguese merchants sent home from Japan nearly three hundred million dollars&apos; worth of bullion, most of which was gold. As the relative value of equal weights of gold and silver was then six to one, while in Europe, at the same time, it was nearly twelve to one, the exchange of silver bullion for gold was by no means an unimportant part of their Business. After the Portuguese, the Dutch continued the exportation of bullion, and the exchange of silver for gold, though with less profit, as the relative value of gold increased with the demand. Between 1649 and 1671 the Dutch traders sent home over two hundred million dollars in bullion, of which, however, nearly two-thirds was silver. In 1671 the Japanese government, alarmed at the rapid rate at which the precious metals were leaving the country, issued an edict forbidding the exportation of gold or silver, under heavy penalties, which had the immediate effect of stopping this trade. Besides bullion, copper formed at this time a most important article of export. According to Dr. Geerts,* who has examined the old

By J. C. Todd

The volume of air needed to move the combustion wave through each acre-foot of the reservoir is a very important quantity for engineering economic analyses. A new method, which involves backflowing the injection well, has been developed for determining the air requirement .for the forward combustion thermal pilot in the Delaware-Childers field. The method depends on measurement of the total volume of air injected and measurement of the pore volume in the zone swept out by the combustion front. The basic premise of the method is that the pore volume of the swept zone contains air, while the formation around this zone contains flue gas, oil and water. The pore volume of the swept zone is determined by blowing down the pilot section of the formation through the injection well after the pilot is shut down. Oxygen balance is used to differentiate between air from the swept zone and flue gas from the surrounding formation. Data indicate that air&apos;is produced from the swept zone by relatively efficient miscible displacement by the flue gas. The pore volume occupied by the air in the swept zone is determined by simple PVT relationships. The average temperature of the swept zone is calculated by heat balance from the total amount of heat generated during the pilot and losses to the surrounding formation. The new method was applied successfully at the conclusion of the pilot in the Delaware-Childers field; the air required for the reservoir conditions involved was calculated to be 19.2 MMscf/acre-ft of reservoir swept. INTRODUCTION One of the most important pieces of information to be found from a forward combustion pilot is the air requirement; that is, the volume of air needed to move the combustion wave through each acre-foot of the reservoir. Compression costs per barrel of oil recovered, which are a direct function of the air requirement, are a large portion of the expenses incurred in the thermal recovery process. Thus, the profitability of thermal recovery depends largely on the air requirement, which is a measure of the amount of fuel deposited and burned in the thermal recovery process. Several attempts have been made to correlate crude oil properties with fuel deposition and, hence, air requirement.l*2 Other attempts have been made by our laboratory to find the air requirement by material balance, gravity survey, pressure transient analysis,3 magnetic survey and the poten-tiometric model. Better methods are needed to predict more accurately the economics of fieldwide application of the process. Another method of finding the air requirement consists of operating a pilot thermal project for several years. This is followed by an extensive coring program to define the volume swept by the combustion wave. The air requirement is found from the total injected air divided by the volume of the swept region found from the coring operation. This method is costly; an adequate coring program usually costs several hundred thousand dollars. A thermal pilot was operated in a watered-out portion of the Delaware-Childers field, Bartlesville sand, from Nov., 1960, until May 3, 1965. One of the primary purposes of this pilot operation was to determine the air requirement for economic calculations which determine the advisability of expanding the project to the entire 128,000 acre-ft field. Barnes4 has described the result of this pilot operation,, including calculation of the air requirement from limited coring data. The value obtained, as calculated, was 15.8 MMscf/acre-ft. One purpose of this report is to describe a new method of finding the air requirement from a thermal pilot operation. A second purpose is to describe the application of this method to the Delaware-Childers thermal pilot. THEORY AND DESCRIPTION OF THE METHOD The combustion zone in the forward combustion process is propagated from injection w producing

Jan 1, 1970