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By WILFRED SYKES

IT is with particular pleasure that I welcome the members of the Open-hearth Conference of the I American Institute of Mining and Metallurgical Engineers to this meeting, as I feel this is one of the most useful activities of the Institute in the field of ferrous metallurgy. For the information of our other members I might say the Open-hearth Conference was organized by Mr. Reynders when he was president, and is made up of open-hearth superintendents and metallurgists. All the plants are invited to send representatives, and practically all do, with the exception of the U. S. Steel Corporation. It meets twice a year to discuss various problems in connection with the manufacture of steel, and its minutes are published for the benefit of those attending, the expense being defrayed by the participating companies. This conference, .1 believe, should be a model for activities in the other branches of the work covered by this Institute. It works, not by reading formal papers, which we all know is not a very satisfactory method to bring out the experience of others, but rather by a round-table method of discussion. The spirit of the meetings is such that each member feels perfectly free to state his experience, and he gets as much as he gives. A series of topics for, discussion is brought to the attention of the chairman and after one is exhausted the next point is taken up. In this way there is a real interchange of ideas and experiences which cannot fail l to be of the greatest benefit to those attending. That these meetings are beneficial is evidenced by the "continued growing attendance and lively discussions at these half-yearly meetings.

Jan 1, 1930

ANNUAL meeting of the Woman's Auxiliary of the American Institute of Mining and Metal-lurgical Engineers convened on Tuesday morn-ing, Feb. 20, the president, Mrs. H. W. Hardinge, presiding. President Hardinge, in opening the meet-ing, said: "I have the honor and great pleasure to welcome you to our seventh annual meeting. It has been a happy year, though I started in fear and trembling. My fear is partly gone and my trembling becomes less as time goes on. Never has a chairman had such splendid cooperation and harmony in her work; no. matter how much was asked nor what the task, I have always received the same answer, `We are with you, of course we can do it.' Often the road has been untried and the way full of snares, but we have all pulled together. Is it any wonder we have had a prosperous year? I cannot thank the governing -board and officers enough for their help." Mrs. Hardinge described her trip through the West last summer, during which she visited many of the local sections of the Auxiliary. She also spoke of the work of the Rossiter Raymond memorial library which has been started as an activity of the Woman's Auxiliary. Mrs. Reynders read the minutes of the last annual meeting, and Mrs. Kemp read the treasurer's report. The latter showed that on Feb. 1, 1922, there was a bank balance of $683.61 and on Feb. 10, 1923, the bal-ance was $947.93. Mrs. Westervelt expressed the sorrow of the Auxiliary for the death -of Mrs. Florence Howe Hall and of Mrs. Levi P. Holbrook.

Jan 4, 1923

By Michel David

One of the most important questions that arises in ore estimation can be stated as follows: What is the error when one extends the grade of a sample to a certain volume? The theory of regionalized variables, with the concept of extension variance, provides a response to that crucial question for any kind of sample extended to any volume. For the usual "extensions" encountered in current mining practice, some simple results can be derived from that theory which was initiated by Dr. G. Matheron. These results have been applied to a stratiform lead-zinc deposit for which several estimations of grade, tonnage and related precision have been made for a series of grid sizes such as might be used in a progressive exploration program.

Jan 1, 1969

By Marius R. Campbell

VARIOUS classes of coals are recognized in this country at the present time. These classes depend largely upon physical characteristics rather than upon chemical composition, and consequently they cannot be accurately defined. The divisions into anthracite, semi-anthracite and semi-bituminous are fairly satisfactory; but the term bituminous embraces so large a variety of coal that it is of little value, and the term lignite is so loosely applied that it has little or no place in a scientific classification. At present there is no way of accurately defining the vari¬ous classes of coal, because no adequate scheme of classification, which applies to lignites as well as bituminous coal and anthracite bas been proposed. The object of this paper is to present such a scheme, which is based upon data obtained dur¬ing the past year by Prof. N. W. Lord,1 in charge of the chemical laboratory of the United States Geological Survey coal-testing plant at the Louisiana Purchase Exposition, St. Louis. All the classifications of coals proposed prior to 1877 were based either on physical characteristics or on proximate analyses, including all of the impurities. These schemes were illogical and highly unsatisfactory, for the physical properties of a coal give little indication of its true composition; and impurities, such as ash and sulphur, are largely the results of acci-

Sep 1, 1905

By R. L. Caldwell, E. E. Glenn, L. J. Norton, A. J. D. Straus, S. V. Holcomb, J. Zemanek

A new and unique logging tool, called the Borehole Televiewer (BHTV), has been developed to inspect boreholes and to evaluate formations. Even though geologists and engineers have had only about 3 years' experience with the BHTV, the thinking of many of them has been radically influenced by the fascinating and revealing "log-picture" recorded with the tool. The BHTV fills a need for a logging tool that can produce a direct and descriptive record of the physical properties of the borehole environment. Although primarily developed to evaluate fractured reservoirs, the BHTV has been used successfully to solve a variety of problems related to formation evaluation and borehole inspection. Geologists and petroleum engineers have been confounded for many years by the problems of locating and evaluating fractures. Interpretation of the usual resistivity, acoustic or radioactivity logs, as well as the analysis of cores, for evaluation of fractured reservoirs is extremely difficult and often not definitive. This is understandable since analysis of cores from fractured formations has reported variously: (a) low porosity, (b) no effective permeability, (c) lack of any matrix oil saturation and (d) oil stains on fracture planes as the only indications of potential production.14 In recent years acoustic amplitude logs have been introduced and used with varying degrees of success to locate fractures.8'9'11"13 Conventional amplitude logs at best give only qualitative answers where quantitative ones are desired. The logs reveal nothing of the orientation of the fractures. In addition to these logs, various types of cameras, television, and rubber impression packers have been used for borehole inspection. (See Appendix.) The BHTV logging tool supplies both the quantitative and the orientation answers about fractures. The borehole can be filled with any homogeneous, gas-free liquid such as fresh water, saturated brine, crude oil or drilling muds. This tool takes an "acoustic picture" of the borehole wall. The resulting log is a representation of the borehole wall as if it were split vertically and laid flat. The log is oriented with respect to magnetic north. Any physical changes in the borehole wall are seen as changes in picture intensity. In this way, fractures, deformation or pits are reflected on the log. Tool Description The fundamental parts of the BHTV are shown in Fig. 1. A piezoelectric transducer probes the borehole wall with bursts of acoustic energy. A flux-gate magnetometer senses the earth's magnetic field and provides the means for determining the orientation of the log. A motor rotates the transducer and mag-

Jan 1, 1970

By H. T. Kennedy, S. M. Avasthi

An equation developed for gaseous hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 0.73 percent when applied to 264 natural gas and condensate systems including 2,043 PVT points. Another equation developed for liquid hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 1.12 percent when applied to 346 crude oil systems including 1,759 PVT points. Both equations require composition of the mixture to be expressed as mole fraction of methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide, together with the characteristics of the heptanes-plus fraction in addition to the temperature and pressure. The equations cover wide ranges of the variables involved, and their accuracy is considerably better than that of other available methods. The equations were differentiated to allow calculation of the coefficients of isothermal compressibility and isobaric thermal expansion. (In this paper the coefficient of isothermal com-pressibility and the coefficient of isobaric thermal expansion will be expressed as compressibility and thermal expansion coefficient, respectively.) Equations to calculate these quantities are presented. INTRODUCTION Calculations of reservoir performance for petroleum reservoirs require accurate knowledge of the volumetric behavior of hydrocarbon mixtures, both liquid and gaseous. Compressibilities are required in transient fluid flow problems, and thermal expansion coefficients are important in thermal methods of production. An accurate laboratory investigation of the PVT behavior of each reservoir fluid encountered would be costly and time consuming. For this reason various correlations for predicting fluid properties have been developed and recorded in recent literature. Correlations have been presented in the form of graphs, tables and equations. Since an increasing number of studies are being conducted with the aid of electronic computers, recent efforts have been directed toward development of correla-tions suitable for computer programming. Application of computers permits the use of more complex correlations which otherwise are not feasible. Moreover, methods for predicting reservoir performance, particularly those based on the compositional material balance, depend upon the capability of accurately expressing the molal volumes and other fluid properties as functions of pressure, temperature and composition. The coefficient of isothermal compressibility c is defined by

Jan 1, 1969

By Irving B. Cadoff, Ernest Levine

The fracture path in a Cu-4 pct Ag alloy wet with mercury was found to he dependent on the heat treatment used prior to tensile testing. Both quenched and slow-cooled alloys were embrittled by the mercury.. For quenched alloys, which were single -phase, the crack path was intergranular. Slowly cooled alloys, which contained precipitate platelets, exhibited transgranular fracture. By comparing stress-strain data for these alloys with similar data on mercury -embyittled solid-solution alloys, it was found that the role of the precipitate and that of the grain boundary in the fracture process were equivalent . THE fracture path which results when metals are strained in a liquid environment appears to be dependent upon the nature of the specific system. Mixed transgranular and intergranular cracking has been observed in the 2024 T4 aluminum alloy when wet with a Hg-Zn amalgam.' Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.' The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.' The effect of a precipitated phase on the fracture path in copper alloys is the subject of the present investigation. Cu-4 pct Ag was chosen so that its behavior could be compared with previous work on embrittlement of copper alloys. PROCEDURE High-purity copper (99.999 pct) was used as a base metal, along with 99.999 pct purity silver. Melting was carried out in graphite crucibles with manual agitation to get adequate mixing. The ingots were homogenized by means of vacuum annealing, chemically cleaned, and cold-rolled with intermediate vacuum anneals, to the desired thickness of 0.025 in. The rolled sheets were sheared to the final specimen size of 1 by 0.025 by 0.1 in. The specimens were then electropolished in phosphoric acid (concentrated) and heat-treated in an evacuated capsule at the solution temperature of 770°C. One batch was slow-cooled and the other quenched in water. The thermal etching which occurred during heat treatment was sufficient to permit grain boundary and precipitate delineation. Tensile tests were carried out in air and in mercury on a Table-Model Instron at a pulling speed of 0.2 in. per min. Wetting was accomplished by electro-polishing in phosphoric acid, rinsing in alcohol, and immersing in a pool of mercury. Once wet the coating was stable throughout the mechanical tests. In our studies it was found that wetting the surface or total immersion in mercury produced identical results. For convenience, the wetting technique was used for the experiments described. The crack pattern was observed directly on the surface by removing the mercury after testing. De-wetting was accomplished by flame heating the samples in a vacuum after testing and before observation of the surface. No etchant or polishing was used so as not to obscure the crack pattern on the surface. The mercury removal, however, resulted in a pitted surface but otherwise left the pertinent features visible. Photomicrographs were taken in this condition so as not to disturb the structure associated with the crack pattern. The average precipitate spacing was measured previous to coating the sample with mercury by use of an optical eyepiece micrometer. RESULTS The microstructure of the quenched specimens was single-phase while that of the slow-cooled specimens contained thin platelets of a second

Jan 1, 1964

By R. W. Parsons

The over-all apparent single-phase permeability of fracture-rock systems was studied using two different two-dimensional models. In a strict sense the results are applicable only to these models, yet may give some insight into real reseruoir behavior. The regular fracture-matrix model can have any number of regular fracture sets. All fractures within each set have the same orientation, width and spacing. The gross behavior is amlytically equivalent to that of an anisotropic permeable medium. In the heterogeneous fracture systems, individual fracture conductivities vary within a two-dinensioml network pattern. A computer program calculates the overall permeability after the conductivities are randomly placed in the network. The calculated permeability depends upon the distribution of these conductivities and the particular fracture pattern into which they are placed. Although detailed information on actual reseruoir fracture systems is not available, this study shows how some of the possible variables may affect obserued gross reservoir characteristics. INTRODUCTION Characteristics of reservoir rocks are determined by direct (core analysis) or indirect (logging and production tests) examination. Both methods, singly and together, are widely used in reservoir evaluations. For fractured reservoirs a problem exists in relating characteristics of cores to the in situ reservoir properties. Knowing fracture characteristics can be of value in determining production mechanisms. Because of the limitations of observation, the intimate details of a fractured rock system will never be known. One approach in analyzing fractures is to study the behavior of some conceptually simple models. The two models analyzed contain features which may be realistic, yet are mathematically tractable. Flow is considered in two dimensions only, with the plane of interest at right angles with the fractures. This concept represents the horizontal flow in a reservoir system with the fractures oriented vertically. Only single-phase, laminar flow is considered. The regular fracture-rock system permeability is calculable from a simple analytical expression. The heterogeneous system requires a computer program for calculating overall permeability.

Jan 1, 1967

By W. L. Saunders

WHEN work was begun in September, 1910, on the rock excavation for the foundation of the gigantic dam at Valhalla, N. Y., which is to convert Kensico lake into an important storage reservoir of the Catskill Aqueduct system, one of the first steps taken by the contractor, H. S. Kerbaugh, Inc., was the development of a quarry to supply the stone needed in the construction work.The importance of a bountiful supply of suitable rock in an accessible location is apparent when it is considered that nearly a million cubic yards of cyclopean masonry will be contained in the completed structure, not to mention dimension and facing stones, concrete blocks, and mass concrete. The dam structure will be over 1800 ft. long and about 170 ft. above the present river bed. However, for a distance of some 800 ft., it will be carried down to solid ledge rock, which will make the finished structure about 300 ft. in maximum height. It will be about 200 ft. thick at the base and directly beneath the coping it will be 28 ft. thick. This dam will raise the reservoir surface 110 ft. above old Kensico lake. The reservoir capacity will be 29,000,000,000 gal.-equal to New York's total needs for over two months. The contract price for this work is nearly $8,000,000 and is second only in amount to the cost, over $12,600,000, of the Ashokan Reservoir work. Fig. 1 is a view of the dam site.

Jan 2, 1914

Jan 1, 1885

By J. Richard Kyle

Lead-zinc ore bodies in the upper part of the Pine Point carbonate barrier complex are localized in paled-solution structures that developed as the result of post-middle Givetian subaerial exposure. Detritus-filled dolines host prismatic ore bodies, and macropores and stratabound permeable zones contain tabular ore bodies. Sulfides are concentrated in these transgressive paleosolution structures that acted as natural bypasses between aquifers and loci for mixing of fluids of different character. Complex ore textures indicate rapid early sulfide precipitation followed by slower sulfide growth. Evidence for both sulfide-carbonate equilibrium and disequilibrium conditions suggest fluctuations in ore fluid composition, perhaps related to periodic supply of reduced sulfur. District and ore body metal distribution pattern may reflect the nature and movement of mineralizing fluids.

Jan 1, 1981

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By C. H. Cheng, C. E. Birchenall

The fundamental problem in the thermodynamics of solid solutions is the determinatiorl or calculation of the activities of the components as a function of temperature and composition. Since the theory of metals is not suficiently developed to allow a priori calculation of these quantities, they must be obtained from experiment. C. Wagner1 has reviewed the literature of this subject for the period before 1940. Although several important and extensive studies have been made in the meantime, the number of systems to which any sort of quantitative information can be assigned is vanish-ingly small. These data have become of great potential importance in studies of the structure of solid solutions2 and intermetallic compounds, the nature of the diffusion process,3,4 and perhaps even the mechanism of mechanical deformation.5 For these reasons, it. seems very worthwhile to extend the experimental data in this field. Although there is little use in duplicating Wagner's review, attention should be directed to the most recently reported investigations. A brief enumeration of the methods of measurement previously employed also should be valuable. The most direct method is the determination of the partial pressure of the components in the vapor phase in equilibrium with the solution. Both equilibrium and kinetic methods have been tried in metal systems, but almost exclusively on liquid phases. Only in the ease of carbon in iron alloys and in the copper-zinc system have extensive measure- ments been made which include solid phases. When one of the components is an element, such as nitrogen or carbon, which forms compounds which are very volatile and stable at normal temperatures and pressures (CH4, Co2, CO NH3), it is frequently possible to equilibrate mixtures containing these (such as CH4-H2, CO2-CO, NH3-H2) independently with the elernents (C, X) and with the metal (Fe, Ni, etc.). Such measurernents have been made for carbon in iron, iron-silicon, and iron-manganese alloys by Smith6 and in iron and iron-nickel alloys by Toensing.7 Differences between carbon activity values at the same temperature and carbon content when carboil is introduced from CH4-H2 rnixtures or CO-CO. mixtures indicate that the effects of hydrogen and oxygen in the system are not negligible, and one can only hope that the true value lies somewhere between these sets of results, probably nearer the CH4-H2 data since hydrogen is less soluble in iron than oxygen. This is essentially an equilibrium method, although flowing gas is employed. A kirletic method has been employed which consists of sweeping an inert gas (generally hydrogen) over the alloy at a series of rates, condensing the metal vapor out,, and analyzing it. The metal content can be extrapolated to zero flow rate (equilibrium). Wejnarth's8 work on Cd-Mg and Zn-Mg is a good example of this frequently used method. A variant of this consists of equilibrating a known volume of inert gas with the alloy, sweeping it out quickly, and analyzing for metal. In common with the above method, it has the disadvantage that the "inert" gas is generally somewhat soluble in the alloy. Moreover, the former continuously displaces the system from equilihrium and may give low values if solid diffusion is involved. The dew point method applied by Hargreaves9 to the alpha and beta brasses and by Schneider and Stolll0 to A1-Zn avoids the introduction of another component to the system, but is useful only in systems in which one component is much more volatile than the other. The alloy sealed in one end of an evacuated silica tube is heated to the desired temperature. The temperature of the other end is lowered until droplets of the volatile component condense. When the temperature is raised slightly, the droplets will evaporate. By careful adjustment of temperature, the range between evaporation and condensation can be narrowed appreciably. An independent determination of the vapor pressure of the . pure volatile component is necessary to give the partial pressure over the alloy. This is the method employed here to determine the vapor pressures of zinc and cadmium over their silver alloys up to 34 pct in cadmium and 76 pct in zinc. The former involves only the a solid solution, but the latter covers the a, ß, y, and e fields. In recent determinations, Herbenar, Siebert, and Duffenbarkl1 used the

Jan 1, 1950

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By Henry A. Stiff, Lawrence E. Davis

A graphic method was developed which can be used to predict the tendency of oil field waters to precipitate calcium Sulfate under a variety of conditions. Application of this method is made to the prediction of sulfate scale formation in heater treaters. boilers. oil wells. cooling systems and water injection wells. INTRODUCTION A solution may be said to be in equilibrium with respect to a given salt when the concentration of that silt in equal to its solubility. If for any reason the concentration of the salt is increased or its solubility decreased. the equilibrium is upset and precipitation of the salt takes place. Thus, if the concentration of a salt in a particular solution is known and its solubility can be calculated for a given set of conditions, the tendency of this salt to form a precipitate under these conditions can be predicted. Based on these principles a method has been developed for determining the tendency of oil field waters to form calcium Sulfate precipitates under various conditions. THE SOLUBILITY DIAGRAM Calcium sulfate precipitation most frequently occurs when two waters are mixed: one containing calcium ions. and the other sulfate ions. As one of these waters is added to the other a point may be reached where the concentration of calcium Sulfate is greater than its solubility. thus causing the formation of a precipitate. The solubility diagram is a graphic device for determining the location of such points, thereby making possible a prediction of the tendency of such a system to deposit sulfate scale. A similar diagram can be used to solve many other problems involving the precipitation of calcium sulfate. Fig. 1 shows a solubility diagram representing the mixing of two waters. Water "A" contains a high concentration of odium, magnesium, and sulfate ions together with a small amount of calcium. Water "B" contains a high concentration of calcium ions together with sodium, magnesium and a small amount of sulfate ions. The percentage mixture of these waters is plotted along the abscissa of a system of rectangular coordi-

Jan 1, 1952

Executive Committee. GEORGE F. KUNZ, Chairman. E. GIBBON SPILSBURY, Vice-Chairman. THOMAS ROBINS, H. J. SEAMAN. Louis D. HUNTOON, Secretary-Treasurer. Meeting, Apr. 4, 1913. A joint meeting of the New York Section of the American Institute of Mining Engineers, the American Society of Mechanical Engineers, and the American Institute of Electrical Engineers was held in the large auditorium of the Engineering Societies Building, 29 West 39th Street, on Friday evening, Apr. 4, 1913, and an exhibition of the Edison Talking Moving Pictures was presented before the Societies, together with exhibitions of the work which is being done by the Edison Co. in making moving pictures to illustrate lectures on natural science and the useful arts for school and college work. Introductory remarks were made by Mr. J. W. Lieb, Jr., and followed by an exhibition of moving pictures illustrating the formation of crystals, the operation of different types of pumps, magnetic forces, electro-magnetic separation of iron ore, the evolution of the fly, and many other most interesting studies. One of the films, entitled The Formation of Crystals, showed a moving picture of a boy, whose laboratory was the kitchen, dissolving salt in a test tube filled with hot water. The boy then poured the solution of hot salt into a watch glass and placed it under the microscope to watch the crystals form. This film was immediately followed by another showing what the boy saw through the microscope. The solution at first was free from crystals. Gradually the crystals commenced to form and increased very rapidly after once starting, shooting across the screen with lightning speed. The film illustrating the separation of iron ores by the Edison electro-magnet showed an ore bin with an electro-magnet set at one side and below the bin. As the ore was dropped from the bin the magnetite was drawn into the. electric field and deposited in a separate rile from the sand.

Jan 5, 1913