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By H. H. Reamer, B. H. Sage

The formation volume and the relative volume of the liquid Phase of mixtures of Condensate and gas from five different parts of a field in the Louisiana area have been established experimentally. These studies included gas-condensate ratios as high as 25.000 cu ft/bbl at pressures up to 5,000 psi. The gravities of the tank condensates were between 53.9° and 63.9° API. The compositions of the condensate and gas samples inves-ligated are presented in tabular form. The formation volume. the relative volume of the liquid phase. and the specific volume of the mixtures are available. A rough correlation of the formation volume as a function of pressure. temperature, and gas-condensate ratio has been presented. This correlation i-considered applicable only to the range of conditions covered in this investigation for systems of similar nature and com-position. INTRODUCTION Often a knowledge of the influence of temperature. Pres sure, and relative quantities of condensate and gas upon the volumetric behavior of fluid*. from a given field has been employed in estimating the Conditions existing in the reservoir. The early work of Beecher and Parkhurst' and the more rrcent Studies of the Dominguez' and San Joaqnin Valley Field;: are examples of experimental studies of this character. Correlation of the volumetric behavior of naturally occurring hydrocarbon mixtures has Proved To be feasible' . at low gas-conden-sate ratios-; for fluids*. from a single geographic area. Progres 5 is being made in the Prediction of the volumetric behavior of distillate systems at high gas-condensate ratios and pressure.. However. the estimation of the retrograde". ' dew-point pressure still remains uncertain and probably can best be established by experiment. For this reason it appears of interest to make available experimental information about the volumetric behavior of mixtures of condensate and gas from five different part.; of a single field. This material shows a rough similarity to data for mixtures of condensate and gas from San Joaqnin ' Valley Fields. In the present paper. 110 attempt has been made to coordinate the available information on tbe volumetric behavior of fluids from condensate fields. It appears hopeful that progress can be realized by the utilization of recently developed equa-tions of state.!' However. the primary problem in any such correlation is the proper identification of the components and constituents of naturally occuring systems. Additional experimental information may be required to permit the determination of the values of the constants of the equation of state for References given at end of paper. Manuscriptt received in the office of the Petroleum Branch June 11. 1951. *For present purposes low gas- condensate ratios will he considered as those below 3,000 cu ft/bbl, and the region of high gas-condensate ratio will be limited to compositions containing more than 5,000 cu ft of pas per bbl of condensate. Mixtures Containing between 3,000 and 5.000 CII ft OF gas per bbl will be considered of intermediate gas-condensate ratio.

Jan 1, 1952

By F. W. Warnaars

The Los Bronces copper deposit is located on the west side of the Andes Mountains in central Chile about 54 km (34 miles) northeast of Santiago. The deposit consists of a hydrothermal breccia complex that was emplaced in the western part of an earlier porphyry copper mineral system. This system exhibits propylitic, sericitic, silicic to potassic hydrothermal alteration with disseminated and stockwork copper-molybdenum sulfide mineralization over an area of about 12 km2 (5 sq. miles). The Rio Blanco Mine, about 800 m (0.5 miles) east of Los Bronces, is an underground block caving mine located in the central part of this system. The mineralization at Rio Blanco is characterized by one of the highest primary copper grades known for porphyry copper systems. Present mining at Los Bronces is from an open pit located in the northern part of a hydrothermal complex that is composed of at least seven different copper-bearing tourmaline breccia pipes. Together these pipe form one large contiguous body about 2 km (1.2 miles) long and 0.7 km (0.4 miles) wide at the surface. This body crops out at elevations of between 3.5 and 4.1 km (2 and 2.5 miles) above sea level. Each breccia pipe has a characteristic shape, matrix, type and degree of mineralization and alteration. Quartz, tourmaline, specularite, anhydrite, pyrite, chalcopyrite, sericite, chlorite, and rock flour are present in significant quantities in most breccia matrices. The clasts consist mainly of quartz monzonite, andesite, and minor amounts of quartz latite porphyry. The seven different breccia pipes are identified, from oldest to youngest, as Ghost, Central, Western, Infiernillo, Fine Gray, Anhydrite, and Donoso. The breccias coalesce, interfinger, or display gradational contacts. In places they form sharp contacts with each other and with the surrounding intrusive or volcanic host rocks. Early breccias are disrupted or cut by subsequent breccia events. Explosive emplacement was followed by collapse after the release of hydrothermal pressures. The Los Bronces breccia complex has sharp contacts with the surrounding intrusive stock and andesites. These contacts dip inward on the north, west, and south margins. The eastern contact is nearly vertical and/or dips slightly outward and suggests a westward tilting of the body of about 15° after emplacement. The breccia complex is not fully explored at depth, but is known to extend at least below the 3 km (2 mile) elevation in its central eastern part, about 1 km (0.6 miles) below the highest breccia outcrop. Primary copper sulfide minerals are most abundant in the Donoso and Infiernillo breccias where the matrix consists mostly of tourmaline, quartz, sulfides, specularite, and/or chlorite with minor amounts of rock flour, sericite, and clay. The volume of the matrix material is mostly smaller than in the other breccias. Secondary enrichment enhanced the primary copper grade in the southern two-thirds of the Los Bronces breccia complex and in much of the surrounding porphyry system. Primary grades of 0.3% to 0.5% copper have been enriched to approximately 0.9%. This enrichment may extend from surface outcrops to a depth of more than 500 m (1, 640 ft) in more permeable parts of the breccia complex. A leached and oxidized capping of variable thickness covers a large part of the enriched layer and exceeds 300 m (984 ft) at one location. The shape and depth of the enrichment blanket and the capping suggest that the enrichment process is still active.

Jan 1, 1983

By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements' of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper' we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

THE notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat- . treatment of steel. In view of the serious thought that even so simple a test as the tensile test, has evoked during the past years, it is not surprising that the notched- bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and un- predictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small- size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even mare complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be con- trolled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors. such as the com- position and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

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Jan 1, 1923

By J. Campbell

The negative pressure developed within a solidifying sphere of pure iron is investigated theoretically assuming an elastic-plastic model. The maximum hydrostatic tension attainable is shown to be an order of magnitude smaller than that required for the homogeneous muclealion of pores in the liquid cove, and four orders of magnilude smaller than that predicted from) a rigid shell model. It is well-known that liquids can withstand large hydrostatic tensile stresses, or negative pressures. The various experimental investigations of the tensile strengths (often called the fracture pressures) of liquids are reviewed by Dean,1 and the theoretical attempts at estimating fracture pressures are critically assessed by wakeshima.2 Using Fisher's3 quation, the fracture pressure of pure liquid iron is about -70,000 atm, which may be too large by as much as a factor of 4, but is certainly correct to within an order of magnitude.' In view of the great importance of the problem of the nucleation of shrinkage cavities in castings it is of interest to determine exactly what tensile stresses can exist in the residual liquid in a solidifying casting; it has often been assumed that, because of the very low strengths of solid metals near their melting points, no interior stresses are developed at all. Nussey4 has determined theoretically the pressure in the liquid core of a solidifying metal sphere assuming that the solidified shell does not deform (i .e., is perfectly rigid), so that because of the contraction accompanying solidification (a) (about 3 pct for most metals) the progressive deposition of solid onto the inner surface of the shell causes the remaining liquid to be expanded to make up this difference in volume. This leads to a relation between the pressure P in the liquid, the initial pressure, PO, the bulk modulus of the liquid, K, and the inner and outer radii of the solid shell, o and b, respectively:

Jan 1, 1968

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks.

Jan 1, 1949

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By M. T. Halbouty

The Laredo oil district, South Texas, includes an area of approximately 200 miles long north and south and 75 miles wide, embracing the following counties: Starr, Zapata, Jim Hogg, Webb, Duval and McMullen. The area is relatively old in respect to the production of oil, as the first oil was discovered and produced in the Piedra Pintas field in Duval County on Sept. 10, 1905. Since that date, continuous new discoveries have contributed to the development of this district until, at the present time, it is one of the important oil-producing and gas-producing areas in the world. The year 1937 also had its share of new discoveries in the district, including not only new oil fields but also new sands in already producing pools and important extensions to existing sands and fields. Among the most important field discoveries, by counties, are: Duval County..... Benavides, Sweden, Thomas-Lockhart, Labbe and Lundell fields Jim Hogg County.. Las Animas field McMullen County. Ezzell field Starr County...... El Tanque field Webb County..... Killam and Oilton fields Of these, Benavides, Oilton, Killam and Ezzell have so far proved themselves most important; the Benavides field, Duval County, showing by far the most activity. For the year 1937, therc were 283 wildcat tests drilled in this district, of which 35 were oil producers, 20 completed as gas wells and 228 abandoned as dry holes. Duval County, as usual, received the greatest amount of wildcat drilling, having 21 oil wells, 5 gas wells and 63 dry holes completed during the year for a total of 89 tests. Next came Webb County with 4 oil wells, 4 gas wells and 53 dry holes for a total of 61 tests.The Laredo oil district, South Texas, includes an area of approximately 200 miles long north and south and 75 miles wide, embracing the following counties: Starr, Zapata, Jim Hogg, Webb, Duval and McMullen. The area is relatively old in respect to the production of oil, as the first oil was discovered and produced in the Piedra Pintas field in Duval County on Sept. 10, 1905. Since that date, continuous new discoveries have contributed to the development of this district until, at the present time, it is one of the important oil-producing and gas-producing areas in the world. The year 1937 also had its share of new discoveries in the district, including not only new oil fields but also new sands in already producing pools and important extensions to existing sands and fields. Among the most important field discoveries, by counties, are: Duval County..... Benavides, Sweden, Thomas-Lockhart, Labbe and Lundell fields Jim Hogg County.. Las Animas field McMullen County. Ezzell field Starr County...... El Tanque field Webb County..... Killam and Oilton fields Of these, Benavides, Oilton, Killam and Ezzell have so far proved themselves most important; the Benavides field, Duval County, showing by far the most activity. For the year 1937, therc were 283 wildcat tests drilled in this district, of which 35 were oil producers, 20 completed as gas wells and 228 abandoned as dry holes. Duval County, as usual, received the greatest amount of wildcat drilling, having 21 oil wells, 5 gas wells and 63 dry holes completed during the year for a total of 89 tests. Next came Webb County with 4 oil wells, 4 gas wells and 53 dry holes for a total of 61 tests.

Jan 1, 1938

By F. H. Allen, R. P. Roe

The performance history of a volumetric gas condensate reservoir is presented. Curves depict the pressure-production relation and illustrate the phace behavior of the reservoir fluid. This performance is compared to calculated performance. This Bacon Lime Reservoir was discovered in 1941 and has been produced to field separators and gas sales. Reservoir performance has been observed by periodic bottom hole pressure sur. veys and companion sample analysis of well effluents, in addition to gas and condensate production data. , The pressure-production history demonstrates that the reservoir has produced under volumetric control. The "retrograde" behavior of the reservoir fluid is illustrated by decreasing butanes-plus content of the well effluent, followed by revaporization as the reservoir pressure approaches abandonment. Calculated performance predictions are compared to actual performance and some discussion offered on apparent discrepancies. INTRODUCTION Since the late 1930's, many gas condensate reservoirs have been developed, the retrograde theory of phase behavior has been generally accepted, and a number of cycling programs have been initiated. Numerous technical papers have since appeared in the literature dealing with the theory and application of cycling the gas condensate reservoirs. Some cycling operations have now advanced to a stage where it is possible to determine performance characteristics to a fair degree of accuracy. Field performance data for gas condensate reservoirs operated by pressure depletion have not been so extensively reported in the literature, although their probable behavior has been discussed in explanation of the retrograde theory. It is the purpose of this paper to compare calculated theoretical reservoir performance with field observations and well stream analyze; which have been obtained throughout the practical producing life of a small volumetric gas condensate reservoir. The reservoir under study is the Bacon Lime Zone of a field located in East Texas. The Bacon Lime occurs in the Lower Glen Rose Formation of Cretaceous Age. This Bacon Lime Reservoir is encountered at an average depth of 7600 ft (7203 ft subsea elevation) and comprises approximately 3100 acres located on a structural high with 80 ft of productive closure. The producing formation consists of approximately 50 ft of dense crystalline fossiliferous dolomite of generally low permeability with typical wide variation in both permeability and porosity, the more permeable stringers measuring 30 to 40 millidarcys. The average porosity is extimated to be 10 per cent with a connate water saturation of approximately 30 per cent of the pore space. The reservoir temperature was found to be 220°F and the original pressure was 3691 psia at -7200 ft elevation. The re ervoir was discovered in November, 1.941, and is now essentially depleted, Throughout most of its productive life, from the standpoint of cumulative withdrawals, the reservoir has been produced by five wells. During its latter stages of depletion, 16 wells were completed in the Bacon Lime.

Jan 1, 1950

By Henry M. Howe, W. P. Barba

When this country went into the war, but two concerns, The Bethlehem Steel Co. and The Midvale Steel and Ordnance Co., knew how to make steel fit for great cannons and at these concerns there were relatively few men who knew the whole art. Fortunately, certain of these men put their knowledge at the service of the Government, and proceeded to instruct the metallurgists at the arsenals and at various steel works. Doctor Howe, then chairman of the Engineering Division of the National Research Council, suggested that this work might be facilitated, and the number of effective gun-steel makers thereby increased, if a detailed description of the best practice could be written, giving the reasons for the various steps, and issued with the endorsement of a committee composed of those who were evidently the most competent authorities. It was thought that something would be gained by clarification of the subject, and something by the eminent authority of the members of the committee. To that end, the Engineering Division appointed a committee, consisting of the gentlemen whose names follow, to mention on1y those who retained their connection with it. At this time there were serious difficulties in the manufacture, for the Government. of aircraft and high-speed engine crankshafts, of certain ordnance forgings, and of shells for both the Army and Navy. This Committee was asked to study and report upon these, with a view to betterment of practice. There were indications that the source of some of the difficulties went back to the melting of the steel and the production of the ingot. Hence, the committee first studied steel melting and ingot production, in order to guide the wartime manufacturers to an even larger percentage of useful production from the steel initially melted. Committee on Steel Ingots W. P. Barba, chairman, Ordnance Dept., U. S. A. (formerly Vice Pres. & Gen. Mgr., Midvale Steel Co., Philadelphia). George K. Burgess, Chief of Division of Metallurgy, U. S. Bureau of Standards, Washington, D. C. Henry M. Howe, Then Chairman Engineering Division, National Research Council.

Jan 1, 1922

By W. P. Barba, Henry M. Howe

When this country went into the war, but two concerns, The Bethlehem Steel Co. and The Midvale Steel and Ordnance Co., knew how to make steel fit for great cannons and at these concerns there were relatively few men who knew the whole art. Fortunately, certain of these men put their knowledge at the service of the Government, and proceeded to instruct the metallurgists at the arsenals and at various steel works. Doctor Howe, then chairman of the Engineering Division of the National Research Council, suggested that this work might be facilitated, and the number of effective gun-steel makers thereby increased, if a detailed description of the best practice could be written, giving the reasons for the various steps, and issued with the endorsement of a committee composed of those who were evidently the most competent authorities. It was thought that something would be gained by clarification of the subject, and something by the eminent authority of the members of the committee. To that end, the Engineering Division appointed a committee, consisting of the gentlemen whose names follow, to mention on1y those who retained their connection with it. At this time there were serious difficulties in the manufacture, for the Government. of aircraft and high-speed engine crankshafts, of certain ordnance forgings, and of shells for both the Army and Navy. This Committee was asked to study and report upon these, with a view to betterment of practice. There were indications that the source of some of the difficulties went back to the melting of the steel and the production of the ingot. Hence, the committee first studied steel melting and ingot production, in order to guide the wartime manufacturers to an even larger percentage of useful production from the steel initially melted. Committee on Steel Ingots W. P. Barba, chairman, Ordnance Dept., U. S. A. (formerly Vice Pres. & Gen. Mgr., Midvale Steel Co., Philadelphia). George K. Burgess, Chief of Division of Metallurgy, U. S. Bureau of Standards, Washington, D. C. Henry M. Howe, Then Chairman Engineering Division, National Research Council.

Jan 1, 1922

By J. Gordon Parr, A. J. Goldak

OgdEN et al.1 and Bumps et al.2 suggested that the solubility of aluminum in a titanium extended to 30 pct.* Sagcl,3 Clark and Terry,4 Anderko et al.,5 Ence and Margolin6 and Saulnier and croutzelles,7 subsequently proposed the existence of an intermetallic compound in the region of 25 pct Al. Although Anderko et al.5 suggested that the structure of this phase, Ti3Al, was of the DO,, (Ni3Sn) type, their conclusion was based only upon the results of a powder photograph that included reflections from ? = 0 to ?= 27° (CuK),some of which were reported to be indistinct. Ence and Margolin,6 referring to a 25 pct alloy (but without indicating whether the figure referred to weight or atomic pct) stated: "The structure of Ti2Al is isomorphous with Ti3Sn DO19, as pointed out by Pietrokowsky". But the point was not proven, because Ence and Margolin did not report values of calculated intensities of Ti2Al with the DO,, structure. In fact, the observed intensities they reported are in poor agreement with the values we calculate for DO19 (see Table I). Saulnier and croutzelle7 concluded, on the basis of electron micrography and microdiffraction studies, that the structure of the 25 pct A1 alloy was ordered hexagonal. Our purpose has been to unequivocally determine the Ti3Al structure. Alloys containing 25 pct Al were prepared from iodide titanium and spectrographic standard aluminum by levitation melting. The levitation chamber was evacuated to 10-6 mm Hg before filling with 99.999 + pct A. After casting, the alloy was chilled to liquid air temperature and crushed to -200 mesh in a percussion mortar. The powder, wrapped in molybdenum foil, was annealed (by induction heating) at 1000 "C for 2 hr in the argon atmosphere of the levitation chamber. No sublimate was seen on the foil or elsewhere, and therefore the assumption is

Jan 1, 1962

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By R. W. Smith. Discussion by D. Watson, R. M. Manser

D. Wotson, R. M. Monser (Watten Spring Laboratory, Stevenage, Herts., U. K.) - This is a valuable and interesting paper and will make an important contribution to the development of a general theory of silicate flotation. In particular the dominance of surface reactions which produce fluosilicic acid and its ions has been convincingly demonstrated. In a paper to be published shortly, however, we offer some evidence which is not consistent with the feldspar activation theory proposed by Prof. Smith. This theory, given in Eqs. 17-20, suggests that activation takes place through the exchange of SiF6 ions for OH- at aluminum sites. This results in a negatively charged site facilitating adsorption of RNH3 Firstly, we have determined the flotation response (using the vacuum flotation technique) and the adsorption of dodecylamine on a natural feldspar (albite) and on the same feldspar after washing with perchloric acid at pH3. This pre-treatment was shown to remove surface adjacent aluminum atoms. It was found that although the acid washed feldspar floated much less easily than the untreated sample, the function of fluoride ion - giving activation over the pH range 4-6.5-was preserved. Moreover, the amount of dodecylamine adsorbed either with or without fluoride present is little affected by acid-washing, despite the depression caused by this treatment. This suggests that surface aluminum atoms can be of little importance in the fluoride activation mechanism. Secondly, we have determined the changes in solution concentration of F- and H+ (or OH-) accompanying reaction of the surface with fluoride ion. The ratio of H+ lost from solution to F- lost is high, ranging from 6.9 at pH4 to 1.0 at pH 7.5. This is consistent with reaction of HF (6 molecules for every Si removed) at the surface, producing SiFi-ions, but not with the re-adsorption of these ions.

Jan 1, 1967

By F. D. Delve

RECENT studies by the author on the reduction of titanium from TiO2-bearing slags have been accompanied by difficulties that are attributed to

Jan 1, 1959