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By Phillip E. La Moreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride. IN June 1940, the U. S. Geological Survey, in cooperation with the Geological Survey of Alabama, began a study of the ground-water resources of the part of Alabama where water is obtained from Cretaceous rocks. The purpose of the study was to determine the quality, quantity, occurrence, and availability of ground water in that area. These studies have been expanded to include ground-water investigations in the area of Tertiary rocks, or southern quarter of the State, and certain areas in northern Alabama. The first report issued on these studies was by C. W. Carlston,1 of the Alabama Geological Survey. In the present paper all references to ground-water data for the Cretaceous area are taken from this earlier publication. In 1945, the Dentistry Division of the Alabama Department of Public Health became interested in the correlation of tooth decay and mottled enamel with the chemical quality of ground water used for public supplies in the State. Through a cooperative arrangement between the State Department of Public Health and the Ground Water Division (now Branch) of the U. S. Geological Survey, a report by the author2 was published in 1948. These two reports give accurate information on the occurrence of fluoride in the Coastal Plain of Alabama. At present, only scattered information is available on fluoride in ground water of the crystalline-rock or Piedmont area and for the Paleozoic area of Alabama, but it is hoped that in the future more complete information on the presence of fluoride in ground water in these areas can be collected. Outline of Geology and Ground Water: As described by Adams,3 the State of Alabama includes parts of two major geologic divisions, the Appalachian region and the Coastal Plain. The boundary between these divisions is irregular and is known as the Fall Line of the Atlantic and Gulf Coast States. The Fall Line enters Alabama near Phoenix City, extends westward to Wetumpka, Clanton, and Tuscaloosa, and then swings northwestward to the northwest corner of the State. The Appalachian region in Alabama includes three major provinces, the Piedmont province, the Appalachian Ridge and Valley province, and the Appalachian Plateau province (fig. 1). The rock formations in the Piedmont province in east-central Alabama are mainly of pre-Cambrian age, chiefly crystalline schists and gneisses injected by younger igneous rocks (fig. 1, I). They are faulted and folded and have a complicated structure. These rocks are the oldest and among the most complex rocks in the State. Generally, only small yields of ground water are obtained from rocks in this area. Even though ground water is of great importance for the development of domestic and farm supplies in rural areas and a few small industrial and municipal wells, yields in the area from individual wells generally range from 5 to 25 gpm and rarely exceed 50 gpm. The geologic formations of the Appalachian Ridge and Valley province and the Appalachian Plateau province (see fig. 1, II, and III) are separated on the basis of their structure. These rocks are of Paleozoic age, ranging from Cambrian to Carboniferous, and comprise a succession of formations consisting chiefly of shale, sandstone, limestone, and dolomite, aggregating many thousands of feet in

Jan 1, 1951

By Phillip E. La Moreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride. IN June 1940, the U. S. Geological Survey, in cooperation with the Geological Survey of Alabama, began a study of the ground-water resources of the part of Alabama where water is obtained from Cretaceous rocks. The purpose of the study was to determine the quality, quantity, occurrence, and availability of ground water in that area. These studies have been expanded to include ground-water investigations in the area of Tertiary rocks, or southern quarter of the State, and certain areas in northern Alabama. The first report issued on these studies was by C. W. Carlston,1 of the Alabama Geological Survey. In the present paper all references to ground-water data for the Cretaceous area are taken from this earlier publication. In 1945, the Dentistry Division of the Alabama Department of Public Health became interested in the correlation of tooth decay and mottled enamel with the chemical quality of ground water used for public supplies in the State. Through a cooperative arrangement between the State Department of Public Health and the Ground Water Division (now Branch) of the U. S. Geological Survey, a report by the author2 was published in 1948. These two reports give accurate information on the occurrence of fluoride in the Coastal Plain of Alabama. At present, only scattered information is available on fluoride in ground water of the crystalline-rock or Piedmont area and for the Paleozoic area of Alabama, but it is hoped that in the future more complete information on the presence of fluoride in ground water in these areas can be collected. Outline of Geology and Ground Water: As described by Adams,3 the State of Alabama includes parts of two major geologic divisions, the Appalachian region and the Coastal Plain. The boundary between these divisions is irregular and is known as the Fall Line of the Atlantic and Gulf Coast States. The Fall Line enters Alabama near Phoenix City, extends westward to Wetumpka, Clanton, and Tuscaloosa, and then swings northwestward to the northwest corner of the State. The Appalachian region in Alabama includes three major provinces, the Piedmont province, the Appalachian Ridge and Valley province, and the Appalachian Plateau province (fig. 1). The rock formations in the Piedmont province in east-central Alabama are mainly of pre-Cambrian age, chiefly crystalline schists and gneisses injected by younger igneous rocks (fig. 1, I). They are faulted and folded and have a complicated structure. These rocks are the oldest and among the most complex rocks in the State. Generally, only small yields of ground water are obtained from rocks in this area. Even though ground water is of great importance for the development of domestic and farm supplies in rural areas and a few small industrial and municipal wells, yields in the area from individual wells generally range from 5 to 25 gpm and rarely exceed 50 gpm. The geologic formations of the Appalachian Ridge and Valley province and the Appalachian Plateau province (see fig. 1, II, and III) are separated on the basis of their structure. These rocks are of Paleozoic age, ranging from Cambrian to Carboniferous, and comprise a succession of formations consisting chiefly of shale, sandstone, limestone, and dolomite, aggregating many thousands of feet in

Jan 1, 1951

By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By R. W. Fountain, John Chipman

The solubility of nitrogen in Fe-B alloys (0.001 to 0.91 pet B) is determined by the Sieverts' technique for temperatures of 950° to 1150°C. The activity coefficient of nitrogen is decreased by boron. The three-phase equilibrium between ? iron, BN, and gas is established and also the four-phase equilibrium between iron, BN, Fe2B, and gas. The above equilibria are calculated for a iron. The relation of these data to hardenability and strain aging of boron-treated steels is discussed. BORON additions are known to enhanbe the hardenability of heat-treatable steels and to assist in the control of strain aging in sheet steel for deep drawing. The increase in hardenability is explained by the theory that adsorption of boron on austenite grain boundaries reduces their free energy and thus retards ferrite and upper bainite nucleation.l,2 Digges and Reinhart3 have shown that the full effectiveness of boron in commercial steels is achieved only when strong nitride formers such as titanium and zirconium are also present. The influence of nitrogen on eliminating the boron contribution to hardenability was also demonstrated by Shyne and Morgan.4 These workers prepared Ni-Mo steels containing either nitrogen or boron or nitrogen plus boron. The nitrogen-plus-boron steels showed the lowest hardenability which was attributed to the presence of stable nucleating particles, presumably nitride. Morgan and Shyne5-7 have shown that boron in the amount of 0.007 pet will completely eliminate strain aging due to nitrogen in low-carbon, open-hearth steels. In addition, by proper control of the boron additions, a rimming steel can be produced. Since the effectiveness of boron on hardenability and eliminating strain aging is influenced by the amount and distribution of the nitrogen in the steel, the present study was. undertaken to determine the influence of boron on the solubility of nitrogen in iron. EXPERIMENTAL PROCEDURE The solubility of nitrogen in Fe-B alloys was measured by the method of Sieverts, which consists of determining the amount of gas dissolved by the metal in a constant volume system. The apparatus employed in this investigation and the experimental details have beendescribed previously.B AMcLeodgage was added to the apparatus to allow measurements at very low pressures. The alloys were melted at reduced pressure in a basic-lined induction furnace using electrolytic iron and ferroboron. Ferroboron was added after the primary deoxidation of the iron with carbon. Since it was difficult to attain a constant low level of oxygen by this procedure, silicon was added after the carbon deoxidation and prior to the ferr obor on addition. The alloys were castas 2-in. sq ingots, heated in argon at 1050loC, and forged to 1/4-in. plate. After forging, 1116 in. was machined from each side of the plate to remove any possible contamination, and it was then cold-rolled to 0.010-in. sheet. The sheet was cut into approximately 1/4-in. squares and pickled in an inhibited H2SO4 solution to ensure a clean surface. In the case of the boron alloys, a hydrogen treatment could not be used for surface cleaning because boron losses resulted. The composition of the alloys is given in Table I. For a solubility determination, a 75-g sample was inserted in a quartz tube and sealed in place in the apparatus. The entire system was evacuated at room temperature and leak tested for 24 hr. If no leaks were observed, the system was heated to the temperature of measurement and again leak tested for 24 hr. If no leaks were detected, the hot volume and solubility determinations were begun. The hot volume was determined at a constant temperature for each run by admitting successive amounts of argon and recording pressure vs volume, which, in all cases, resulted in a straightline relationship. The argon was then removed and the procedure repeated with nitrogen. Successive additions were made until the desired nitrogen content of the metal and equilibrium pressure of the system were obtained. The

Jan 1, 1962

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.&apos; Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-&apos;3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

ONE of the fundamental reasons for the extreme rapidity with which the Porphyries developed after the trail had been blazed at Bingham was the amenability of the deposits to prospecting and proving of the ore either by churn-drilling or by diamond-drilling. At Ray churn-drill data formed the principal basis for early calculations of ore reserves; and in 1913, Inspiration floated its first bond issue for $6,000,000 on the strength of the estimate of 45,000,000 tons of sulphide ore assaying just over 3 per cent copper. The money was obtained in spite of the fact that no one ever had actually laid eyes on more than a minute fraction of that ore. The customary method of developing a copper deposit before the Porphyry era had been to sink shafts or drive adits and then to follow and expose the veins or lodes with horizontal and vertical underground workings-drifts, crosscuts, raises, and winzes. The excavated material sometimes was sampled in bulk; but always the walls of the openings would be channeled at intervals to obtain small samples representative of the ore left in place. This process was known as "blocking out" ore. It was costly and it required a great deal of time to prove the existence of immense tonnages. The early development at Utah was done in this way; likewise, at Miami. This fact helps to explain why only 3,000,000 tons of ore was reported as being developed when J. Parke Channing wrote the report on which the original Miami financing was based in March, 1908. Fortunately, his 3,000,000 tons averaged 3&apos;per cent copper. At Ray, Seeley W. Mudd estimated 3,000,000 tons of ore in June, 1908, developed principally by underground working; but by the end of 1909, Henry Krumb was able to report 50,000,000 tons as the fruit of a little more than a year of churn-drilling.

Jan 1, 1933

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.&apos; Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe&apos;s treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.&apos; This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By Jean Howard

THERE are two mechanisms by which secondary crystals can develop in bcc alloys, namely 1) impurity inhibition and 2) strip-thickness inhibition. This paper reports some studies of each mechanism; the alloys were Si-Fe, A1-Fe, Cr-Fe, Mo-Fe, and Ge-Fe, as well as iron itself. All the alloys, which were of interest as part of a program of work on soft magnetic materials, were made by a powder-metallurgy process, using carbonyl iron (Grade MCP) as the starting material. Earlier phases of the work have already been published. Work described previously1 shows how the oxygen content of the sintering. atmosphere can be used to produce silica in the material which acts as a grain-growth inhibitor. Since then it has been found more convenient to make use of the oxide in the iron powder to control the silica content of the material. The compacts are sintered in vacuum which allows a direct reaction to take place between the iron oxide and the silicon. Details are given elsewhere.4 By this method, and by suitable adjustment of the rolling schedule, material with cube-on-edge secondary crystals has been produced in thicknesses from 0.1 to 0.001 in. in iron containing from 2-1/2 to 4-1/2 pct Si. It was also found possible to process 6-1/2 pct Si-Fe to 0.001 in. This was achieved by refinement of the sintered-compact grain size by using fine-particle silicon (i.e., <200 mesh). The brittleness of the material necessitated hot rolling to 0.020 in., from which thickness cold rolling was possible. If the conditions of sintering and the cold-rolling schedule were correct (i.e., as given elsewhere4 for 3-1/4 pct Si-Fe) secondary crystals of (110) [001.] orientation could be developed. The size of the secondary" crvstals" could not be

Jan 1, 1965

By H. Bartholomew, L. Bernstein

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

Jan 1, 1967

By J. H. Scaff, W. G. Pfann

The effects of impurities on the electrical properties of silicon are discussed in a companion paper by Messrs. Scaff, Theuerer, and Schumacher.&apos; It was shown that an ingot of silicon which contained boron and phosphorus in certain concentrations consisted partly of p-silicon and partly of n-silicon2 and that the common boundary between these regions was the source of a photo-voltage. These features were ascribed to the segregation of boron and phosphorus during solidification of the ingot. Because of different rates of segregation the first portion of the ingot to freeze contained a molar excess of boron over phosphorus and hence was p-silicon. The last-solidified region contained a molar excess of phosphorus and was n-silicon. This paper is concerned with the microscopic examination of such ingots. The microstructures are rather unusual in certain respects and their study has helped to show how the segregation of minor elements modifies the electrical properties of silicon. The microstructures of ingots prepared from two lots of silicon, designated 1 and 2, will be described. These lots were obtained from the Electro Metallurgical Co. Both contain 99.8+ pct silicon, but they differ in impurity analysis. For each lot will be shown the microstruc-ture of a slowly cooled ingot, for which the time of solidification is 6 min., and that of a rapidly cooled ingot, for which the time of solidification is 2 min. The ingots were prepared from 45 g charges of silicon. When an alloy freezes a cored structure is generally produced because of insufficient diffusion to remove concentration differences established during freezing. As a result of coring the first portion of a crystal to freeze is usually poorer in solute than equilibrium requires, while the last material to solidify is richer. In a columnar grain, growth is principally unidirectional and coring can produce a concentration gradient along the entire grain. By carrying the picture of the coring process from a single grain to an entire ingot in which columnar grains are aligned more or less radially, one can easily see that a composition gradient could be established between the outside and center of the ingot. This, to a considerable extent, occurs during the solidification of a slowly cooled ingot of silicon. Slowly Cooled Ingot In slowly cooled ingots of both lots of silicon, columnar grains which are approximately radial in direction and longest at the top of the ingot enclose a region in which the shapes and align- ment of the grains are considerably less regular. The central region is last to solidify and contains cavities and inclusions. The sketch of Fig 1 illustrates some of these features, as well as others which will be described below. If a polished section of an ingot is etched in a mixture of 2 parts of 20 pct HF and 98 parts of HNO3 the p-n barrier becomes visible. The overall shape of the barrier in a slowly-cooled ingot is roughly oval, as may be seen in Fig 1. The proportion of n-silicon, that is, the region enclosed by the barrier, is considerably greater in ingots of lot 1 than in those of lot 2. A sample about 34 x 1/8 X 1/8 in. was cut from a slowly cooled ingot of lot 1 with its long direction extending from the top of the ingot to the porous region. Thus its upper half was psilicon, its lower half n-silicon. A longitudinal face was polished and etched in the acid mixture. The areas of interest are identified in Fig 2. A band of parallel markings extends across the sample in the columnar region. These striae are roughly parallel to the upper surface of the ingot and cross grain boundaries with only slight deviations. They are quite distinct in the n-silicon,

Jan 1, 1950

The amount of coal used in the Colonies before the Revolutionary War was very small, and few records of it can be found, these all being in the Public Records Office in London. The exports and imports for the years 1768 to 1772, inclusive, are shown in Table 3, which apparently do not include the early shipments from the Virginia field. For the three years 1769 to 1771, the imports from Great Britain-their only source-totalled 17,943 tons, or an average of 5,981 tons per year. If the shipments from Richmond for the same period were available, this average would probably not exceed 6,800 tons per year. In Table 4 the shipments of coal from the James River ports for the period 1758 to 1769 are shown. A few of them are re-exports of coal brought from England, but the great majority are undoubtedly of coal produced in Virginia, and the movement was partly to West Indian ports but mainly to Atlantic ports from Baltimore to Portsmouth, N. H. (Piscataway). In Table 5 the data in Tables 3 and 4 are combined, the exports being deducted, and this summarizes all the available data on the amount of coal consumed in the Colonies before the separation from England. As has already been stated there has been a tremendous amount of work done in the Richmond field over a long period of time, many mines were opened and in some cases operated for years, and practically no accurate data remain or have been published to show what was done. There are undoubtedly manuscripts still remaining that will contribute to much of the knowledge of this field, and it is well worth the while of the proper state authorities to collect all the information that can be found anywhere, to enable the future development of these coal deposits to benefit by the record of what was done in the past. Table 22 shows all the methods of shipment from this field, and all of the data available about tonnages moved over each of them. The shipments by the Chesterfield and Clover Hill Railroads are largely duplicated in some of the other columns, but allowance has been made for this in the estimated totals. In addition to the difficulties experienced with similar data for the other states, these Virginia records have one peculiarly their own; it was the custom to allow 5 pecks to the bushel of coal at the pit and only 4 pecks at the docks or at vessel side. In most of the figures it is not stated to which point they apply, and a considerable error may exist due to this cause, although certainly it does not apply to all of them. The notes show the sources of the figures used, and while it is probable that the totals are lower than the actual amounts produced, the data given are the most complete that can now be assembled.

Jan 1, 1942

By J. C. Melrose

The contact angle is one of the boundary conditions for the differential equation specilying the configuration of fluid-fluid interfaces. Hence, applying knowledge concerning the wettability of a solid surface to problems of fluid distribution in porous solids, it is important to consider the complexity of the geometrical shapes of the individual, interconnected pores. As an approach to this problem, the ideal soil model introduced by soil physicists is discussed in detail. This model predicts that the pore structure of typical porous solids will lead to hysteresis effects in capillary pressure, even if a zero value of the contact angle is maintained. The model is generalized to situations in which the contact angle takes on values between zero and 40 degrees. For the imbibition branch of the capillary- pressure function, the model predicts a considerable departme ftom the usually assumed cos 0 relationship. In fact, according to the model, it is possible that a displaced wetting phase will not be able to reimbibe, even when the contact angle does not exhibit hysteresis. INTRODUCTION The subject of capillarity in porous media has long been of interest in many branches of engineering and applied science. The earlier investigators were those concerned with the physics of soils. 1-5 More recently, petroleum engineers and others dealing with the problems of petroleum production from reservoir rock have given much attention to the subject.6-10 Also, important additions to the literature of capillarity have been contributed from the field of chemical engineering.11-12 These attest to the wide range of industrial applications in which capillary phenomena play a role. The present paper is concerned with the role which wettability plays in capillary action in porous media. As is well known, capillary-rise (or capillary pressure) phenomena have frequently been interpreted with the aid of a model employing the concept of a cylindrical capillary tube. This approach has enjoyed a certain degree of success in correlating experimental results.13 The generalization of this model, however, to situations which involve varying wettability, has not been established and, in fact, is likely to be unsuccessful. In this paper another approach to this problem will be discussed. A considerable literature relating to this approach exists in the field of soil science, where it is referred to as the ideal soil model. Certain features of this model have also been discussed by Purcel114 in relation to variable wettability. The application of this model, however, to studying the role of wettability in capillary phenomena has not previously been attempted in detail. In the present paper, additional features of the model are introduced. These features are critical in determining the quantitative behavior of the model. GENERAL FEATURES OF CAPILLARY HYDROSTATICS BASIC PRINCIPLES When the interstices of a typical porous solid are occupied by two or more immiscible fluid phases, the fluids are microscopically commingled. Hence, fluid-fluid interfaces are found within a certain fraction of the pore openings. The fundamental equation of capillarity specifies the configuration of these fluid-fluid interfaces. This is known as the Laplace equation, when derived from mechanics, and as the Gibbs-Kelvin equation when derived thermodynamically.15 Given two fluid phases, a and ß, in hydrostatic equilibrium, the Laplace equation states that the respective fluid pressures in regions close to the interface are related by Here oaß is the surface or interfacial tension and rl and r2 are the principal radii of curvature of the surface or interface. The pressure difference, Pa-Pß, is the capillary pressure, PC. As Buff15 has shown, Eq. 1 states the condition for hydrostatic equilibrium within the two-phase confluent region, which is referred to as the interface. It thus can

Jan 1, 1966

By Oren C. Baptist, Carlon S. Land

Laboratory research has been conducted to evaluute the effect of clay hydration on the permeability to gas of water-sensitive reservoir sands. Samples of a .sandstone containing trace amounts of montmorillonite and a sample of montmorillonite were .studied in the laboratory to detertnine whether swelling or dispersion was the cause of permeability reduction in these samples. Heliuin, containing various amounts of water vapor, was used to hydrate the clay minerals and to determine the gas permeability at various stages of clay hydration. The amount of water adsorbed by the samples using this method is small. The nonwetting-phase permeability at higher water saturations war investigated by saturating the with water and measuring the permeability to humid helium while decreasing the water saturation, Relative-permeability curves obtained from results of these procedures were used to estimate the effect of the swelling of trace amounts of mont/tlorillonite on the permeability of the .samples. Most of the damage to the permeability when reservoir sands containing trace amounts of montmorillonite are exposed to fresh water is due to dispersion and movement of clays. Blockage of pores by the increased volume of expanded montmorillonite is believed to result in permeability damage that is small in comparison to the observed damage to the samples tested. INTRODUCTION Studies have shown that permeability is severely damaged when sands containing only small amounts of montmorillonite are contacted by fresh water.15 When samples of sands containing large amounts of montmorillonite are placed in fresh water in the laboratory, these samples may completely disintegrate, forming an unconsolidated mass of larger volume than that occupied by the dry sample." In this case, it is apparent that the swelling of montmoril-lonite has destroyed the pore structure of the sand. If only a trace of montmorillonite is present in a sand. samples may remain intact when saturated with water, although the permeability to water is a small fraction of the gas permeability of the dry sample. Many workers in the field of water sensitivity have attributed this reduction in permeability to the blocking of pores and reduction of pore size by the increased volume occupied by expanded mont- niorillonite. if the sand contains a detectable amount of montmorill&apos;onite or mixed-layer clay containing rnontmorillonite. Logically3 the smaller amount of montmorillonite present in a sand, the smaller should he the effect of montnlorillonite swelling on permeability; however, the quantity of montmorillonite sufficient to cause severe damage by swelling is not known. Although hundreds of samples have been tested in our laboratory, no correlation has been established between the amount of montmorillonite in samples and the permeability reduction caused by fresh water. To many petroleum engineers, the phrase "clay swelling" is synonymous with "water sensitivity", or "permeability reduction" implying that any formation damage due to the hydration of clays is caused by swelling. Although all clays adsorb water on their surfaces, montmorillonite is the only clay mineral commonly found in reservoir rocks which adsorbs water between intercrystalline layers, resulting in expansion of the clay particle. As montmoril-lonite swells, the first few layers of water adsorbed between platelets are strongly held and well oriented, and the montmorillonite retains its crystalline structure, although expanded. As swelling of sodium montmorillonite continues, the platelets become farther apart and the forces orienting the platelets in the crystalline structure become weaker, resulting in a less orderly orientation of platelets. In an abundance of water, small groups of platelets may become detached from the original monl-rnorillonite particle and may be dispersed throughout the water phase. Because of its swelling properties, sodium montmorillonite is very easily dispersed in water. Particles of other clay minerals. such as illite and kaolinite may also be dispersed in water. causing water sensitivity of sands not containing montmorillonite. The presence of an immobile layer of water adsorbed on the surface of clays has been considered a possible cause of the low permeability to water of dirty sands. Grim states that the thickness of the layer of immobile water held by sodium montrnorillonite is three nlolecular layers or 7.5 A (angstroms), with some orientation of water extending to 100 A. Assuming a very thick, immobile water layer adsorbed on the surface of a pore represented by a capillary tube, the maximum effect of the water layer on permeability can be calculated. Using a pore radius of 10 &apos; cm and an immobile water layer of 50 A. the calculation shows the permeability to be reduced only 2 per cent. Similar calculations can be used to show that the effect of electro-osmotic counterflow is of the same order of magnitude as that of bound water. The reduction of the permeability to water by either an immobile water layer

Jan 1, 1966

By T. D. Mueller, F. C. Miller, Jr. Earlougher R. C.

In analyzing pressure buildup tests for field wells producing both oil and gas, the common practice is to use a modification of single-phase flow theory. Validity of such an approximation has been demonstrated for single-well solution-gas-drive systems. This paper indicates that such approximations are also valid for two-well solution-gas&apos;-drive systems. From this it is inferred that the technique can be used for multiple-well systems. A computer was used to simulate the behavior of a two-well solution-gas-drive reservoir to test the validity of the above type of analysis. Simulation results indicate that pressure buildup tests in such a system can be analyzed within engineering accuracy for formation permeability and pressure. A rule of thumb is given for estimating the length of time a well must be shut in for the pressure in a nearby producing well to increase significantly. To observe such an increase, the shut-in well would have to be left shut in much longer than normal. INTRODUCTION An important technique for obtaining data concerning a producing petroleum reservoir is the pressure buildup test. Such a test, when properly conducted and analyzed, provides information on the average reservoir pressure and the permeability in the major drainage area of a well. The theory upon which the analysis of a pressure buildup test is based assumes that the behavior of the fluid in the reservoir is adequately described by the diffusivity equation.1 Use of the diffusivity equation implies that a single fluid of small and constant compressibility is flowing. To analyze a pressure buildup test in situations which involve more than one fluid phase, the single-fluid analysis is extended. This paper verifies the extension of pressure buildup analyses to two-phase, two-well systems. Miller, Dyes and Hutchinson1 have presented a technique for analyzing pressure buildup tests in circular bounded reservoirs. Their method requires that the reservoir be producing at pseudo-steady state (constant pressure gradients) prior to shut-in. An alternate reservoir model, presented by Horner,2 assumes that the reservoir is infinite. The Homer model does not assume a Pseudo-steady state prior to shut-in, but the assumption that the reservoir is infinite implies that the average pressure can be determined only if the total production prior to shut-in is small compared to the total fluid originally present. Limitations imposed by the pseudo-steady state and infinite reservoir assumptions are avoided by the technique proposed by Matthews, Brons and Hazebroek.3 Their method can be used to calculate both the Permeability and the average pressure in bounded single-well systems which are not necessarily at steady state. They also suggested determining the average pressure of a multi-well reservoir producing from pseudo-steady state by volumetrically averaging the static pressures of the individual wells. Matthews and Lefkovits4 used numerical simulation techniques to verify that this method does produce adequate results for single-phase, multiple-well systems. Perrine5 proposed modifications to the single-phase theory so that pressure buildup tests in multiple-phase systems could be analyzed. He suggested replacing the single-phase mobility (k/µ) by the sum of the mobilities of the individual phases, and replacing the fluid compressibility by an average compressibility weighted by the saturations of the separate phases. By using numerical techniques to solve the two-phase flow problem for a single-well system, he concluded that this approximation gives results within engineering accuracy. More recently, Weller6 has shown that, for a gas-oil system with a single well at the center of a circular reservoir, pressure buildup tests can be analyzed adequately by using the modification proposed by Perrine. Feller&apos;s results also indicate that, as the gas saturation increases, this analysis becomes less accurate. To date, no evidence is available to show that the Perrine approximations can be combined with the Matthews-Brons-Hazebroek technique to calculate the average pressure of a multi-well,

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer&apos; and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith&apos; indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.&apos;&apos; Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970